The present invention was made with government support under grant # DE-FG02-96ER14632 from the Department of Energy and grant no GM36238 from the National Institutes of Health. The U.S. government has certain rights in the present invention.

The scope of the invention

The present invention relates to solar cells, in particular to regenerative solar cells, and chains for accumulation of light suitable for use in such solar cells.

The level of technology

Molecular approaches to the conversion of sunlight into electrical energy have a rich history, as measured about ″the photoelectric effect″ was first reported in 1887 in Vienna (Moser, J. Montash. Chem. 1887, 8, 373.).The most promising designs were developed in the main parts in the 1970-ies (Gerischer, H. Photochem. Photobiol. 1972, 16, 243; Gerischer, H. Pure. Appl. Chem. 1980, 52, 2649; Gerischer, H.; Willig, F. Top. Curr. Chem. 1976, 61, 31). Two common approach is depicted in figure 1, they both use molecules selectively absorb sunlight, called photosensitizers, or simply sensitizers (S) and covalently associated with conductive electrodes. The absorption of light by the sensitizer leads to an excited state, S*, which injects an electron in the electrode, and then oxidizes the particle of a substance in solution. The right part of izobrajaet the simplified photoelectrochemically element. This element produces electrical energy and chemical products. To work depicts the way in the last few decades there have been developed many molecular approaches to decomposition of water into hydrogen and oxygen. In the left part shows a regenerative element which converts light into electricity without any chemical products. In the present regenerative solar cell having a place on the photoanod oxidation reactions are traded on the dark cathode.

The principal difficulty with these designs of solar cells is that the molecular monolayer of sensitizer on a flat surface does not absorb a significant portion of the incident visible light. As a result, even if the quantum yields of electron transfer in relation to absorbed photons are high, the efficiency of conversion of solar energy will be unacceptably low because of the small amount of absorbed light. This problem was noticed at an early stage of research, and tried to work around by using a thick film of sensitizers. This strategy is the use of thick absorbing layers was unsuccessful because of intermolecular quenching of excited States in a thick film of sensitizer reduces the output of injects the district of electrons in the electrode.

One of the thick-film classes of sensitizers is proposed in the so-called organic solar cells (Tang, C.W. and Albrecht, A.C. J.Chem.Phys. 1975, 63, 953-961). In this case, the film thickness of from 0.01 to 5 μm, typically consisting of phthalocyanines, perylenes, chlorophyll, porphyrins or their mixtures, is deposited on the electrode surface and is used in the wet solar cells, such as those shown, or in the form of solid-state devices, where the second metal is deposited over the organic film. The organic layer is assumed, is a semiconductor with a narrow gap and photoconductivity either n-or p-type, and the proposed mechanisms for the conversion of light into electrical energy include exciton energy transfer between pigments in the film to the electrode surface, where the electron transfer across the boundary. However, the importance of these proposed mechanistic steps is not obvious. Efficiency, which is caused by the vector energy transfer between pigments, is not convincingly demonstrated. In addition, the length of diffuse excitons reported, are short compared to the penetration depth of light. Accordingly, most of the light is absorbed in the region where the energy cannot be transferred to a surface the particular semiconductor. Excitons are also easily extinguished with the help of additives or trapped solvent, which leads to significant problems related to reproducibility and complexity of manufacture. Currently known in the art organic solar cells are a multi-layered organic film ″heterojunctions″ or doped organic layers, which give ˜2%efficiency at low levels of exposure, however, the efficiency decreases significantly when the irradiation is approaching the intensity of sunlight (Forrest, S.R. et al., J.Appl.Phys. 1989, 183, 307; Schon, J.H. et al., Nature 2000, 403, 408).

Another class of solar cells on a molecular basis are so-called photovoltaic cells, which were the main devices for solar energy conversion at the molecular level in 1940-1950-s (Albery, W.J. Acc.Chem.Res. 1982, 15, 142). These elements differ from those discussed above, the fact that the excited sensitizer is not affected by the electron transfer across the boundary. Elements often contain sensitizers, enclosed in a membrane that allows for transport of ions and charge transfer; membrane physically separates the two dark metal electrode and photogenerated redox equivalent. The geometric arrangement which prevents their direct electron transfer in the excited state of the chromophore to the electrodes, or Vice versa. Instead, occurs intermolecular charge separation, and reducing and oxidising equivalents diffuse to the electrodes, where the electron transfer across the border. Membrane Nernst potential can be generated by transferring electrons under the action of light occurring in the membrane. In photoelectrochemically galvanic elements can also be formed by chemical combustible materials. This General strategy sensitization electrodes dyes were used in various incarnations for many years, but the absolute efficiency remained very low. Albery concluded that theoretically in water regenerative photovoltaic element can be achieved efficiency ˜13%. However implemented to date, efficiency, typically constitute less than 2%.

In 1991 Gratzel and O'regan reported breakthrough (O'regan, B. et al., J.Phys.Chem. 1990, 94, 8720; O'regan, B. and Gratzel, M. Nature 1991, 353, 737). By replacing the planar electrodes thick porous film of colloidal semiconductor surface area for binding of the sensitizer has increased more than 1000 times. Gratzel and O'regan demonstrated that a monolayer coating of sensitizer deposited on the particles of the semiconductor, leading to absorb essentially all of the incident light, and the efficiency of conversion of energy and the incident photons in the energy of the electrons constitute the unit of the individual wavelengths of light in regenerative solar cells. Moreover, the global efficiency ˜5% was implemented in lighting conditions with respect to air masses 1.5 (i.e. the ratio of the weight of the atmosphere on the real path between the observer and the sun to the mass in the case when the observer is at sea level and standard atmospheric pressure, and the sun over his head); this efficiency has increased to the value 10,69%confirmed now (Gratzel, M. in ″Future Generation Photovoltaic Technologies″ McConnell, R.D.; AIP Conference Proceedings 404, 1997, page 119). These solar cells type "Gratzel" have already found their niche in the market and are commercially available in Europe.

These films of colloidal semiconductors with high surface area (elements of type "Gratzel") achieved a high level of absorption, but also have the following significant disadvantages: (1) for high efficiency required liquid transition (because of the very irregular surface structure makes the precipitation of the solid-state conductive layer is essentially impossible). (2) Film of colloidal semiconductors stages require high temperature annealing to reduce internal stresses. Such high temperatures impose severe restrictions on the types of conductive substrates that can be used. For example, can not be used polymeric substrate, which melt at temperatures lower contribuye temperature annealing. (3) Significant losses associated with charge transfer through the thick film semiconductor. These losses do not reduce significantly the photocurrent, but have a great effect on the output voltage, and thus, the power is significantly reduced (Hagfeldt, A.; Gratzel, M. Chem. Rev. 1995, 95, 49). In accordance with this, the need for new molecular approaches to the design of solar cells still remains.

The invention

Accordingly the present invention provides, among other things, a chain for the accumulation of light suitable for use in the manufacture of solar cells. Chain accumulation of light contains:

(a) a first substrate containing a first electrode; and

(b) the layer of rods for accumulation of light, is electrically connected with the first electrode, each of the rods for the accumulation of light contains a polymer of the formula I:

where:

m is at least 1 and can range from two, three or four to 20 or more;

X¹is a group of charge separation, with an excited state with energy equal to or lower than y X².

X²-X^m+1are chromophores.

In the rods for the accumulation of light according to the formula I X¹preferably contains a porphyrin macrocycle, the which may be in the form of bunk sandwich compounds. In addition, X²-X^m+1also preferably contain porphyrin macrocycles.

In one preferred embodiment variants of the rods for the accumulation of light according to the formula I and at least one (e.g. two, three, many, most, or all) X¹-X^m+1selected/selected from the group consisting of a chlorin, bacteriochlorin and somacarisoprodol.

A particular variant embodiment chains for accumulation of light, described above, provides for the movement of holes in the opposite direction (moving) energy of the excited state along some portion or the entire length of the rods for the accumulation of light, and contains:

(a) a first substrate containing a first electrode; and

(b) the layer of rods for the accumulation of light, is electrically connected to the first electrode, each of the rods for the accumulation of light contains a polymer of the formula I:

where:

m is at least 1 (usually two, three or four to twenty or more);

X¹is a group of charge separation, with an excited state with energy equal to or lower than y X²;

X²-X^m+1represent the chromophores; and

X¹-X^m+1chosen in such a way that with injection of either electrons or holes of X in the first electrode, the corresponding hole or electron from X¹tolerated at least to X²not necessarily the X³X⁴and all the way up to X^m+1. In a variant of the embodiment preferred at present, X¹-X^m+1chosen so that during the injection of electron from the X¹in the first electrode, the corresponding hole of the X¹tolerated at least to X²and optionally up to X^m+1.

Chains for accumulation of light provide an intensive absorption of light and deliver (transfer) of the resulting excited state at a specified position within the molecular chain. There are many different applications of chains for accumulation of light. Chains for accumulation of light can be used as components in systems for detecting low levels of light, in particular where it is desirable to control the wavelength of light that is collected. Chains for accumulation of light can be used as input elements in optoelectronic devices and as an input node and system delay energy in the signal systems on a molecular basis. One of the applications of the latter involves the use of fluorescent sensors on a molecular basis. The sensor on the molecular basis uses a set of the Rupp probes (which are associated with the analyzed substance), United with the main molecular chain, which is exposed to the energy transfer of the excited state. The binding of a single analyte with any of the groups of probes leads to the formation of the complex, which can suppress an excited state, which is freely migrates along the main chain (i.e., the exciton). The phenomenon of damping leads to a decrease in the fluorescence of the main molecular chain. Since only one attached to an analyte may cause the phenomenon of extinction, the sensitivity is much higher than if you attended a ratio of 1:1 groups of probes and fluorescent groups. Previously, such fluorescent sensors on the molecular basis used in the main molecular chain chromophores that absorb in the UV or near-UV region. Chains for accumulation of light, described herein are ideally suited as components of a new class of fluorescent sensors on a molecular basis, which strongly absorb (and fluoresce in the visible and near infrared region.

Special application chains for accumulation of light, described here, is the application in solar cells. Solar cell, as described herein typically contains:

(a) a first substrate containing a first electrode;

(b) a second substrate, sod is readuy the second electrode, while the first and the second substrate are arranged to form a space between them, and at least one item from (i) the first substrate and the first electrode and (ii) the second substrate and the second electrode is transparent;

(c) the layer of rods for the accumulation of light, is electrically connected with the first electrode, each of the rods for the accumulation of light contains a polymer of the formula I:

where:

m is at least 1 (and typically two, three or four to twenty or more);

X¹is a group of charge separation, with an excited state with energy equal to or lower than the X²;

X²-X^m+1represent the chromophores; and

X¹electrically connected with the first electrode; and a solar cell further comprises

(d) an electrolyte in the space between the first and second substrates. The carrier mobility of the charge can, optionally, be included in the electrolyte composition.

In a particular variant embodiment of the above item (sometimes referred to here as ″design II″), a solar cell includes:

(a) a first substrate containing a first electrode;

(b) a second substrate containing a second electrode, the first and second substrates are arranged with the formation of the space between the two, and at least one item from (i) the first substrate and the first electrode and (ii) the second substrate and the second electrode is transparent;

(c) the layer of rods for the accumulation of light, is electrically connected with the first electrode, each of the rods for the accumulation of light contains a polymer of the formula I:

where:

m is at least 1 (and typically two, three or four to twenty or more);

X¹is a group of charge separation, with an excited state with energy equal to or lower than the X²;

X²-X^m+1represent the chromophores;

X¹electrically connected with the first electrode; and

X¹-X^m+1chosen in such a way that with injection of either electrons or holes of X¹in the first electrode, the corresponding hole or electron from X¹transferred to X²(and, optionally, to X³X⁴and in some cases all the way up to X^m+1); the solar cell further comprises:

(d) an electrolyte in the space between the first and second substrates; and

(e) optionally, but preferably, the carrier mobility of the charge in the electrolyte.

In a variant of the embodiment preferred at present, X¹-X^m+1selected so that during the injection of electron from the X in the first electrode, the corresponding hole of the X¹transferred to X²-X^m+1.

Another particular variant embodiment (sometimes referred to here as ″design III″) solar cell, described above, contains:

(a) a first substrate containing a first electrode;

(b) a second substrate containing a second electrode, the first and second substrates arranged to form a space between them, and at least one item from (i) the first substrate and the first electrode and (ii) the second substrate and the second electrode is transparent;

(c) the layer of rods for the accumulation of light, is electrically connected with the first electrode, each of the rods for the accumulation of light contains a polymer of the formula I:

where:

m is at least 1 (and typically two, three or four to twenty or more);

X¹is a group of charge separation, with an excited state with energy equal to or lower than the X²;

X²-X^m+1represent the chromophores;

X¹electrically connected with the first electrode; and

X^m+1electrically connected with the second electrode; a solar cell further comprises

(d) an electrolyte in the space between the first and second substrates.

Again, X¹X ^m+1can be chosen so that during the injection of electrons or holes (preferably, electrons) of X¹in the first electrode, the corresponding hole or electron from X¹transferred to X²or, optionally, to X³or X⁴or all the way up to X^m+1.

Many different electrical devices containing a solar cell described above and having the schema (typically, resistive load electrically connected to it, can be obtained with the solar cells of the present invention, as discussed in more detail below.

The present invention is explained in more detail using the accompanying drawings and the description below.

Brief description of drawings

Figure 1. Scheme two common molecular approaches for converting light into electrical energy.

Figure 2. The General scheme of linear chains of chromophores (rods for accumulation of light).

Figure 3. The energy migration along the rod for the accumulation of light and the use of mobile charge carrier for the regeneration of the site of charge separation after injection of electrons (design I).

Figure 4. The energy migration and migration of holes by a hopping mechanism in opposite directions (design II).

Figure 5. The energy migration and migration of holes by a hopping mechanism is in opposite directions in the case when the rods for the accumulation of light enclosed between two electrodes (design III).

Figure 6. Bunk sandwich molecules that can serve as sensitizers.

Figure 7. Mechanisms of sensitization of n-type semiconductor by using a sensitizer S. E_CBand E_VBrepresent respectively the energy of the conduction and valence band of the semiconductor. E_Frepresents the Fermi level of the semiconductor. E^o(S^+/0and E^o(S^+/*) represent, respectively, the formal potentials of recovery for the ground and excited States. also shows the distribution of donor and acceptor levels of the sensitizer by Gerischer.

Figure 8. A simplified view of the mechanism of sensitization TiO₂using the sensitizer S. the Excitation light sensitizer forms an excited state S*, which injects the injected electron in a semiconductor with a rate constant k_inj. Then the oxidized sensitizer S⁺regenerated using an external electron donor (e.g., iodide) with a rate constant k_red. V_OCrepresents the open circuit photopotential, which represents the maximum free energy Gibbs, which, in principle, can be obtained from the element under the conditions of constant illumination. Competition for energy production is the recombination of the charges of the k_cr,that may happen (from a semiconductor) with oxidized sensitizer or the oxidized product of a mobile charge carrier (for example, triiodide).

Figure 9. Regenerative solar cell, constructed for the operation similar to that described in figure 8, except that the solid-state hole conductor replaces active in the oxidation-restoration of the iodide electrolyte/triiodide.

Figure 10. Examples of building blocks that can be assembled in the chromophore chain.

Figure 11. The synthetic approach (method) preparation of linear chromophore chain.

Figure 12. Rational synthesis of a constituent unit based on a porphyrin dimer to prepare the chromophore chain.

Figure 13. Solid-phase synthesis using binding Suzuki to get chains containing porphyrin associated p-phenylene.

Figure 14. Solid-phase synthesis using binding Suzuki to get chains containing chlorine associated p-phenylene.

Figure 15. Bifunctional building blocks for use in polymerization Suzuki.

Figure 16. Rational synthesis of a constituent unit based on a bifunctional porphyrin for use in Polimeri is the Nations Suzuki.

Figure 17. Solid-phase synthesis of chains containing meso, meso-linked porphyrin with attached carboxy-handle.

Figure 18. Solid-phase synthesis of chains containing meso, meso-linked porphyrin with attached atenolol handle.

Figure 19. Join meso, meso-linked chains to contain zirconium bunk sandwich molecule.

Figure 20. Example migration energy, but not the migration of holes in the chromophore chain.

Figure 21. An example of the migration energy and the migration of holes in opposite directions in the chromophore chain.

Figure 22. An example of cascading migration energy and the migration of holes in opposite directions in the chromophore chain migration holes occurs in a certain region of the chain.

Figure 23. Another example of solid-phase synthesis using binding Suzuki to get chains containing chlorine with atenolol handle associated p-phenylene.

Figure 24. Attach chain containing chlorine associated p-phenylene, bunk sandwich molecule containing zirconium.

Figure 25. An example of a reversible migration energy and irreversible migration of holes in the chromophore chain.

Figure 26. Chain containing bacteriochlorin associated with diphenylamine.

Figure 27. Building blocks based on chlorine, which have substituents (functional handle and in two of the meso-positions, and no one in β-provisions.

Figure 28. In the porphyrin having the highest populated molecular orbital (HOMO) a_2uthat has electron density mainly in the meso-positions, and small - β-provisions, higher speeds (2.5-10-fold) are observed when the linkers are meso, and not in β-provisions.

Figure 29. Four different components of the block on the basis of chlorine, as well as the nomenclature of chlorin showing designations A-D rings according to IUPAC-IUB.

Figure 30. The orientation of the transition dipole moment for the long-wavelength absorption band in chlorin free base and metalochlor.

Figure 31. The pair interaction of the components of the blocks on the basis of chlorine when entering a covalently linked chain.

Figure 32. The highest occupied molecular orbital of chlorine is an orbital of a₂that has appreciable electron density at each of the meso - and unrestored β -positions.

Figure 33 illustrates the synthesis of a constituent unit based on the TRANS-chlorin with two β-substituents.

Figure 34A. Synthesis of a new β-substituted Eastern half in the synthesis of chlorin.

Figure 34B. Synthesis of a new β-substituted Eastern half in the synthesis of chlorin, continuing the process illustrated in figure 34A.

Figure 35 illustrer is no synthesis of new β -substituted Western half of the constituting unit based on chlorine.

Figure 36. Other components of the blocks based on the chlorine, which can be obtained using the same synthetic strategy shown above, and which have essentially the same physical properties.

Figure 37. The synthesis of the components of the blocks on the basis of TRANS meso-substituted chlorin (type III) by extending the process for the preparation of chlorine, bearing adjacent (CIS) meso-substituted chlorins.

Figure 38. A second process of obtaining the components of the blocks on the basis of TRANS meso-substituted chlorin (type III).

Figure 39. The various components of the blocks on the basis of meso-substituted chlorin, which can be obtained using the synthesis described above.

Figure 40. The relationship of antenna complexes and reaction center to get holes and electrons from the excitation energy flowing down from the antenna.

Figure 41. Chains for accumulation of light, which absorb light and undergo efficient intramolecular energy transfer.

Figure 42. Here presents a new tool for removal of oxidation equivalent of the site of charge separation. The energy flows along the chain for the accumulation of light to the site of charge separation (protective relays), while the oxidizing equivalent (hole) flows in the opposite direction from protective relays to p is the position of the antenna, where subsequent reactions with electron transfer.

Figure 43. The design according to figure 42 has two major branches. (1) Only two channels for access is required for the protective relays: one for the emission of electrons, and the one where flows the excitation energy and the flow of oxidizing equivalents (holes).

Figure 44 illustrates a linear chain based on the zinc - porphyrins with different meso-substituents.

Figure 45 illustrates a linear chain of Mg - and Zn-porphyrins with different meso-substituents.

Figure 46 illustrates a linear chain metalloboranes with different meso-substituents.

Figure 47 illustrates a linear chain of porphyrins and chlorins with different meso-substituents.

Figure 48 illustrates a linear chain β-substituted chlorins and meso-substituted chlorins.

Figure 49 illustrates a linear chain of components of porphyrin, chlorin, and phthalocyanine.

Figure 50 illustrates the cascade (cataractous). cataract) linear chain using a domain consisting of a set of isoenergy pigments.

Figure 51 illustrates the reaction, suitable for use in the preparation of oligomers rods for accumulation of light.

Figure 52. Polymerization in situ, leading to the rod for the accumulation of light on the surface (e.g. the, Au or TiO₂), which will serve as one of the electrodes of the solar cell.

Figure 53 illustrates the synthesis of meso-substituted chlorins using the techniques described earlier.

Figure 54 illustrates the synthesis of precursors of the Eastern half (EAP) β-substituted chlorin.

Figure 55 additionally illustrates the synthesis of precursors of the Eastern half β-substituted chlorin.

Figure 56 illustrates the synthesis of the Western half (RFP) β -substituted chlorin.

Figure 57 illustrates the synthesis of β-substituted chlorin.

Figure 58 illustrates the synthesis of TRANS β-substituted chlorin.

A detailed description of the preferred options of the incarnation

Solar cells described here require the use of linear chromophore chain rods for accumulation of light), which provide a strong absorption of light. In addition, when this is desirable, as described here, solar cells provide energy migration and the migration of charge in opposite directions. Thus, the chromophore chain absorb light and can be straighten at the molecular level in the flow energy of the excited state and holes in the ground state.

Without any desire to limit the present invention it is possible to notice that some of the potential advantages the and solar cells, described here include the following: they are thin (for example, the rods have a length of not more than 500 or even 200 nm), light, portable, flexible, with good efficiency, solid-state (in one variation of the embodiment), easy to manufacture and have a rational molecular design. In fact, it is expected that this invention will make it possible, where this is desirable, quantitative conversion of incident photons into electrons at the individual wavelengths of light and with the overall efficiencies of >5% in the sunlight.

I. Definitions

Here we use the following terms and phrases:

The substrate, as here used, is preferably a solid material (which may be flexible or rigid), suitable for use when attaching one or more molecules. The substrate can be formed from materials including, but not limited to, glass, organic polymers, plastic, silicon, minerals (e.g. quartz), semiconductor materials, ceramics, metals and the like. The substrate may be in any usable form, including flat, planar, curved, rod-like, and the like. The substrate may be inherently conductive and serve as the electrode itself, or the electrode may be is formed on the substrate or connected with it by appropriate means (for example, deposition of a layer of gold or a layer of a conductive oxide). Either one or both of the substrate in solar cells can be transparent (i.e., the wavelengths of light that excite the chromophores can pass through the substrate and the corresponding electrode even if they visually look muddy). Chains for accumulation of light, the substrate and the electrode can be of any usable type. One of the substrates can be opaque with respect to the wavelengths of light that excite the chromophores. One of the substrates may be reflective or provided with a reflective coating so that light that passes through chains or rods, reflected back in chains or rods.

The term ″electrode″ refers to any medium capable of carrying a charge (e.g., electrons) to the terminal for the accumulation of light and/or from him. Preferred electrodes are metals (e.g. gold, aluminum), nonmetals (e.g., conductive oxides, carbides, sulfides, selenides, tellurides, phosphides, and arsenides, such as cadmium sulfide, cadmium telluride, diselenide tungsten, gallium arsenide, gallium phosphide, and the like), and conductive organic molecules. The electrodes can be prepared with almost any 2-dimensional or 3-dimensional form.

The term ″conducting oxide″, as it is used here refers to any usable conducting oxide, including binary metal oxides such as tin oxide, indium oxide, titanium oxide, copper oxide and zinc oxide, or triple (tertiary) metal oxides, such as strontium titanate and barium titanate. Other examples of usable conductive oxides include, but are not limited to, indium oxide tin, titanium dioxide, tin oxide, indium gallium oxide, zinc oxide, and zinc oxide India. Semiconductors based metal oxide can be private or doped with small quantities of materials to control conductivity.

The term ″heterocyclic ligand″, as it is used here, refers generally to any heterocyclic molecule consisting of carbon atoms and containing at least one, and preferably multiple heteroatoms (e.g. N, O, S, Se, Te), and these heteroatoms may be the same or different, and this molecule is able to form a sandwich coordination compounds with other heterocyclic ligand (which may be the same or different) and metal. Such heterocyclic ligands, as a rule, represent the macrocycles, in particular, derivatives of tetrapyrrole, such as phthalocyanines, porphyrins and porphyrazines.

The term ″porphyrin macrocycle″ refers to the porphyrin or porphyrin derivative. Such a derivative is include porphyrins with additional rings, ortho-condensed or ortopedi-condensed with porphyrin core; porphyrins, with the substitution of one or more of the carbon atoms of the porphyrin ring by an atom of another element (skeletal replacement); derivatives with substitution of the nitrogen atom of the porphyrin ring by an atom of another element (skeletal replacement of nitrogen); derivatives having other substituents than hydrogen positioned on the peripheral (meso-, β-) or internal atoms of the porphyrin, derivatives with substitution of one or more links of the porphyrin (hydroporini, for example, a chlorin, a bacteriochlorin, usabacterial, decahydronaphthalene, corfini, and so procarbine this); derivatives obtained by coordinating the binding of one or more metals with one or more atoms of the porphyrin (metalloporphyrins), derivatives having one or more atoms, including pyrrole and pyrromethene blocks inserted into the porphyrin ring (extended porphyrins), derivatives having one or more groups that have been removed from the porphyrin ring (compressed porphyrins, for example, Corrin, Chorrol) and combinations of the above derivative (for example, phthalocyanines, porphyrazines, naphthalocyanine, subphthalocyanines and isomers of porphyrin). Preferred porphyrin macrocycles contain at least one 5-member of the second ring.

The term porphyrin refers to a cyclic structure, usually consisting of four pyrrole rings along with four nitrogen atoms and two hydrogen atoms, which can easily be replaced by atoms of different metals. Typical porphyrin is a gemin.

″Chlorine″ is essentially the same term as the porphyrin, but differs from porphyrin that has partially saturated pyrrole ring. The main chromophore of chlorophyll, i.e. the green pigment for photosynthesis of plants, is chlorine.

″Bacteriochlorin″ is essentially the same as the porphyrin, but differs from porphyrin that has two partially saturated not adjacent to each other (i.e. TRANS) pyrrole rings.

″Usabacterial″ is essentially the same as the porphyrin, but differs from porphyrin that has two partially saturated neighboring (i.e. CIS) pyrrole rings.

Terms ″sandwich coordination compound″ or ″sandwich coordination complex″ relates to the compound of formula LⁿM^n-1where each L is a heterocyclic ligand, such as porphyrin macrocycle, each M is a metal, n is 2 or more, most preferably 2 or 3, and each metal is located between a pair of ligands and the binding is seen with one or more heteroatoms (and usually with many heteroatoms, for example, 2, 3, 4, 5) in each ligand (depending on the oxidized state of the metal). Thus, the sandwich coordination compounds are ORGANOMETALLIC compounds such as ferrocene, in which the metal unites with the carbon atoms. Ligands in the sandwich coordination compound, usually housed in a package (i.e. are oriented generally facing each other and coaxially aligned with each other, although they may or may not be able to rotate around this axis with respect to each other). See, for example, D. Ng and J. Jiang, Chem. Soc. Rev. 26, 433-442 (1997). Coordination sandwich compounds may be ″gomolepticheskimi″ (where all the ligands L are the same) or ″getrelationship″ (where at least one ligand L is any different than all the other ligands in it).

The term ″bunk sandwich coordination compound″ refers to a sandwich coordination compound as described above where n is 2, and, thus, have the formula L¹-M¹-L²where each of the L¹and L²may be the same as any other or different from them. See, for example, J. Jiang et al., J. Porphyrins Phthalocyanines 3, 322-328 (1999).

The term ″multiporphyrin chain″ refers to a discrete number of two or b is more covalently-linked porphyrin macrocycles. Multiporphyrin chains can be linear, cyclic or branched, but are preferably linear. Considering the stakes for the accumulation of light preferably represent multiporphyrin chain. The rods for the accumulation of light or multiporphyrin chains can be linear (that is, all the porphyrin macrocycle can be connected in TRANS-positions) or may contain one or more bends or ″breaks″ (for example, by incorporating one or more non-linear linkers in the rod for the accumulation of light or by incorporating one or more CIS-substituted porphyrin macrocycles in the rod for the accumulation of light). Some of porphyrin macrocycles can further comprise additional ligands, in particular, porphyrin macrocycle, with the formation of the sandwich coordination compounds, as further described below. The rods are optional, but preferably oriented essentially perpendicular to one of the electrodes, and most preferably to both, i.e. the first and second electrodes.

"Chromophore" means light absorbing node, which may be a node inside a molecule or may comprise a molecule. Typically, the chromophore is a coupled system of alternating double and single bond, which may include unbound electrons, but they are not limited to alternating single and double bonds as triple and a single bond, a mixture alternating triple/single and double bonds are also chromophores. Double or triple bond itself is a chromophore. The heteroatoms can be included in the chromophore). Examples of chromophores include cyclic conjugated system with 18 PI-electrons, which gives the color of the phthalocyanine pigments, a linear system of alternating single and double bonds in the visual pigment of the retinal or carbonyl group of acetone.

"The group of charge separation" or "separation unit charge" refers to molecular particles, which when excited by direct absorption or energy transfer from another absorber) transfer an electron to another part of the same molecule or transfer an electron to another molecule, semiconductor or metal. "The group of charge separation" or "site of charge separation gives you the opportunity to keep some part of the energy of the excited state when moving or electron transfer. As a rule, the group of charge separation" or "separation unit charge is located at the end of the chain or rod for accumulation of light, which is the energy of the excited state. "Group separation C is the number of" or "site of charge separation that makes or causes the conversion of the energy of the excited state in a separate electron conductivity, or a hole, or into a pair of electron-hole. The electron can be ejected in a semiconductor by using the "group of charge separation" or "site of charge separation". Is it possible to "charge separation" or "separation unit charge removed an electron from another molecule, or a semiconductor, thereby creating a negative charge on the group split charge" or "site of charge separation and a hole in another molecule or semiconductor. The reaction center of bacterial photosynthesis is the main example of the "group of charge separation" or "site of charge separation". Synthetic molecules porphyrin-quinone or porphyrin-ball molecule (fullerene) function by absorbing light and using the resulting energy for charge transfer.

The term ″Deputy″, as it is used here in formulas, in particular, marked with S or Sⁿwhere n is an integer, in a preferred variant embodiment refers to groups (subuser) with an excess or lack of electrons, which can be used to determine the redox potential (potentials) of the connection. Preferred substituents include, but are not limited to, H, aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxy, alkylthio, perfluoroalkyl, Perfora the sludge, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, amido and carbarnoyl. In preferred embodiments, embodiments of the substituted aryl group is attached to the porphyrin or the porphyrin macrocycle, and the substituents on the aryl group are selected from the group consisting of aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perforare, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, amido and carbamoyl. Optional substituents include, but are not limited to, 4-chlorophenyl, 4-triptoreline and 4-methoxyphenyl. Preferred substituents provide a range of values of the redox potential is less than approximately 5 volts, preferably less than about 2 volts, more preferably less than about 1 volt.

The term ″aryl″ refers to a compound whose molecules have the ring structure characteristic of benzene, naphthalene, phenanthrene, anthracene, and the like (that is, either ring with 6 carbon atoms of benzene or the condensed ring with 6 carbon atoms other aromatic derivatives). For example, the aryl group may be a phenyl (C₆H₅) or naphthyl (C₁₀H₇). You may notice that the aryl group, when it acts as the batch is of Italia, may itself be more substituents (for example, the substituents envisaged as Sⁿin the various formulas given here).

The term ″alkyl″ refers to a paraffinic hydrocarbon group which may be derived from an alkane by removal of one hydrogen atom from the formula. Examples are methyl (CH₃-), ethyl (C₂H₅-), propyl (CH₃CH₂CH₂-), isopropyl ((CH₃)₂CH-).

The term ″halogen″ refers to one of the electronegative elements of group VIIA of the Periodic table (fluorine, chlorine, bromine, iodine, astatine).

The term ″perfluoroalkyl″ refers to an alkyl group where each hydrogen atom replaced by a fluorine atom.

The term ″perforare″ refers to an aryl group, where each hydrogen atom replaced by a fluorine atom.

The term ″pyridyl″ refers to an aryl group, where one CR node is replaced by a nitrogen atom.

The term ″sulfoxyl″ belongs to the group of composition RS(O)-, where R is some alkyl, aryl, cycloalkyl, performanceline or bertorello group. Examples include, but are not limited to, methylsulfonyl, phenylsulfonyl and the like.

The term ″sulfonyl″ belongs to the group of composition RSO₂-, where R is some alkyl, aryl, cycloalkyl, perfe is alkyl or bertorello group. Examples include, but are not limited to, methylsulphonyl, phenylsulphonyl, p-toluenesulfonyl and the like.

The term ″carbarnoyl″ belongs to the group of R¹(R²)NC(O)-, where R¹and R²represent H or some alkyl, aryl, cycloalkyl, performanceline or bertorello group. Examples include, but are not limited to, N-ethylcarbazole, N,N-dimethylcarbamoyl and the like.

The term ″amido″ belongs to the group of R¹CON(R²)-, where R¹and R²represent H or some alkyl, aryl, cycloalkyl, performanceline or bertorello group. Examples include, but are not limited to, acetamido, N-ethylbenzamide and the like.

The term ″acyl″ belongs to the group of organic acids in which the-OH of the carboxylic group is replaced by some other substituent (RCO-). Examples include, but are not limited to, acetyl, benzoyl and the like.

In preferred variants of the embodiment, when the metal is denoted by ″M″ or ″Mⁿ″, where n is an integer, you can see that the metal can be associated with a counterion.

A linker is a molecule that is used to link two different molecules, two sobeslav molecule or molecules and mean the LCD. When they are all covalently linked, they form the nodes of a single molecule.

The term ″electrically connected″, when used in relation to the terminal for the accumulation of light and the electrode or chromophores, to groups of charge separation and to the electrodes, refers to the relationship between this group or molecule and related group or electrode, so that electrons move from medium/molecule for storage to the electrode or from the electrode to the molecule and thereby alter the oxidized state of the molecule for storage. Electric binding may include direct covalent bond between medium/molecule for storage and electrode-mediated covalent binding (e.g., via a linker), direct or indirect ion binding between medium/molecule for storage and the electrode or other binding (for example, hydrophobic binding). In addition, may not require any real binding, and a rod for the accumulation of light may simply be in contact with the surface of the electrode. Also there is no strict need for contact between the electrode and rod for accumulation of light, when the electrode is sufficiently close to the terminal for the accumulation of light to allow electron tunneling between medium/molecule and the electron is born.

"The energy of the excited state" refers to the energy stored in the chromophore in a metastable state after absorption of light (or energy transfer from the absorber). For the excited singlet (triplet) state the amount of "energy of the excited state is determined by the energy of the shortest wavelength bands of fluorescence (phosphorescence). The amount of energy of the excited state is greater than or equal to the energy of the separated electrons and holes after the separation of the charge.

The electrolyte used for the implementation of the present invention may be aqueous or non-aqueous electrolytes, including polymer electrolytes. The electrolyte may contain a solid or consist of him, and in this latter case, the solar cell can be manufactured with the exception of the fluid in the space between the first and second substrates. The electrolyte consists of or contains a substance that increases the electrical conductivity of a carrier medium. Most electrolytes are salts or ionic compounds. Examples include sodium chloride (table salt), lithium iodide or bromide of potassium in water; tetrabutylammonium hexaphosphate or tetraethylammonium perchlorate in acetonitrile or dichloromethane; or an ionic polymer gel.

"Mobile charge carriers" refer to Jonah, the molecule is whether other particles, capable of moving charges (electrons or holes) between two electrodes in a solar cell. Examples include the quinones in the water, molten salts and iodide in polymer gel, such as polyacrylonitrile. Examples of mobile charge carriers include, but are not limited to, iodide, bromide, tetramethyl-1,4-phenylenediamine, tetraphenyl-1,4-phenylenediamine, p-benzoquinone, C₆₀C₇₀pentacene, tetrathiafulvalene and methylviologen.

II. SOLAR cells CONTAINING RODS FOR

The ACCUMULATION of LIGHT

A. Introduction

The purpose of the development of ultrathin solar cell with a high absorption rate is achieved using linear-chain chromophores, which serve as terminals for the accumulation of the light (AU). The General design of linear chains of chromophores is depicted in figure 2. Pigments (i.e. molecules containing chromophores) are connected covalently by using linkers with the formation of the linear architecture. At one end of the chain is a sensitizer or the site of charge separation (protective relays). Protective relays are also attached to the electrode using a linker and a functional group, denoted by Y. the far end of the rod for the accumulation of light is a finite group, denoted by Z. Finite group can consist of simple alkyl or aryl substituent or may contain a link is to attach to the surface or to the counter-electrode. When joining a linear molecules AU/protective relays to the electrode through a connecting group Y the rods will be oriented more or less vertically. When this linear rod-like architecture makes it possible multilayer packaging of pigments, where each pigment in the rod is held near the neighboring pigments in the same rod using the linker L. the Structure (model) of the package and the distance between the rods is controlled by deputies, integrated with pigments. In General, they are referred to as ″chain chromophores″, and this term is used interchangeably with linear rods for the accumulation of light (both terms indicate a linear architecture related pigments that effectively absorb the light and accumulate energy (and holes) in a controlled way). Note that the terms ″sensitizer″ or ″separation of charge″ are used interchangeably; the latter term emphasizes the fact that fotovozbuzhdenii agent (photosensitizer), which injects electrons into the semiconductor can consist of multiple nodes (e.g., porphyrin-chlorin, chlorine-quinone, bacteriochlorin-spherical molecules (fullerenes)).

Three different designs are described for chain chromophores (see below). Mainly for all the constructive schemes is the fact that the chain will accumulate a large portion of the incident solar radiation. The strategy of using monolayer molecular sensitizers on the planar surface of the electrode has historically been rejected, because it is absorbed only a small fraction of the incident sunlight. The described invention kontseptualizirovat new molecular approach in which the prior chain of chromophores will be arranged on the surface of the electrode. By assembling chains perpendicular to the electrode surface monolayer coverage, will lead to a substantial increase light absorption. For example, phthalocyanines, typically have coefficients of extinction ˜250000 M^-1cm^-1in the red part of the visible spectrum (600-700 nm, depending on the state of the metallation). A monolayer of such phthalocyanines on a flat surface corresponds to ˜10^-10mol/cm²and will absorb an estimated 5.6% of the incident light. A chain of 20 phthalocyanines with additive absorption (i.e. no new absorption bands associated with the aggregation and/or electronic interactions), spatially organized in such a way that it occupies the same surface area, absorbed 68% of the incident light. If the number of phthalocyanines is increased to 40 or roughness factor of the electrode surface was equal to two, were absorbed least 90% of incident light. Many of the surface electrodes is iznachalno are rough, so monolayer of chains 20 chromophores (i.e. each chain consists of 20 chromophores) should lead essentially to the quantitative absorption of light. This ″ledge″ (thickness) looks very favorably in comparison with the roughness factor of the surface ˜1000 required for efficient accumulation of light, as currently used in the elements of Gratzel type.

In the construction of the first terminals of the AC/protective relays attached to one of the electrodes through the connecting group Y (figure 3). The element includes a movable (i.e. diffusing) charge carriers. Linear rods speakers, usually containing 5-20 pigments absorb light. The excitation energy transfer between pigments in the terminal using the transmission mechanisms through space and/or through the link leads to the fact that energy reaches protective relays (illustrated in stage 2, figure 3). Then Horny protective relays injects an electron into the conduction band of the electrode (stage 4). The resulting hole remains protective relays and cannot migrate into the backbone of the speakers, because the oxidation potential of protective relays is lower than the directly neighboring pigments in terminal speakers. The diffusion of mobile charge carrier near the oxidized protective relays leads to the transfer of electrons/holes, regenerating protective relays and leaving a hole on a mobile charge carrier. Catamarca moves under the influence of the diffusion of mobile charge carrier and/or the subsequent migration of holes between the mobile charge carriers as long until you reach the counter-electrode at the far end of the rod AC (near Z; not depicted).

In design II rods AU/protective relays attached to one of the electrodes through the connecting group Y (figure 4). The element includes a movable (i.e. diffusing) charge carriers. All the features are the same as in design I, except that the hole formed in the protective relays (electron injection electrode), can migrate within the linear rod AC. This has two consequences. (1) the lifetime of a state of charge separation increases, giving a significant decrease in the recombination of charges at the interface of the protective relays-electrode. (2) the Mobile charge carriers can access the hole in regions remote from the electrode surface. Region remote from the surface, as expected, are more accessible, and thereby facilitated the transfer of holes and their migration (through diffusion) to the counter-electrode.

In design III terminals AC/protective relays attached to one of the electrodes through the connecting group Y (figure 5). The opposite end of each rod is attached to the counter-electrode. No moving (i.e. the diffusion of charge carriers in the element is not present (although the electrolyte may be present). The absorption of light, the energy migration between pigments and per the nose of the electron in protective relays is exactly the same as the same processes in structures I and II. However, the hole in the protective relays, resulting from injection of an electron in the electrode migrates through a hopping mechanism of transfer of holes between the pigments in the rod as, and then transferred to the counter-electrode. There are several varieties of this design. (1) No diffusing charge carriers are not present in the element. (2) Only two different channel access are necessary in protective relays; one for electron transfer at the electrode and one provided by the rod as, for migration inside the excitation energy and transfer out of the resulting hole. In contrast, the design of I requires three channels for access to protective relays: one for the migration energy inside, one for the electron transfer to the outside and one for mobile charge carriers in order to access the hole. The absence of mobile charge carriers in design III leads to the creation of solid-state solar cell.

In previous studies of the phenomena of accumulation of light were created chains in the shape of stars, consisting of porphyrins and phthalocyanines (Li, J.; Lindsey, J.S.J.Org.Chem. 1999, 64, 9101 -9108; Li, J et al., J.Org.Chem. 1999, 64, 9090-9100; Li, F. et al., J.Mater.Chem. 1997, 7, 1245-1262), a cluster of boron-dierenbach dyes surrounding the porphyrin (Li, F. et al SOC. 1998, 120, 10001-10017), and a linear chain of four porphyrins and one boron-dipirona (Wagner, R.W.; Lindsey, J.S.JAm.Chem.Soc. 1994, 116, 9759-9760), and cyclic chains (Li, J. et al., SoC. 1999, 121, 8927-8940). Also studied the effect of different metals in metalloporphyrins when the modulation rate of energy transfer (Hascoat, P. et al., Inorg.Chem. 1999, 38, 4849-4853). Were also characterized the effects of various linkers on the rate of energy transfer (Hsiao, J.-S. et al., J.Am.Chem. Soc. 1996, 118, 11181-11193; Yang, S. I. et al., J.Phys.Chem. 1998, 102, 9426-9436), the composition of the orbitals (Strachan, J.P. et al., J.Am.Chem. Soc. 1997, 119, 11191-11201) and the location of the linker on the porphyrin pigment (Yang, S.I. et al., J.Am.Chem. Soc. 1999, 121, 4008-4018). It was also done modeling migration energy in a linear chain chromophores with the aim of evaluating the performance of various designs of the architecture of molecules (Van Patten, P.G. et al., J.Phys.Chem.B 1998, 102, 4209-4216). These synthetic molecules accumulating light, strongly absorb in the visible region and are very efficient energy transfer. As part of these studies, the study of the properties of the oxidized complexes showed a rapid transfer of holes by a hopping mechanism between components (Seth, J. et al., SoC. 1994, 116, 10578-10592; Seth, J. et al., SoC. 1996, 118, 11194-11207). The features proposed here for use when designing linear chromophore chains and described in the present invention are confirmed, but not all of them are expected based on all these previous works, the components of the level of tech is I. The synthesis methods for making chains for accumulation of light are sufficient for a specialist in this area to get the molecules described herein. In particular, there are many ways to prepare porphyrin constituent units (a) Lindsey, J.S. et al., Tetrahedron 1994, 50, 8941-8968. (b) Lindsey, J.S. In The Porphyrin Handbook; Kadish, K.M.; Smith, K.M.; Guilard, R., Eds.; Academic Press, San Diego, CA 2000, Vol.1, pp.45-118; Cho, W.-S. et al., J.Org.Chem. 1999, 64, 7890-7901; Wagner, R.W. et al., SoC. 1996, 118, 11166-11180; Balasubramanian, T.; Lindsey, J.S. Tetrahedron 1999, 55, 6771-6784)constituting the blocks on the basis of chlorine (Strachan, J.P. et al., J.Org.Chem. 2000, 65, 3160-3172), phthalocyanines (Yang, S.I. et al., J. Mater. Chem. 2000, 10, 283 -297; Tomoda, H. et al., Chem. Lett. 1980, 1277-1280; Tomoda, H. et al., Chem. Lett. 1983, 313-316) and related chromophores (Wagner, R.W.; Lindsey, J. S. Pure Appl. Chem. 1996, 68, 1373-1380). Methods compounds containing chromophores (i.e. pigment) components of the units in the linear chain is also installed (Wagner, R.W. et al., J.Org.Chem. 1995, 60, 5266 -5273; DiMagno, S.G. et al., J.Org.Chem. 1993, 58, 5983 -5993; Wagner, R.W. et al., Chem. Mater. 1999, 11, 2974 -2983), and they include, but are not limited to, methods of binding, mediated by the Pd. Were synthesized more developed architecture, consisting of chains for accumulation of light and nodes of charge separation, which demonstrate very high efficiency (Kuciauskas, D. et al., J.Am.Chem. Soc. 1999, 121, 8604-8614).

B. Components

Key requirements for pigments intended for accumulation SV is the are intense absorption in the visible region, a narrow distribution of energies of the excited state (note the sharp absorption bands and fluorescence), the lifetime of the excited singlet state, sufficient to transfer energy (typically a few nanoseconds) and compatibility with the approach to synthesis, using building blocks and leading to the linear architecture. The pigments selected for use in the linear rods speakers are chosen from porphyrin family (tetrapyrrole macrocycle). Examples include porphyrin, chlorin, bacteriochlorin, tetraazaporphyrin (porphyrazines), phthalocyanines, naphthalocyanines and derivatives of these compounds. Porphyrin pigments can be supplemented with additional pigments, such as members of families perylene, Liapunov, xantinol and dipyrromethene. Absorption spectra of these pigments are well known to experts in the art and can be seen in various reference sources (Du, H. et al., Photochem. Photobiol. 1998, 68, 141 -142).

Important requirements for the linkers connecting the pigments are as follows. (1) Support for fast energy transfer processes of the excited state (through communication and/or through space), (2) support the migration of holes in the ground state by a hopping mechanism that is necessary is some cases (design II and III), and (3) achieving compatibility with the approach to synthesis, using building blocks and leading to the linear structure of the pigments. Selected linkers to connect pigments in the form of linear rods speakers include 4,4'-diphenylamin, 4,4'-diphenylbutadiyne, 4,4'-biphenyl, 1,4-phenylene, 4,4'-stilbene, 1,4-bicicletta, 4,4'-azobenzene, 4,4'-benzylideneaniline, 4,4"-terphenyl and the absence of the linker (i.e. direct C-C bond). Linkers on the basis of p,p' -diphenylamine and p-phenylene, as shown, to support the rapid energy transfer of the excited state and the migration of holes in the ground state by a hopping mechanism between porphyrin molecules.

One of the important requirements to the site of charge separation (protective relays) is that he had the energy of an excited state that is equal to or smaller than the adjacent pigments in the chain of speakers (in other words, absorbing light with wavelengths equal to or greater than the pigments in the chain AU). For solar cells based on semiconductors reduction potential of the excited state must be larger than the edge (bottom) of the conduction. Additional requirements for protective relays lies in the fact that he was subjected to rapid electron transfer in the excited state, had enough energy to injection of an electron into the conduction band of the electrode, and gave stabilny cation-radical. The molecules selected for protective relays, also chosen from porphyrin family, including porphyrin, chlorin, bacteriochlorin, tetraazaporphyrin (porphyrazines), phthalocyanines, naphthalocyanines and derivatives of these compounds. A particularly attractive group of derivatives consists of bunk sandwich molecules with a Central metal, such as zirconium (Kim, K. et al., Inorg.Chem. 1991, 30, 2652-2656; Girolami, G.S. et al., Inorg.Chem. 1994, 33, 626-627; Girolami, G.S. et al., Angew. Chem.Int.Ed.Engl. 1996, 35, 1223-1225; Collman, J.P. et al., Inorg.Chem. 1997, 36, 5603-5608). Examples bunk sandwich molecules is depicted in figure 6. These two compounds can be obtained from any of the ligands in the family of tetrapyrrole macrocycles.

In the porphyrin family elektrohimicheskiy the potential of the porphyrin can be selected within a wide range by including in the composition of the deputies, discharging an electron or electron releasing (Yang, S.I. et al., J. Porphyrins Phthalocyanines 1999, 3, 117-147). Examples of such substituents include aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perftoran, pyridyl, cyano, thiocyanato, nitro, amino, N-alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido and carbarnoyl. The Monomeric porphyrins change elektrokhimicheskogo capacity can also be achieved through various Central metals (Fuhrhop, J.-H.; Mauzerall, D. SOC. 1969, 91, 4174-411). A large variety of metals can be included in the porphyrins. Those metals that are photochemically active, include Zn, Mg, Al, Sn, Cd, Au, Pd and Pt. It is clear that some metals are counterion. Porphyrins, as a rule, form a very stable cation radicals (Felton, R.H. In The Porphyrins; Dolphin, D., Ed.; Academic Press: New York, 1978; Vol.V, pp.53 -126).

The linkers connecting the protective relays with the surface of the electrode, to provide a linear architecture, support the electron transfer through space and/or through the link and have a functional group suitable for use when attaching to the electrode. Examples of suitable functional groups include ester, carboxylic acid, boric acid, thiol, phenol, silane, hydroxy, sulfonic acid, phosphonic acid, alkylthiol and the like. Linkers can be composed of 4,4'-diphenylamine, 4,4' -diphenylbutadiyne, 4,4'-biphenyl, 1,4-phenylene, 4,4'-stilbene, 1,4-bicycloheptane, 4,4'-azobenzene, 4,4'-benzylideneaniline, and 4,4"-terphenyl, 1,3-phenyl, 3,4'-diphenylamine, 3,4'-diphenylbutadiyne, 3,4'-biphenyl, 3,4'-stilbene, 3,4'-azobenzene, 3,4'-benzylideneaniline, 3,4"-terphenyl, and the like.

C. Materials

The invention synthesized chromophoric chains, designed for vector energy transfer and charge in when they gather on the surfaces of the electrodes, gives who is very useful to use conductive materials as substrates for conversion of solar energy. This diversity of materials makes it possible constructive development of solar cells for specific applications, some of which are described above. The following describes the materials and mechanisms of solar energy conversion (design I-III), which are expected to yield improved efficiency of conversion.

1. Transitions semiconductor-chromophore chain. Generation of anodic photocurrent represents the most common and effective mechanism by which solar energy can accumulate in semiconductors using molecular chromophores (Gerischer, H. Photochem. Photobiol. 1972, 16, 243; Gerischer, H. Pure Appl.Chem. 1980, 52, 2649; Gerischer, H.; Willig, F. Top.Curr.Chem. 1976, 61, 31). Semiconductor materials such as TiO₂(rutile or anatase), ZnO, SrTiO₃, SnO₂and In₂O₃,are thermodynamically stable and can be obtained in the form of thin films, polycrystalline substrates, thin films of colloidal particles or crystals with high transparency in the visible region. Large Smoking area (>3 eV) ensures that the direct excitation of the semiconductor will be minimal for the case of applications on earth. In addition, materials such as SnO₂are commercially available on flexible polymer substrates.

A graphical representation of the chart type Gerischer for registration of birth, the STN accepted mechanism shown in figure 7 for molecular sensitizer S. For the depicted case, the potential recovery of the excited state lies above the edge (bottom) in the conduction band by an amount greater than the energy reorganization [E^o(S^+/*)-λ>E_CB]. This energy positioning leads to maximum overlap of the donor levels of the excited state of the sensitizer and continuing the conduction band of the semiconductor, which, in turn, provides the maximum rate of electron transfer, that is barrier-free electron transfer across the boundary. The excess energy of the injected electron dissapered with lattice vibrations (phonons) as electron thermalized at the bottom of the conduction band. For this reason, the injection of an electron is irreversible, and in fact, the redistribution of the population of the excited state is never observed.

The death of the injected electrons, as expected, depends on the bias conditions (warp zone) in the semiconductor. If the injection is carried out when the semiconductor is close to the state of the flat areas (a in figure 7), then the expected rapid recombination with the oxidized dye, because there is no region of the electric field to promote spatial separation of the injected electron and the oxidized holes. If Polop Vodnik is in conditions of impoverishment, the injected electron is deflected in the direction of displacement of the surface electric field, and recombination slows (b in figure 7). Therefore, the emergence of current when measuring characteristics depending on the photocurrent-voltage can be taken as a rough estimate of the absence of curvature zones. The increased lifetime of the separated state of charge on the boundary of the molecule-semiconductor in conditions of impoverishment makes possible the regeneration of the sensitizer via an external electron donor for applications in regenerative solar cells.

Simplified regenerative solar cell based on molecular sensitizer on the n-type semiconductor is depicted in figure 8. Excited sensitizer S* injects an electron into the semiconductor with a rate constant k_inj. Molecules of the oxidized dye accept an electron from the donor (i.e. mobile charge carrier)present in the electrolyte, k_red. Iodide is a donor, shown in the figure. The products of the oxidation of iodide restored on the dark cathode. The total process provides the opportunity for the generation of electric current by light with energy smaller than the forbidden zone of the semiconductor, and without the total chemical transformations. Recombination of charge k_crcan occur before OK is Lenogo sensitizer S ⁺or to the oxidized particles donor. Depicts the donor is an iodide, which can be dispersed in water, an organic solvent or polymer gels. Alternative active in the oxidation-restoration (i.e. electrochemically active) electrolytes include Br^-/Br₂, quinone/hydroquinone and inorganic coordination compounds.

Can be used with solid elements, which would use instead of active in the oxidation-restoration of electrolyte ″hole″ conductors, semiconductors p-type or perhaps metals. The first two alternatives have precedent, and hole conductors, such as TPD (N,N-diphenyl-N',N'-bis(3-were)-1,4-phenylenediamine) or OMeTAD [2,2',7,7'-tetrakis(N,N-bis(p-methoxyphenyl)amine]-9,9'-spirobifluorene known (Salbeck, J. et al., Synth. Met. 1997, 91, 209). In this regard, we also used the p-type semiconductors, such as CuNCS (O'regan, B.; Schwartz, D.T. Chem.Mater. 1998, 10, 1501).In both cases, the materials must be thermodynamically capable of restoring oxidized component in the chain of chromophores. An example of how this item can work with hole conductor is presented on figure 9.

Through the use of the chromophore chains instead of a single monolayer of molecules of the sensitizer S can be realized a significant increase in e is the efficiency. For example, in the construction of the first sensitizer S is replaced by the protective relays, which covalently binds the hard chain chromophores. The chain extends generally normal to the electrode surface. The advantage of this approach is that the actual surface area occupied on the surface of the electrode is comparable with such square for a single sensitizer S, but the efficiency of the accumulation of light is much greater. In the described solar cells conversion efficiency of incident photons in the current (IPCE) is a product of three parameters according to equation 1.

IPCE=LHE×Φ_inj×η (1)

The term LHE indicates the efficiency of the accumulation of light and is equivalent to the term α IUPAC (the absorption coefficient), which is equal to the fraction of light absorbed (that is, (1-T), where T represents the ratio of the passage). The term Φ_injrepresents the quantum yield of electron injection into the electrode through the interface. The term η is a collection efficiency of electrons, i.e. the fraction of the injected electrons, which reaches an electric circuit. Chain chromophores in the design I should increase LHE without reducing the remaining parameters, and for this reason it is expected a higher degree of conversion of solar is about light.

Application of design II for sensitized semiconductor electrode is expected to provide a higher conversion efficiency of sunlight in comparison with the construction of I, because the "hole" will move to the target chromophore in the chain and away from protective relays and semiconductor electrode. This migration of holes to prevent the recombination of an electron in a semiconductor with a ″hole″ in the chromophore chain. In addition, because the stage of regeneration will occur further from the electrode surface, is expected to decrease recombination with the oxidation products of the donor. Both of these improve the kinetics should raise ηi.e. the collection efficiency of electrons in equation 1, and therefore it is expected a higher photocurrent. In addition, as expected, will increase fotoaprata open circuit V_OC. In regenerative solar cells maximum of the Gibbs free energy, which can be obtained, corresponds to the energy difference between the Fermi level of the semiconductor and the redox potential of the electrolyte V_OC. To prevent recombination of the injected electrons, the Fermi level increases, and V_OCincreases. This effect can be very large. For example, in the element type Gratzel losses by recombination to the product of oxidized iodide take into account what I just like the loss of photocurrent in several nanoampere, while spent ˜200 mV V_OC. Since power is the product of current and voltage, this represents a significant loss.

It may even be possible to exclude active in the oxidation-restore electrolytes, hole conductors or vias with a semiconductor p-type and just use the chromophore chain to bounce ″holes″ directly in the metal counter-electrode, as shown in structure III. Associated with this process, as you can imagine, happens in the film ″organic semiconductor″, described above, and is very desirable because the mediating migration of holes to the counter-electrode always requires potential energy. Quenching of the excited state of the chain chromophores metal surfaces is an expected problem (see below). However, because the chain of chromophores is illuminated through the transparent semiconductor and the chain is strongly absorbing, very few excited States will be created near the metal counter-electrode. Accordingly, the availability of linear chromophore chain can make it possible to make effective items by using the metal surfaces.

2. Metal-chromophore chain. There are two possible the process of electron transfer in the excited state through the interface, which may occur from the molecular excited state S*, formed on the metal surface: (a) Metal accepts an electron from the S* with the formation of S⁺; or (b) the metal transfers the electron S* with the formation of S^-. None of these processes have not been observed directly. These two processes must compete, and if there are any benefits, in the amount of any charge is not transferred across the boundary. To obtain stationary photoelectrochemical response back to S⁺(or S^-reactions with electron transfer across the border with the receipt of the products in the ground state should also be excluded. The energy transfer from the excited sensitizer to the metal is thermodynamically favorable and as permitted by the mechanism Forster and mechanism of Dexter. There are theoretical predictions and experimental data describing the damping of the "energy transfer" molecular excited States of metals.However, these studies include measurements of photoluminescence (PL) and real damping mechanisms, including electron transfer or energy, leaving only the object of discussion. However, competitive quenching by energy transfer is often used to explain the low efficiency of the photocurrent on sensibilizirovannoy the interfaces with metals. However, there are many reasons to predict bad outputs sensitization to metal electrodes (Gerischer, H. Photochem. Photobiol. 1972, 16, 243; Gerischer, H. Pure Appl. Chem. 1980, 52, 2649; Gerischer, H.; Willig, F. Top. Curr. Chem. 1976, 61, 31).

Chain chromophores described here are designed to transfer energy to the photoanod and holes away from photoanod (design II and III). This internal rectification must be made available to the preferred injection of electrons in the illuminated electrode, and the migration of the holes away from the electrode. In this case, the depletion layer contributing to charge separation that occurs on the surface of semiconductors, may not be necessary, because the relative speed of injection and recombination of charge at the interface will cause the effective energy conversion. Although the kinetic control of the dynamics of electron transfer through the boundary was proposed earlier as a practical scheme for the conversion of solar light, reported in the publications of efficiency are very low, and the photocurrents are nanoampere range (Gregg, B.A.; Fox, M.A.; Bard, A.J. J.Phys.Chem. 1990, 94, 1586). If successful, the use of metals would give the opportunity to use any conductive substrate for energy conversion. Large lot ″transparent metal″, then there is a subtle meta is symbolic of films or nets such as Au, Al or Pt, on transparent substrates are available for this application.

D. Synthetic approaches

Two different approaches are available for the preparation of linear rods AU/protective relays. One approach involves sequential synthesis, and the other approach involves the polymerization process. Both approaches use building blocks based pigments that carry a at least one, and typically two synthetic handles.

One example of a stepwise synthetic approach uses etin (E), and component units based on the iodine-substituted pigments (figure 10). Mediated by palladium (Pd) binding of iodine-substituted pigment and a bifunctional component of the block-based pigment, carrying idgruppo and trimethylsilyl-protected etin (TMSE), gives covalently-linked dimer of pigments (figure 11). Cleavage of the trimethylsilyl-protected Atina using tetrabutylammonium fluoride makes possible the second binding reaction, mediated by Pd. In this way we construct a linear architecture, starting from the far end and working your way towards the middle end. The final reaction involves the joining component protective relays. Forming unit protective relays bears the connecting group Y that is required to connect with the surface of the electrode. Taco is the same method used to prepare multiporphyrin chains, related Atina, as described here in other places.

You can imagine a large number of constituting units based pigments, as noted here and in other places. In addition, can be used multidimensional components of the blocks based on the pigments. One example includes a porphyrin dimer, carrying p-itfinally group and n-[2-(trimethylsilyl)ethinyl]phenyl group. The resulting chain for accumulation of light consists of a porphyrin dimers associated p-phenylene, which are connected together using p,p'-diphenylamino groups. The dimers of this approach to component units can be obtained by rational as shown in figure 12.

Polymerization approach is illustrated in figure 13 using the methods of linking Suzuki to connect the components of the block-based pigments. forming unit on the basis of pigment bearing carboxy group and boric ether complex attached to the solid phase resin. Currently, there are many resins; especially attractive are the Wang resin or a similar resin. The Wang resin is a resin based on cross-linked polystyrene, which makes it possible to easily attach compounds bearing carboxylic acid and removing reached which is by treating it with a weak acid in organic solvents. Linking Suzuki is carried out using a mixture of bifunctional components of the block-based pigments and the destination node and one of the well-known sets of conditions using Pd catalysts and ligands, which give high turnover and high activity. Here bifunctional component block based pigment bears a group of complex boric ester and iodine-group, while a leaf node carries only the iodine group. The polymerization is carried out in the presence of the solid phase. The distributions of the lengths of the linear rods is controlled by a ratio of bifunctional components of the block-based pigments and leaf nodes; usually used the ratio of 10:1 or so. After binding solid-phase Suzuki resin is washed to remove unreacted starting material and by-products link, then the desired product is obtained by cleavage from the resin under standard conditions. For porphyrin pigments and acid conditions removal is expected demeterova of metal, and it may be offset by subsequent metallation. Then the mixture of oligomers fractionized size using exclusion chromatography. Note that shows the synthesis comes from the host protective relays out to the far con is, causing the receiving line terminal AC/protective relays with attached functional group (in this case, carboxy), for connection to the electrode.

The same approach can be proposed for the components of the blocks on the basis of chlorine, as illustrated in figure 14. A more extensive list, illustrating other components of the blocks based on the pigments suitable for binding Suzuki, depicted in figure 15. Two noteworthy examples include forming unit on the basis of the dimer pigments and Monomeric porphyrin bearing two boron-dipyrromethene dye. Bor-dipyrromethene dyes strongly absorb in the blue-green region of the solar spectrum and very effectively transmit energy covalently attached to the porphyrin. Example of synthesis of porphyrin, carrying one iodine-group and one derived complex of boric ester, depicted in figure 16. This method uses established methods to generate dipyrromethene, acylation dipyrromethene selectively in positions of 1.9, recovery of the resulting diketone to dipyrromethene-decursinol and condensation dipyrromethene-decursinol and dipyrromethene with the formation of the corresponding porphyrin (Cho, W.-S. et al., J.Org.Chem. 1999, 64, 7890-7901). Subsequent iodination in the only free meso-position gives the desired forming unit, when odny to use when linking Suzuki.

Polymerization is not limited to linking Suzuki. An example of meso,meso-linking is illustrated in figure 17. Porphyrin with one free (unsubstituted) meso-position is attached to the solid phase, is then processed to obtain conditions meso, meso-binding (AgPF₆or similar oxidant) in the presence of a mixture of porphyrins to create a rod AC (Osuka, A.; Shimidzu, H. Angew. Chem. Int. Ed. Engl. 1997, 36, 135-137; Yoshida, N. et al., Chem. Lett. 1998, 55-56; Nakano, A. et al., Angew. Chem. Int. Ed. 1998, 37, 3023-3027; Senge, M.O.; Feng, X. Tetrahedron Lett. 1999, 40, 4165-4168). Porphyrin undergoing polymerization, has two free meso-position, and the porphyrin, which serves as the target particle has only one free meso-position. Meso,meso-linked oligomers strongly split and userauth strip, Sore and that is an attractive feature to achieve absorption across the spectrum of sunlight.

The same polymerization approach can be implemented to obtain meso,meso-linked oligomer carrying Atin at the end of the chain (figure 18). This synthesis is carried out using the new linker for attaching ethinyl porphyrin to the solid phase. After removal of substituted Atina meso,meso-linked oligomer may then be subjected to the procedure stepwise binding to attach the protective relays. An example illustrating the joining of Zirconia porphyrin-CFT is luzyanina, depicted in figure 19. Alternatively, other pigments can be attached using stepwise procedures associate before joining the protective relays. Selected molecules protective relays include a chlorin, a bacteriochlorin, phthalocyanines, naphthalocyanines or zirconium bunk sandwich molecules. The same synthetic approach is particularly attractive for use with the oligomers linked chlorin (see below).

Each of the two synthetic approaches has its advantages and disadvantages. Stepwise approach gives the oligomeric product of a given length and makes possible the inclusion of various pigments in the specified positions. However, the sequential approach requires a sufficiently large number of manipulations in the synthesis, including many cycles unprotect and binding, to obtain the desired product. polymerization approach quickly gives a linear oligomers of sufficient length. However, the oligomers obtained polydisperse, and the synthesis does not provide control over the location of the various pigments in the chain. Because of these characteristics, these two approaches have different applications.

For structures I and II, where the same pigments are used around the terminal of the speaker, can be used for polymerization approach. For structure III, where the terminals of the AC/protective relays must be defined and uniformly the length for placement between the electrode and counter-electrode, must be used the stepwise synthesis. The only exception may occur when the fractionation by size can give the desired uniformity in length, as can happen when desired are rather short oligomers, and in this case can be used in the polymerization. For structures I, II and III, where in the core the AU should be included various pigments should be used stepwise approach. May also occur in Association stepwise procedure and polymerization.

Specific examples of porphyrin macrocycles that can be used as ligands for the implementation of the present invention include the following compounds of formula X, formula XI, formula XII, formula XIII, formula XIV, formula XV, formula XVI and formula XVII (formula XII-XVII represent different chlorins, including the bacteriochlorin and usabacterial).

where:

M represents a metal, such as metal selected from the group consisting of Zn, Mg, Pt, Pd, Sn and Al, or M is absent (in this case, the ring heteroatoms K¹-K⁴replaced by H,H, required to meet conditions of neutral Valen the property);

K¹, K², K³, K⁴, K⁵, K⁶, K⁷and K⁸are heteroatoms, such as heteroatoms, independently selected from the group consisting of N, O, S, Se, Te, and CH;

S¹S²S³S⁴S⁵S⁶S⁷S⁸S⁹S¹⁰S¹¹S¹²S¹³S¹⁴S¹⁵and S¹⁶represent independently selected substituents, which are preferably provide a redox potential of less than about 5, 2 or even 1 volt. Examples of the substituents S¹S²S³S⁴include, but are not limited to, H, aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perftoran, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido and carbarnoyl.

In addition, each pair of S¹and S²S³and S⁴S⁵and S⁶S⁷and S⁸may independently form a ring arenas, such as benzene, naphthalene, or anthracene, which in turn may be unsubstituted or substituted one or more times by the Deputy, which preferably provides a redox potential of less than about 5, 2 or even 1 volt, such as H, aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxy, alkylthio, perftoran the sludge, perftoran, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido and carbarnoyl. Examples of such ring arenes include, but are not limited to:

(You can understand that all rings are properly mated to save the aromaticity of condensed rings); here each Deputy S′ is chosen independently and preferably provides a redox potential of less than about 5, 2 or even 1 volt. Examples of such substituents include, but are not limited to, H, aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perftoran, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido and carbarnoyl. Specific examples of compounds as described above containing ring of the arena below in formulas XX-XXIV.

In addition, S¹-S¹⁶may contain a linking group (-Q-), covalently linked to adjacent the porphyrin macrocycle X¹-X^m+1or linking group covalently associated with a first electrode. In one variation of the embodiment of the present invention linking group of each porphyrin macrocycle is oriented in a TRANS-position; in another variant is NTE embodiment of the present invention one or more porphyrin macrocycles contain a linking group, oriented in CIS-positions relative to each other so that the rods for the accumulation of light contain bends or kinks, or the linker itself is nonlinear or distorted.

Examples of porphyrin macrocycles that contain circular arena, as described above, include, but are not limited to, porphyrin macrocycles of formula XX, XXI, XXIII and XXIV are presented below:

where each Deputy S′ is chosen independently and preferably provides a redox potential of less than about 5, 2 or even 1 volt. Examples of such substituents include, but are not limited to, H, aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perftoran, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido and carbarnoyl. Again, to link the porphyrin macrocycle with a substrate or other compound, such as another porphyrin macrocycle, the methods described above, porphyrin macrocycle must contain at least one Deputy, and preferably two Deputy S′that is a linker (which are linkers), in particular linker containing a reactive group (when INR is estvo of linkers are substituents on the ligand, the linkers may be the same or independently selected). Such linkers described above.

Specific examples sandwich coordination compounds, which can be used when implementing the present invention have the formula XXV (bunk sandwich compounds):

where:

M¹is a metal from a number of lanthanides and Y, Zr, Hf, Bi, and in some actinides Th and U (radioactive elements, such as Pm, as a rule, are less preferred);

L¹and L²are independently selected ligands (e.g., porphyrin macrocycles); and

Q¹and Q²may be present or absent, and when present, they are independently selected linkers described above (the linker preferably comprises a protected or unprotected reactive group, such as tio, selenium or tellura-group). Preferably there is at least one element of Q¹or Q².

You can also understand that each ligand L may be substituted by one individual linker Q or may be repeatedly replaced by linkers Q, as explained in more detail below. Thus, the molecule of formula XXV can be covalently associated with the electrode or the substrate with at least the underwater of Q ¹or Q².

Each ligand L may optionally be substituted without deviating from the scope of the compounds of formula XI above. For example, as explained in more detail below, the ligands can be covalently linked to other the porphyrin macrocycle, with another ligand sandwich coordination compounds and the like.

To link the porphyrin macrocycle (which may or may not be a component of the sandwich coordination compound) with a substrate or with another compound such as another porphyrin macrocycle, the methods described above, at least one ligand in the porphyrin macrocycle must contain at least one, and preferably two Deputy S¹-Sⁿor S′, which represents a linker, particularly a linker containing a reactive group (where multiple linkers are substituents on the ligand, the linkers may be the same or independently selected). Such linkers are denoted here as Y-Q-, where Q is a linker, and Y represents a substrate, an active position or group that can covalently to contact the substrate, or an active position or group, which may be ionic contact with the substrate.

Q can represent a linear linker or skewed linker, with linear linkers at the present time the I are preferred. Examples of skewed linkers include, but are not limited to, 4,3′-diphenylamin, 4,3′ -diphenylbutadiyne, 4,3′-biphenyl, 1,3-phenylene, 4,3′-stilbene, 4,3′-azobenzene 4,3′-benzylideneaniline and 4.3′′-terphenyl. Examples of linear linkers include, but are not limited to, 4,4′-diphenylamin, 4,4′-diphenylbutadiyne, 4,4′-biphenyl, 1,4-phenylene, 4,4′-stilbene, 1,4-bicicletta, 4,4′-azobenzene, 4,4′ -benzylideneaniline, 4,4′′-terphenyl, 3-mercaptophenyl, 3-mercaptoethanol, 3-(2-mercaptoethyl)phenyl, 3-(3-mercaptopropyl)phenyl, 3-(2-(4-mercaptophenyl)ethinyl)phenyl, 3-carboxyphenyl, 3-carboxymethyl and the like.

Y can be a protected or unprotected active reactive position or group on the linker, such as tio, selenium or tellaro group.

Thus, examples of linear linkers for Y-Q - are: 4-[2-mercaptoethyl)phenyl, 4-[3-mercaptopropyl)phenyl, ω-alkylthiol form HS(CH₂)_n-, where n=1-20, 4-carboxyphenyl, 4-carboxymethyl, 4-(2-carboxyethyl)phenyl, ω-alkalicarbonate acid in the form of HO₂C(CH₂)_n-, where n=1-20,

4-(2-(4-carboxyphenyl)ethinyl)phenyl,

4-(2-(4-carboxymethyl)ethinyl)phenyl,

4-(2-(4-(2-carboxyethyl)phenyl)ethinyl)phenyl,

4-(2-(4-mercaptophenyl)ethinyl)phenyl, 4-mercaptomethyl, 4-hydrosaline Anil, 3-(2-(4-hydrosalinity)ethinyl)phenyl, 4-hydrocalumite and 4-(2-(4-hydrocalumite)ethinyl)phenyl.

Examples of skewed linkers for Y-Q - are: 3-(2-(4-mercaptophenyl)ethinyl)phenyl, 3-mercaptoethanol, 3-hydrosalinity, 3-(2-(4-hydrosalinity)ethinyl)phenyl, 3-hydrocalumite and 3-(2-(4-hydrocalumite)ethinyl)phenyl; and the like.

Other suitable linkers include, but are not limited to, 2-(4-mercaptophenyl)ethinyl, 2-(4-hydrosalinity)ethinyl and 2-(4-hydrocalumite)ethinyl.

Thus, the linkers between adjacent the porphyrin macrocycles inside the rod for the accumulation of light or between the porphyrin macrocycle and the electrode, as a rule, are such as to make possible surhomme link between the chromophores (indirect message of electrons between the chromophores, which enables or permits the transfer and/or exchange energy of the excited state of electrons and/or holes). Examples of suitable linkers can in General be represented by the formula-Q-, where Q may be a direct covalent bond or linking group of the formula:

where:

n is 0, or 1 to 5, or 10;

R³may or may not be present (giving a direct covalent bond when R³absent and n is 0); and

R¹, R²and R³are, each independently, selected from the group consisting of Athena, Atina, aryl and heteroaryl groups (for example, phenyl, and derivatives of pyridine, thiophene, pyrrole, phenyl and the like, and these aryl and heteroaryl groups can be unsubstituted or substituted one or more times, the same substituents as listed above in connection with the porphyrin macrocycles).

The geometry of the linkers in relation to different chromophores and groups of charge separation in the rods for the accumulation of light can change. In one variant embodiment, at least one of X²-X^m+1contains meso-linked porphyrin macrocycle. In another variant embodiment, at least one of X²-X^m+1contains TRANS meso-linked porphyrin macrocycle. In another variant embodiment of the X²-X^m+1consist of meso-linked porphyrin macrocycles. In another variant embodiment of the X²-X^m+1consist of TRANS meso-linked porphyrin macrocycles. In another variant embodiment, at least one of X²-X^m+1contains β-linked porphyrin macrocycle. In another variant embodiment, at least one of X²-X^m+1contains TRANS β-linked porphyrin macrocycle. In another variant embodiment of the X²-X ^m+1consist of β -linked porphyrin macrocycles. In another variant embodiment of the X²-X^m+1consist of TRANS β-linked porphyrin macrocycles.

E. Examples of structures

Examples of specific molecules that can be obtained in various designs presented in the following diagrams. The example design I is depicted in figure 20. Zn-porphyrins are the core of the AU, and Mg-porphyrin is protective relays. The energy transfer is reversible between Zn-porphyrins, but is irreversible (in the deeper potential pit) to Mg-porphyrin (Hascoat, P. et al., Inorg.Chem. 1999, 38, 4849-4853). In this construction each of the Zn - and Mg-porphyrins has identical neisvaziuosiu meso-substituents. When splitting the charge hole remains on the Mg-porphyrin. The hole cannot move to the Zn-porphyrins as Mg-porphyrin is at a lower potential than that of Zn-porphyrins (Wagner, R.W. et al., SoC. 1996, 118, 3996-3997). The oxidation potential protective relays can be selected by changing the inductive effects of two nesvezhih meso-substituents. By replacing nesvezhih meso-substituents on Zn-porphyrins, again, the hole is forced to stay on the Mg-porphyrin (protective relays). The example design II is depicted in figure 21. This design is similar to the one depicted in figure 19, but neisvaziuosiu meso-substituents Zn - and Mg-porphyrins are different. Strongly discharging electrons substituents are placed on the Mg-porphyrin (protective relays), but not Zn-porphyrins. As a consequence, the injection of an electron in the electrode hole on protective relays is transferred to the Zn-porphyrins in chain AC. Transfer holes is advantageous, since Zn-porphyrins are at a lower potential than that of Mg-porphyrin.

Related sample design II is depicted in figure 22. Here the linear rod AC consists of a series of m Pereladova components and the number of n Zn-porphyrins, and protective relays consists of Zn-chlorin. Energy flows irreversibly from a set of perylene to the Zn-porphyrin and Zn-chlorin. A hole formed in the protective relays during the injection of an electron in the electrode migrates to the Zn-porphyrins with lower potential but may migrate to the number of perylene. This number is synthesized using a constituent unit based on perylene, carrying etin and iodine-group, similar to the components of the blocks based on the porphyrin.

Additional examples illustrating the structures I and II, shown in figures 23 and 24. Here in the rod AC is used β,β'-substituted chlorins, and zirconium bunk porphyrin-phthalocyaninato sandwich molecule serves as protective relays. Zirconium bunk porphyrin sandwich molecules, are known to be photochemically active. The synthesis involves linking with Suzuki coord is m rod ACE of chlorine, the associated p-phenylene, which uses the linker to attach etina the solid phase. Upon cleavage from the solid phase and removing the protection ethinyl-substituted terminal speakers can be attached to zirconium bunk molecule using indirect Pd reaction etiolirovaniya. Zirconium bunk molecule can be obtained using known methods, using the desired TRANS-substituted porphyrin. Choosing the types of substituents in the porphyrin and phthalocyaninato components bunk molecules can be chosen according to the desired oxidation potential. In the absence of electron releasing substituents oxidation potential is very low, and the hole (formed by injection of an electron in the electrode) remains protective relays (design I). When deputies selecting an electron (for example, when R=F or perfluoroalkyl; Ar¹=Ar²=perfluoroalkyl or pentafluorophenyl), the oxidation potential is increased, and the hole migrates to the Zn-chlorines in terminal AC (design II).

The example design III is depicted in figure 25. Rod AC consists of a number of metalloboranes. The linker for attachment to the electrode is a derivative of benzoic acid as a linker to join the counter-electrode is thioacetate. Such S-acetyl-protected thiols are split with with the Prikosnovenie with a strong base or in contact with the electrochemically active surfaces, such as gold (Gryko, D.T. et al., J.Org.Chem. 1999, 64, 8635-8647). Components AC and protective relays are designed to facilitate the migration of holes from the protective relays to the far end, where the connection to the counter-electrode.

Another type of pigment that can be used in these constructions is bacteriochlorin. The bacteriochlorin strongly absorb in the blue region, like porphyrins, but also strongly absorb in the near infrared region, but also throughout the visible region (for example, tetraphenylethylene, ε_Nm=160000 M^-1cm^-1that ε_Nm=160000 M^-1cm^-1,

ε_Nm=130000 M^-1cm^-1)(Whitlock, H. W. et al. SoC. 1969, 91, 7485). The structure of the linear rod AC, consisting of bacteriochlorin depicted in figure 26.

F. a comparative discussion of architectures and internal straightening

A very attractive feature of structures II and III is that the sequence of pigments in the rods for the accumulation of light causes irreversible flow of energy from the absorption of protective relays. Modeling shows that such energy gradients provide the dramatic increase in quantum efficiency for excitation energy reaching the trap (in this case, site of charge separation) (Van Patten, P.G. et al., J.Phys.Chem. B 1998, 102, 4209-4216). Additional features : the capacity of the structure III, the hole (formed in the protective relays) proceeds irreversibly by a hopping mechanism of migration of holes from protective relays in a counter-electrode. The appropriate choice of pigments makes the rod AU possible irreversible energy flow and holes in opposite directions. Linear rods, which allow for the flow of energy and holes in opposite directions, are ideally suited for incorporation in ultrathin solar cells described here.

The phenomena described above, enable these structures for internal rectification. Internal rectification may include (i) the irreversible flow of energy or electrons of the excited state along some portion or the entire length of the rod to the accumulation of light, (ii) the irreversible flow of holes along some portion or the entire length of the rod to the accumulation of light, or (iii) both (i)and (ii) above, with holes and energy or electrons move in opposite directions.

For irreversible migration energy (internal straightening energy or electrons), the rod for the accumulation of light should have such a structure that the E^*(X¹)<E^*(x²)<E^*(x³)...<E^*(Xⁿ), where E^*(Xⁱ) represents the energy of the excited state of i-chromophore components the NTA X.

For irreversible migration of holes by a hopping mechanism (internal straightening holes) terminal for accumulation of light should have such a structure that the E_1/2(X¹) > E_1/2(X²) > E_1/2(X³)... >E_1/2(Xⁱ), where E_1/2represents the value elektrokhimicheskogo oxidative capacity in some mid-point for the i-th chromophore component X.

Although the chromophores rods for accumulation of light can be isoenergy, the condition of internal rectification, as described above, is preferred. However, the internal straightening should not occur around the rod to the accumulation of light, and even should not be provided near the site of charge separation. For example, one or more isoenergy chromophores may be present near the site of charge separation and the internal straightening holes and/or energy can occur anywhere inside the rod for the accumulation of light, for example, in the middle or the far segment. Thus, the term ″internal straightening″ energy of the excited state of the holes and/or electrons by a rod to the accumulation of light refers to the internal straightening, which occurs along any segment or part of the specified terminal for accumulation of light.

G. Fabrication of the solar cell

OS is the establishment of linear molecules AU/protective relays on the electrode is accomplished by interaction of the electrode with a solution of molecules AU/protective relays, with the subsequent washing to remove any unbound particles. May be homogeneous or heterogeneous deposition. There may be deposited a homogeneous population of molecules or can be used a mixture of molecules AU/protective relays. One advantage of the latter procedure is that can be used molecules with different components in the chain as, for overlapping the entire spectrum of sunlight. Different types of chains AU include, but are not limited to, the following: a chain of all-chlorin, bacteriochlorin, porphyrin+phthalocyanine, meso, meso-linked porphyrins, perylene+porphyrin. Mixtures of these types of chains speakers can be used in a solar cell to ensure the effective overlap of the entire spectrum of sunlight. In this way, it is not important that each terminal of the AC/protective relays provided for the full overlap of the entire spectrum of sunlight.

Solar elements such as photovoltaic, can be made by positioning the site of charge separation away from the electrode surfaces. The incorporation of the driving force for electron transfer to the anode and the driving force for the migration of holes to the cathode should lead to efficient energy conversion. A potential advantage of this approach is that the accumulation of light and nutrimedical the RNA the charge transfer will occur at some distance from the surfaces of the electrodes, thereby minimizing harmful side interaction of excited States and the electrode, such as the quenching of the excited state.

III. Building BLOCKS ON the BASIS of CHLORINE TO CREATE

CHAINS FOR ACCUMULATION of LIGHT

A. Introduction

Chlorins have three advantages compared with porphyrins in use for the collection and use of sunlight. (1) Chlorins strongly absorb in the blue region and the red part of the visible region (green), effectively converting a large part of the spectrum of sunlight, while porphyrins strongly absorb only in the blue region (due to their red color). (2) the Transition dipole moment in the long wavelength absorption of the chlorine is linearly polarized along the axis N-N, giving increased focus to energy transfer to neighboring pigments through space. In contrast, in the metal of the transition dipole moment of area of the long wavelength absorption lies in the plane of the macrocycle, effectively localized along both axes N-N (planar oscillator), and for this reason there is less focus energy transfer. (3) the Chlorines are oxidized more easily than the porphyrins, and for this reason are best photovoltaically.

Was recently described method of synthesis, which is in charge of the AET access to a new set of components of the blocks on the basis of chlorin (Strachan, J.P. et al., J.Org.Chem. 2000, 118, 3160-3172). Building blocks based on chlorine demonstrate typical chlorine absorption spectra and fluorescence. Building blocks on the basis of chlorin have substituents (functional pen) in two of the meso-positions, and no one in β-positions (figure 27). In previous studies of energy transfer in multiporphyrin chains, there are several facts relevant to the design of pigments for inclusion in chains for accumulation of light, consisting of covalently-linked pigments: (1) the process of energy transfer involves the transfer mechanisms through space (TS)and through communication (TB), and the observed rate of energy transfer is the sum of these two processes (Hsiao, J.-S.; et al., SoC. 1996, 118, 11181-11193). (2) the Rate of TB-energy transfer depends on the nature of the molecular orbitals of the donor to the energy acceptor energy and linker linking the donor and acceptor (Strachan, J.P. et al., SoC. 1997, 119, 11191-11201; Yang, S.I. et al., SoC. 1999, 121, 4008-4018). In particular, a wider distribution of the electron (and a higher speed of transfer) occurs when attaching a linker in the areas of donor and acceptor, where adjacent molecular orbitals have high electron density compared to areas of low electron density. As a clarification, in the porphyrin, and iusem a _2uHOMO (which has electron density mainly in the meso-positions and very little in β-provisions), higher speed (2.5-10-fold) observed for linkers in meso-and not in β-positions (figure 28). Similarly, in the porphyrin having a_1uHOMO (which has electron density mainly in the β-the provisions of, and very little, if at all, in the meso-positions), higher velocities are observed for linkers rather β-than in the meso-positions.This difference in velocity is associated with each stage of the energy transfer from pigment to pigment in the linear Multisegmented chains, and it manifests itself as a great influence on the overall rate and output energy transfer (Van Patten, P. G. et al., J.Phys.Chem. B 1998, 102, 4209-4216).

Factors that affect TS-energy transfer (mechanism Forster), is well known. Two key determinants are the power oscillator to the donor in the excited state (reflected in the rate of radiation for the transition into the state of lowest energy) and the power oscillator to the acceptor in the ground state (reflected in the molar absorption coefficient for the transition with the lowest energy). Chlorins are ideal candidates for TS-energy transfer due to their large power oscillator for far-field absorption, especially if cf is univali with porphyrins, with their low power oscillator (i.e. a weak absorption in the red region. Another key determining factor includes the orientation of the transition dipole moments of donor and acceptor. Orientation member (κ²for TS energy transfer by Forster takes the values 0 (orthogonal), 1 (parallel but not collinear) and 4 (collinear) depending on the orientation vectors of the transition dipole moments. The most efficient energy transfer is carried out in such a mutual arrangement of the molecules, when the transition dipole moments of donor and acceptor are collinear, and the least efficient transfer occurs at orthogonal orientations (Van Patten, P.G. et al., J. Phys. Chem. B 1998, 102, 4209-4216).

Predictions related to the energy transfer properties of chains containing chlorins can be summarized. In related diphenylamino multiporphyrin chains (meso-linked, a_2uHOMO) observed the rate of energy transfer from the zinc porphyrin to the porphyrin in the form of a free base, as found, is (24 psec)^-1while the contribution of the TS-migration is (720 psec)^-1and TB migration (25 psec)^-1. For chlorine, the rate constant of radiation increases ˜4 times, and the molar absorption coefficient increases ≥10 times compared with porphyrins. R is smotrina inclusion of chlorine in the ideal geometry for wrapping Forster with the same intermediate diphenylamino linker causes that orientation member (κ²should be up to ˜2 compared with 1,125 for porphyrins. The net effect is expected to increase up to 100 times the speed of TS energy transfer chlorine compared with porphyrins. The rate of TB-migration chlorines are difficult to assess, but it must fall within the range observed for porphyrins, which is in the range from (25 psec)^-1to (360 psec)^-1depending on the density of orbitals in the area of attachment of linker. TS-migration for chlorine should be 40-100 times more rapid than for porphyrins (that is, from (18 psec)^-1to ˜(7 psec)^-1). Accordingly, the expected rate of energy transfer from one chlorin to the other must be in the range of ˜(10 psec)^-1to ˜(20 psec)^-1.

In the transition from multiporphyrin chains linked by diphenylamino, chains, associated p-phenylene, the observed rate of energy transfer increases from (24 psec)^-1up to (2 psec)^-1. During the transition to p-venelinova the linker for chlorins shorter distance should cause ˜100-fold increase in the contribution TS into speed. In this case, TS is the predominant mechanism over speed TB. Accordingly, the speed of energy transfer from chlorine to chlorine in the chain, the associated p-phenylene, expected to be in sub-picoseconds the ohms range for chlorine, substituted as in meso-and β-provisions.

These rough calculations illustrate that the chlorines, as expected, have a great TS-component observed in the process of energy transfer in multicarinata chains. A higher rate of energy transfer to chlorine compared with porphyrins in combination with excellent spectral properties (i.e. absorption in the blue and red areas) chlorine compared with porphyrins give a strong impetus to construct chains for accumulation of light containing chlorine. Considered as building blocks on the basis of meso-substituted chlorin, and building blocks based on β -substituted chlorin.

B. Molecular design

Here presents the components of the blocks based on the chlorine, designed to obtain efficient energy transfer chains for accumulation of light containing chlorine. The objectives are: (1) preparation of chlorins with two functional handles so that the chlorine could easily be included in a linear chain, (2) design components of the blocks on the basis of chlorine to obtain the highest possible value orientation member for TS-energy transfer, and (3) that they were connected properly to obtain the most extensive process TB-energy transfer. That represents the t of the best areas on the chlorin to attach the linker? Four possible TRANS-substituted chlorin depicted in figure 29. Two β,β'-substituted chlorin depicted as two chlorin, each of which bears two meso-substituent. To assess the components of the blocks on the basis of chlorine should be considered: (1) steric effects of any substituents, (2) the orientation of the transition dipole moment for the long-wavelength transition, and (3) the composition of the frontier molecular orbitals.

The four study components of the blocks on the basis of chlorine in the figure 29 proves steric restrictions in the chlorin IV due to the interaction of meso-substituent adjacent to the side of the dual methyl groups of the ring D. the Other three chlorine I-III do not have such steric interactions, so they are superior to IV in this regard.

The transition dipole moment for the transition in the far red region polarized in the chlorines along the axis N-N, perpendicular to the recovered ring (D) and intersecting rings A and C, but not rings B and D (figure 30). Assessment of all four possible TRANS-chlorines, depicted in figure 29, requires consideration of the geometries obtained when covalently linked chains. The pair interaction is depicted in figure 31, where definiately linker is used to connect chlorins (other linkers, including p-fenelonov group, can also be used). For meso-related chlorins κ²por the terms of the boundary values of 0.25 and 2.25 depending on orientation. Assuming free rotation for the life time of the excited state (dynamic averaging), the average value of the κ²is 1,125. Note that free rotation is expected around a cylindrically symmetric Atina, but the speed may be insufficient to make all the molecules go through all conformations within a few nanoseconds lifetime of the excited state. Thus, molecules that are in orientation, characterized by the value of κ²equal or close to zero, will not cause effective TS-energy transfer. β,β'-Substituted chlorins have boundary values κ²˜1,6, and this value is >1 regardless of the dihedral angle around Edinboro linker. (Note that in this case the distance between the centers slightly varies during rotation around Edinboro linker.) Thus, β,β'-substituted chlorins have a slightly better collinearity of the transition dipole moment with the axis of substitution (which should be linear axis of multicarinata chain)than obtained for meso-substituted chlorins. In the end, building blocks on the basis of chlorin I and II are slightly more preferable compared to III and IV for the TS-energy transfer.

The highest populated molecular orbital of chlorine t is aetsa orbital of a ₂that puts the electron density in each of the meso - and β-positions (figure 32). Accordingly, it is difficult to assess the relative strengths of the meso-positions compared to βpositions for attachment of the linker in relation to effective TB-energy transfer. In the absence of such knowledge β-substituted chlorins and meso-substituted chlorins, as expected, have a comparable suitability for use. In any case, since the distance separating the ring becomes very short, TS-mechanism will prevail, and TB-mechanism will make a relatively small contribution to the observed velocity. The main drawback of meso-substituted TRANS-chlorins derived from the possible deformation of the macrocycle due to the steric perezagruzhennosti when partially saturated ring. The TRANS-configuration can be achieved when connecting rings A and C. Comparing the four possible TRANS-chlorin depicted in scheme 4, in relation to TB-energy transfer, you can see that meso-substituted chlorins (III, IV) are the worst compared to β,β'-substituted chlorins (I, II).

In the end, building blocks on the basis of chlorin I, II, and III are suitable for construction of chains for accumulation of light. From the viewpoint of synthesis of the constituting unit based on the chlorine I can be obtained easier than II. Note that the previous is the first set of components of the blocks on the basis of chlorin, received, provides the typical properties of the absorption of chlorine, but is not suitable for linear chains, because they have a synthetic handles in two adjacent (CIS) meso-positions instead of two TRANS meso - or β-positions (figure 27). In contrast, chlorins I and II are the ideal components of synthetic chains for accumulation of light and should provide high speed transfer.

C. Synthesis

Synthesis β-substituted components of the blocks on the basis of chlorine (class I) follows the General method established previously for the preparation of meso-substituted chlorins, as discussed above. In this way the Eastern half and the Western half are subjected to condensation, and then oxidative cyclization of obtaining chlorine. The same approach is used here for the new Eastern half and Western new halves, each of which bears one β-Deputy (figure 33).

Synthesis of a new β-substituted Eastern half is depicted in figures 34A and 34B. The synthesis, which is built on well-known from the literature work on developing ways to β-substituted components blocks porphyrin (Balasubramanian, T.; Lindsey, J. S. Tetrahedron 1999, 55, 6771-6784), described below in example 1.

Synthesis of a new β-substituted Western half is depicted in figure 35. This method begins with that is about the same critical intermediate compounds, which is used for the Eastern half, 2-formyl-3-arylpyrol (figure 34A). Then the Western half is prepared, following the same sequence of reactions, which is used for unsubstituted Western half. The last method is in the process of research.

Component block based on chlorine, depicted in figure 33, bears a single 4-(TMS-ethinyl)phenyl group and 4-itfinally group. This particular component unit should make possible the synthesis of related diphenylamines containing chlorine chains in a linear architecture. Other components of the blocks based on the chlorine, which can be obtained by using the same synthetic strategy and which have the same desirable physical properties, depicted in figure 36.

The synthesis of the components of the blocks on the basis of TRANS meso-substituted chlorin (type III) are obtained in two ways. One way involves spreading method, installed recently, for the preparation of chlorine, bearing adjacent (CIS) meso-substituted chlorins (figure 27) (Strachan, J.P. et al., J.Org.Chem. 2000, 118, 3160). Treatment of CIS-meso-substituted chlorin using NBS (DiMagno, S.G. et al., J.Org.Chem. 1993, 58, 5983-5993), as expected, gives a selective bromination, as shown in figure 37. Alternatively, it may be iodination using iodine and AgPF (Nakano, A. et al., Tetrahedron Lett. 1998, 39, 9489-9492). Woodward showed that the two provisions Metin attached to the side of the ring D, are highly reactive toward electrophilic reagents (Woodward, R.B.; Skaric, V.J.Am.Chem. Soc. 1961, 83, 4676-4678). Position between rings A and D is sterically difficult due paired methyl substituents, which should be sufficient for selective engagement in the provisions of the Metin between rings D and C. Then the following indirect Pd cross-linking (DiMagno, S.G. et al., J.Org.Chem. 1993, 58, 5983-5993) gives the desired TRANS-substituted (Ar², Ar³) constituting unit based on chlorine.

The second way of obtaining TRANS meso-substituted components of the blocks on the basis of chlorine (type III) is depicted in figure 38. prepare the new Western half, which bears attached to a partially saturated ring Deputy, which is designed to be relevant meso-Deputy.

Various meso-substituted building blocks based on chlorine, which can be obtained in this way and which are suitable for use when synthetic pathways for the accumulation of light, depicted in figure 39. You may notice that the deputies, who should be used as the aryl units (Ar), can be used in owani to adjust the value of the electrochemical potential, for the purposes of solubility or to control the packing of the chains for accumulation of light in self-assembled structures.

For all components of the blocks on the basis of chlorine can be used in numerous metals, provided that the metals meet the requirement for photochemically active excited state. Preferred variants of such metals are Zn, Mg, Pd, Sn, and Al. Can also be used chlorine free base (M=H,H). When used in the synthesis reaction of formation of chlorine gives the zinc-chlorine, which is easily demetallised using a weak acid with obtaining chlorine free basis. The desired metalochlor can then be obtained using well-known reactions of metallation.

IV. OPPOSITELY DIRECTED STREAMS of ENERGY of the EXCITED STATE AND HOLES IN the ground STATE IN the CHAINS FOR ACCUMULATION of LIGHT

A. Introduction

The sunlight is weak, and in this lies one of the main problems in the development of effective tools to use sunlight as an energy source. The strategy used by photosynthetic organisms, is the absorption of sunlight by using Multisegmented antenna complexes, and then in the direction of the resulting energy of the excited state between the p is gentami thus, the excitement reaches the reaction center (i.e. the site of charge separation). In the reaction center is a reaction of charge separation, giving the recovery equivalents (electrons) and oxidation equivalent (the hole). In plants reducing and oxidising equivalents ultimately used to recover carbon dioxide with the formation of carbohydrates) and oxidation of water (with the release of oxygen), respectively. Thus, electrons flow from the reaction center and to the reaction center (filling the hole formed due to charge transfer). For this reason, the reaction center must have three channels: a channel for the flow of excitation energy from the antenna, the channel for the emission of electrons after the separation of charge and the entry channel of electrons intended for the regeneration reaction center after the separation of charge (figure 40). Note that the flow of electrons inside and migration of holes to the outside are equivalent processes, and these terms are used as synonyms.

From the point of view of the size of the antenna complexes are far superior to the reaction centers. While chlorophyll molecules contained in the antenna complexes and reaction centre, the bulk of the chlorophyll is located in the antenna complexes. For example, in the reaction center fotosintesis the soup bacteria are, typically, about six molecules of chlorophyll or chlorophyll compounds), while in the antenna complexes can contain up to several hundred chlorophyll molecules. Antenna systems are used to collect the scattered light and reaction centers initiate energy transfer of the excited state in chemical fuel through stable state with separated charge.

Generation of stable separated charges in the reaction center includes a number of stages of electron transfer along a series of electron acceptors. At each stage of the overall return rate of electron transfer (i.e. recombination) becomes slower. After three stages of the ratio of the velocities of the initial stage of the forward transfer (k_f) and the recombination rate (k_recomb) is the k_f/k_recomb˜10⁶. A number of fast breaks forward and slow reverse transfers provides fast and efficient separation of electrons and holes at a great distance.

Many attempts have been devoted to the development of synthetic antenna molecules and synthetic nodes of charge separation (i.e. the equivalent of the reaction center). In General, all antennas, received to date, contain 10 or fewer pigments (Li, J.; Lindsey, J. S. J.Org.Chem. 1999, 64, 9101 -9108). Designed and other molecules, which create small is nanny, attached to the site of charge separation (protective relays) (Kuciauskas, D. et al., SoC. 1999, 121, 8604-8614). These molecules have demonstrated effective accumulation of light (i.e. the light absorption and energy migration) and the effective charge transfer. Mostly synthetic antenna, protective relays and integrated antenna system-protective relays have been studied in solution. Such studies can provide in-depth understanding of the mechanisms and properties, but rarely solve problems related to the organization of the Assembly of antennas for the accumulation of light and protective relays, as this should be done when designing any practical system for use with sunlight.

Should be designed and synthesized chains for accumulation of light, which absorb light and undergo efficient intramolecular energy transfer. Examples of such molecules is depicted in figure 41. With diphenylamino linker rate of energy transfer from the zinc porphyrin to the porphyrin free base is (24 psec)^-1. With p-phenylenebis linker rate of energy transfer from the zinc porphyrin to the porphyrin free base is (2 psec)^-1. To probe the role of the linker when mediating energy transfer of the excited state between the porphyrins investigated the electrochemical properties of these multiporphyrin chains. Electrochemical potentials of the Indus the individual pigments are retained for inclusion in the chain. However, the hole formed in multiporphyrin chain is delocalized, as determined by analysis by EPR. The rate of migration of holes by a hopping mechanism between porphyrins in the chain in a liquid solution is higher than that which can be detected using EPR techniques that involves a rate of > 10⁷s^-1(Seth, J. et al., SoC. 1994, 116, 10578-10592; Seth, J. et al., SoC. 1996, 118, 11194-11207). These studies show that there is considerable interaction between the electron ground state in multiporphyrin chains and that the interaction must be mediated by using a linker that connects the porphyrins. As a result, multiporphyrin chains have the desired characteristics of light absorption and migration energy of the excited state, which are important for efficient accumulation of light, and in addition possess the unexpected property of facilitating the migration of holes by a hopping mechanism in the ground state during the formation of the oxidized complexes.

B. Design of linear chains

One of the challenges when designing solar cells involves the integration of various components, which include the antenna, protective relays, and ways for the flow of electrons from the protective relays to him. It provides new tools for re is edenia oxidizing equivalent away from the site of charge separation. Basically the antenna is constructed in such a way that energy flows along the chain for the accumulation of light to the site of charge separation, while oxidizing equivalent (hole) flows in the opposite direction from protective relays to position the antenna where there may be subsequent reactions of electron transfer (figure 42). This design has two significant varieties. (1) for access to protective relays require only two channels: one for the emission of electrons and one where the excitation energy flow, and oxidative equivalents (holes) flow (figure 43). The existence of two channels instead of three eases constraints on the organization of antennas for accumulation of light around protective relays in 3-dimensional packaging. (2) the Migration of holes away from the site of charge separation leads to stabilization of the separated state of charge. The vast majority of approaches developed for the stabilization of the separated state of the charge in synthetic systems focus on the use of a number of electron acceptors to move electrons away from the hole. A similar approach (described here) uses the number of acceptors of holes to move the holes away from the electron, and thereby to obtain the steady state divided by the charge.

Porphyrin molecules are Central to this design. Porphyrins strongly absorb the light and d is jut a stable cation radicals during oxidation. A characteristic feature of porphyrins is that the nature of the substituents, electron discharging or releasing an electron attached to the porphyrin, causes corresponding changes in elektrokhimicheskikh potentials of porphyrins, but does not alter significantly the absorption spectra of the porphyrins (Seth, J.; Palaniappan, V.; Wagner, R.W.; Johnson, T.E.; Lindsey, J.S.; Bocian, D.F. SOC. 1996, 118, 11194-11207). Therefore, elektrokhimicheskie potentials of porphyrins can be adjusted without changing the energy levels, which play a role in the migration energy. In other words, the substituents shift the energy levels as HOMO and LUMO, causing changes accordingly in the oxidation and reduction potentials. absorption spectrum depends on the difference between the energies of HOMO and LUMO; if both HOMO and LUMO are shifted equally, any change in the forbidden zone HOMO-LUMO not observed, and therefore the absorption spectrum remains unchanged. The ability to adjust the oxidation potential without affecting the absorption spectrum makes possible the design of cascades with the transfer holes, at the same time maintaining associated with the energy transfer properties of the chains. Careful selection of pigments with different absorption spectrums in combination with structural modifications for electrochemical adjustment allows energy and holes to flow into the region with the smaller p is potential energy in opposite directions.

The following examples illustrate the opposite flow of excitation energy and holes in the ground state. On the figures 44-49 diagram of the energy levels are illustrative.

(1) a Linear chain zinc porphyrins that bear different meso-substituents (figure 44). All four porphyrin are essentially identical absorption spectra, therefore, the energy migration takes place between four isoenergy the porphyrins. The energy transfer is reversible between all four porphyrins. Electrochemical potentials are in cascade, the highest potential is close to protective relays, and the lowest potential is far from protective relays. For this reason, the migration of holes occurs irreversibly moves from high to low potential.

(2) a Linear chain of Mg - and Zn-porphyrins that bear different meso-substituents (figure 45). Mg-porphyrins absorb at slightly greater wave length (˜5-10 nm)than Zn-porphyrins, and easier to oxidize (i.e. have a lower potential)than Zn-porphyrins (Li, F. et al., J. Mater. Chem. 1997, 7, 1245-1262; Hascoat, P. et al., Inorg.Chem. 1999, 38, 4849-4853). The sequence Zn, Zn, Mg, Mg when moving towards protective relays leads to a reversible energy transfer between the two isoenergy Zn-porphyrins, irreversible migration of energy from Zn - Mg-porphyrin and reversible lane the nose of energy between the two isoenergy Mg-porphyrins. Although Mg-porphyrins are oxidized more easily than Zn-porphyrins (with identical substituents), placing highly discharging electrons substituents on Mg-porphyrins and releasing electrons substituents on Zn-porphyrins causes circulation of the order of oxidation potentials (Yang, S.I. et al., J. Porphyrins Phthalocyanines 1999, 3, 117-147). For linear chains of porphyrins shown in figure 45, the location of such substituents creates a cascade from the high potential near protective relays to a low potential away from protective relays. Thus, this system creates a cascade with a smooth transition for the migration energy and a stepped cascade for migration of holes in the opposite direction.

(3) a Linear chain of metalloboranes, bearing different meso-substituents (figure 46). Chlorins strongly absorb in the blue and red areas, effectively blocking a large part of the spectrum of sunlight. Chlorins are members of the family of porphyrins (i.e. cyclic tetrapyrrole). As porphyrins, elektrokhimicheskie potentials of chlorins change rational and predictable way in the presence of the discharging electron or electron releasing substituents. However, the absorption spectra are essentially not affected by the inductive effects of the substituents. Thus, the location of the chlorines in a linear chain leads to arr is a valid migration of energy between isoenergy pigments, but to irreversible transfer of holes when you move away from the protective relays.

(4) a Linear chain of porphyrins and chlorins, bearing different meso-substituents (figure 47). Band long-wavelength absorption (and hence the energy of the excited singlet state) of the metal falls into the region of shorter wavelengths (higher energies)than the band corresponding metallothionine. On the other hand, the chlorine easier oxidized (lower potential)than the corresponding metal. The energy cascade and the cascade of holes can be created this way, as shown in figure 47. Strongly discharging electrons deputies used in conjunction with chlorine, and releasing electrons deputies used together with porphyrins, shifting the chlorines to a higher potential than that of the porphyrins. Reversible energy transfer is performed between a pair of porphyrins, irreversible transition is effected from the porphyrin to the chlorine, and reversible transfer is carried out between a pair of chlorines. Reversible transfer of holes is carried out between a pair of chlorins with subsequent irreversible transfer of holes from chlorine to porphyrin and again from the porphyrin to the porphyrin.

(5) a Linear chain of β-substituted chlorins and meso-substituted chlorins (figure 48). β-Substituted chlorins, which are currently the time not bear the third Deputy to adjust elektrokhimicheskogo potential, as do the meso-substituted chlorins. In addition, β-substituted chlorins can fruitfully be incorporated, as shown in figure 48. This location gives a reversible energy migration and cascading the process of moving holes. Note that the chlorines can be located with a partially saturated ring, located towards the protective relays or from him; different orientations presented in figure 48, is not called no differences in performance.

(6) the Linear chain of the porphyrin, chlorin, and phtalocyanines components (figure 49). Phthalocyanines are characterized by a very strong absorption in the red range (ε˜250000 M^-1cm^-1) and high oxidation potentials (Li, J. et al., J.Org.Chem. 1999, 64, 9090-9100; Yang, S.I. et al., J.Mater.Chem. 2000, 10, 283). Chain depicted in figure 49, shows a cascade of sequentially changing energies from Zn-porphyrin to Mg-porphyrin, chlorin and phthalocyanine. the migration of holes is carried out in the opposite direction when adjusting the potentials of Mg-chlorin and Zn-porphyrin using meso-substituents.

C. Other formulations

The family of porphyrins include various pigments, many of which can be used in a linear architecture the migration energy of electrons and holes in opposite directions. The main members of the family include tetraazaporphyrin, heteroatom-modified porphyrins (e.g., N₃O - or N₃S - instead of the standard N₄-porphyrins) (Cho, W.-S. et al., J.Org.Chem. 1999, 64, 7890-7901), Chorrol and numerous stretched and compressed porphyrins (Van Patten, P.G. et al., J.Phys.Chem. B 1998, 102, 4209-4216).

Overall, a great many deputies are available to adjust elektrokhimicheskikh potentials, including various aryl and alkyl groups. Halogenated aryl group are particularly attractive for fine adjustment elektrokhimicheskikh potentials.

All chains are shown in figures 44-49, use diphenylethanone or p-phenylenebis linkers. The rate of energy transfer in the transition from diphenylamino linker to the n-venelinova the linker increases by about 10 times for porphyrins (˜(2 psec)^-1)⁵and 100 times for chlorins (sub-PS). Although these linkers are quite attractive, can be used also by other linkers.

D. Other design

The availability of fast energy transfer processes (i.e. using chlorine or porphyrins associated p-phenylene) has an important consequence for the design of chains for accumulation of light. Modeling the impact velocity of energy transfer in quantum yield of energy transfer into the trap of RA is put at the end of the linear chain, shows the following (Van Patten, P.G. et al., J.Phys.Chem.B 1998, 102, 4209-4216): when the reversible transfer between isoenergy pigments quantum yield decreases very rapidly with increase in the number of pigments. However, the quantum yield is also very sensitive to the speed of transfer. Increased speed, even for reversible transfer between isoenergy pigments, slows the fall of the quantum yield with increasing amounts of pigments. For speeds in the range of a few psec to share psak linear chains of reasonable quantities isoenergy pigments (for example, up to 20) should give acceptable quantum yields for excitation reaching the trap (that is, protective relays). Similarly, at low transfer rates (tens of picoseconds) high quantum yield in a linear chain of similar sizes can be obtained only by use of the energy cascade (i.e. irreversible stages of energy transfer). In the end, a linear chain consisting of several identical (isoenergy) pigments, will ensure efficient energy transfer, if the transfer rate is very high.

An example of a chain that uses many isoenergy pigments, is illustrated in figure 50. This chain includes the same pigments based on Zn-porphyrin, Magnesium porphyrin is Zn-chlorin, what are used in the figure 49. Linkers are solely p-phenylenebis group. The architecture uses a set of n Zn-porphyrins, then the set of n Mg-porphyrins, and then one Zn-chlorin. Energy transfer and holes is reversible between the elements of the given collection, but the transfer between the different sets is irreversible (towards lower potentials). The location of pigments reminiscent of the type of architecture of the waterfall with lots of pools. This design illustrates the concept that it is not necessary to have a stage of energy transfer to a lower potential, carried out in each pigment to achieve efficient energy transfer from the position of the absorption of light to the protective relays.

For fast energy transfer ideal election is the use of p-filinovich of linkers with porphyrins (with a_2uHOMO and linkers in the meso-positions) (Yang, S.I. et al., SoC. 1999, 121, 4008-4018) and/or chlorine (with linkers in meso - or β-provisions). For quick migration of holes by a hopping mechanism, the linker must be connected with position on the pigment, with significant electron density in the HOMO. while the energy transfer can occur by mechanisms TS and/or TB, the migration of holes from the ground state hopping mechanism is solely for TB-mechanism (at measures which, for the observed high velocities). Factors that affect TB-migration energy are similar to those that affect the migration of holes from the ground state hopping mechanism. Thus, chains with rapid TB-migration energy should also be given a high rate of migration of holes by a hopping mechanism. For efficient migration of holes by a hopping mechanism is not important to have a stage migration of holes by a hopping mechanism to a lower potential, carried out at each pigment to achieve effective transfer from protective relays to a position remote from him, in the antenna for the accumulation of light.

Although these structures the energy of the excited state and holes in the ground state are formed in the same chain, under conditions of rapid migration dynamics energy and low beam of sunlight the probability of the simultaneous presence of the excited state and holes is very low. Accordingly, the quenching of the excited state of holes in the ground state, as expected, is a rare event.

V. SYNTHESIS of POLYMERS by in situ ACCUMULATION of LIGHT ON the ELECTROCHEMICALLY ACTIVE SURFACES

The synthesis of the oligomers of the constituent units (C) based pigments or rods for the accumulation of light may occur by reactions of several different types. G is avna problem is to the reaction that is used to connect the components of the block-based pigments in dyadic architecture, also would create a linker that provides a message of electrons between the two pigments. Accordingly, in General, is considered a more limited set of reactions than the one that exists in all of organic chemistry. Methods for the synthesis of the polymer chains of the constituent units based pigments include, but are not limited to, the following types of reactions (figure 51):

linking by Glaser (or Eglinton) components of the blocks on the basis of Monomeric pigment (generation bufadienolide linker).

linking by Cadiot-Chodkiewicz two different components of the block-based pigments (generation bufadienolide linker connecting block copolymer).

Linking by Sonogashira two different components of the block-based pigments (generation Edinboro linker connecting block copolymer).

The Heck reaction or Wittig two different components of the block-based pigments (generation alkinoos linker connecting block copolymer).

Linking Suzuki two different components of the block-based pigments (generation venereologia or biphenylenes linker connecting block copolymer).

Polymerization of the components of the block-based pigments, chosen to replace is in itself a Vice, such as two or more thiophene group (generation rohitjenveja linker) or two or more of the pyrrole groups (generation polypyrrole linker).

Synthesis of oligomers can be performed using stepwise methods or using methods of polymerization. Both methods usually require two reactive groups attached to the constituting unit based on the pigment, to obtain a polymer, where the components of the blocks based on the pigment are integral components of the main polymer chain. (Alternatively, less attractive design results in polymers with side groups, where the components of the blocks based on the pigments are joined through a single bond to the main chain of the polymer.) Step-by-step method of synthesis generally requires the use of protective groups for masking one of the reaction centres, and one of the cycles of the reaction then involves binding with subsequent removal of the protection. In the method of polymerization of the protective groups are not used and the polymer is obtained in the process in one flask.

The polymerization processes can take place in solution or can be made using polymer, growing from the surface. The polymerization can be carried out, starting with the solid substrate, as in the solid-phase synthesis of peptides is whether DNA with the subsequent removal, cleaning and further processing for specific applications. Polymerization of the obtained polymer attached to the electrochemically active surface, generates the desired material for the accumulation of light in situ. The latter approach is very attractive, eliminating the need for processing of polymers. The ability to exclude manipulation of polymers makes possible the synthesis of compounds that do not exhibit sufficient solubility in most solvents for convenience of manipulation (dissolution, purification, processing, characterization solution).

Can be created polymers, which consist of identical nodes or from different sites, as in block copolymers or random copolymers. Alternatively, it may be carried out polymerization to create a linear chain, where the composition of the various components of the block-based pigments are organized in the form of a gradient. The latter approach enables the creation of an energy cascade to the flow of the energy of the excited state and/or back flow holes in the ground state in a systematic way along the length of the chain, as described elsewhere in this application.

The following further describes the synthesis in situ of cascade polymers on the electrochemically active surface, such as C the Lotto or TiO ₂: the polymerized unit (a constituent unit based on the pigment or the linker) attached to the surface (Au Tolna connecting group is used as the Y¹; TiO₂connecting the group of carboxylic acid is used as the Y²). Adding the first component block based pigment (PY¹), and linking reagents are added to implement the polymerization (for example, binding on Glaser). The surface is then washed to remove the binding reagents (reagents on the basis of copper in the case of binding by Glaser) and any unreacted BB¹. Then add the second component block based pigment (PY²), then linking reagents and polymerization enable to continue. The same procedure for rinsing is carried out again, and then added the third building block-based pigment (PY³), and then linking reagents and polymerization enable to continue. Repeating this process makes possible the systematic building of the linear chain of the constituent units based pigments with monotonically changing energy levels for the flow energy of the excited state and holes in the ground state. The last attached monomer carries a single reaction rate is R (J-L-(BB)-(L-Y), and the connecting group Y is used for subsequent bonding with the opposite surface. Characterization of immobilized on the surface of the polymer is achieved by absorption spectroscopy, IR spectroscopy, reflection spectroscopy and time-of-flight mass spectrometry with laser desorption.

In the above example (see figure 52) to the surface of Au is used Tolna connecting group (X), forming a self-assembled monolayer on gold. Such self-assembled monolayers are known for derivatizing thiols porphyrins (Gryko, D.T. et al., J.Org.Chem. 1999, 64, 8635-8647). For other surfaces, consisting of TiO₂to join using a connecting group of the carboxylic acid (Y). The polymerized groups can be of any type described above, using different personal reactions (Glaser, Sonogashira, Cadiot-Chodkiewicz, Heck, Wittig, Suzuki, and the like). The final polymer product consists of domains of the various components of the block-based pigments [(BBⁱ)_n] in the form of a linear chain.

VI. The application of SOLAR cells ACCORDING to the PRESENT INVENTION

Solar cells of the present invention can be used in many different electrical devices. Such devices typically include a solar cell, as described above, and kotarou scheme (for example, resistive), electrically connected with the specified solar cell (for example, by creating a first electrical connection scheme with one of the electrodes of the solar cell, and a second electrical connection scheme with the other electrode of the solar cell). The solar cell may provide the only power source for the circuit, may be an auxiliary power source, can be included for charging the battery (the battery) and the like. Any of a variety of different electrical devices may include a solar cell of the present invention, including, but not limited to, radios, TV sets, computers (such as personal computers, processors, calculators, phones, devices for wireless communication, such as pagers, watches, devices for emergency locating, electric vehicles, power sources for emergency power generators, devices for lighting or lamps and other lighting fixtures, devices for monitoring device for inspection, radiation detectors, devices for imaging device for optical connection.

The following examples are provided to illustrate certain aspects of the present invention and are not intended to be limited to what Iceni.

Examples

Rational synthesis β-substituted components of the blocks on the basis of chlorin

In these examples presents a synthesis of β-substituted components of the blocks on the basis of chlorine. Constructed two new Eastern half, each of which bears one β-Deputy and one (not attached to the adjacent component unit) meso-Deputy, and made one new Western half, which bears one β-Deputy. These new precursors are used in combination with the previous Western half (1) after receiving three new chlorins, each of which bears one βand one meso-Deputy. Also prepare a chlorine bearing one meso-substituent and the substituents in positions 2 and 12. Such building blocks is still not available, and in combination with meso-substituted chlorins, previously described (synthesis presented in figure 53), should open up opportunities for a variety of fundamental studies, including studies of the impact of the area of attachment of linker to the message of electrons in multiple architectures on the basis of chlorine.

Results and discussion

The synthesis of the Eastern half (EAP): Synthesis β-substituted EAP begins the same way as known from the literature synthesis β-substituted dipyrromethene (Balasubramaian, T.; Lindsey, J.S. Tetrahedron 1999, 55, 6771-6784), but uses a number of significant improvements (figure 54). Itfinal-substituted pyrrole (3) are easily prepared from 4-identilied, monoethylamine and toiletrieschoice. Ethoxycarbonyl group removed by treatment with NaOH in ethylene glycol at 160°C with 3-(4-itfinal)pyrrole (4) with the release of 91% in the form of pale brown crystals. It is noteworthy that this one-step decarboxylation is predominant in comparison with the two-stage conversion to such pyrrole compounds (Pavri, N.R.; Trudell, M.L. J.Org.Chem. 1997, 62, 2649-2651). Formirovanie by Vilsmeier-Haack 4 gives a mixture of two regioisomers (attitude ˜6:1), which are easily distinguished using¹H NMR spectroscopy (see experimental section). The main isomer is preferably a compound (5) and obtained in pure form by recrystallization to yield 62%. Protection of the pyrrole nitrogen using BOC group (Tietze, L.F.; Kettschau, G.; Heitmann, K. Synthesis 1996, 851-857) gives the pyrrole 6 with a quantitative yield. The recovery of the alcohol 7 is achieved by treatment with LiBH₄at low temperature (longer reaction times or higher temperatures lead to priostanovleno and deprived of protection connection 2-methyl-3-(4-itfinal)pyrrole). Treatment of alcohol 7 with excess pyrrole under acidic the conditions results in β substituted, monoamino dipyrromethene 8 yield 68%. Excess pyrrole is necessary to minimize the formation tierralta, while protection of the pyrrole nitrogen is needed to facilitate the reaction, eliminating samarangense and making possible the subsequent selective monocalibre. This method gives a β-substituted dipyrromethene as the only regioisomer as opposed to more sensitive methods, which give a mixture of two regioisomers (Balasubramanian, T.; Lindsey, J.S. Tetrahedron 1999, 55, 6771 -6784).

Developed methods for the acylation of 5-substituted dipyrromethene, which include getting pyrrole Grignard reagent followed by treatment with acid chloride (Lee, C.-H.; Li, F.; Iwamoto, K.; Dadok, J.; Bothner-By, A. A.; Lindsey, J.S. Tetrahedron 1995, 51, 11645 -11672). In this case, the N-protected dipyrromethene held for selective monocalibre αposition in unprotected pyrrole node. Processing dipyrromethene 8 2.5 equivalents of EtMgBr in THF, and then p-toluoyl chloride gives monocularly dipyrromethene 9 with the release of 66% (figure 54). However, the same reaction in toluene yields a mixture monoarylamino product, the connection is removed from protection and some unspecified impurities. The control experiment involves the manipulation of dipyrromethene 8 small excess of EtMgBr at 0° C in THF for 1 hour, and the usual extraction gives the source material with a quantitative yield, thereby proving that the BOC group is stable to the conditions of acylation. The removal of the BOC group under standard conditions (Hasan, I. et al., J.Org.Chem. 1981, 46, 157-164) gives compound 10. Electrophilic bromination of compound 10 using NBS (1 EQ.) in THF at -78°C, following previously described methods (excess NBS results in significant amounts of dibromo compound), gives compound 11.

The second β-substituted dipyrromethene prepared by linking by Sonogashira (Sonogashira, K. et al., Tetrahedron Lett. 1975, 4467-4470) itfinal-substituted compound 10 using trimethylsilylacetamide. In this way trimethylsilylethynyl dipyrromethene 12 get with quantitative yield (figure 55). Interaction of compound 12 with NBS at -78°C leads to the corresponding bromopyrimidine 13 with the release of 91%.

Preparation dipyrromethene, carrying the substituent in the other β-position, using the same protected BOC dipyrromethene 8 is also possible when handling order acylation and remove the protection that results in the connection 10. Thus, removing protection from dipyrromethene 8 using NaOMe/MeOH gives β-substituted dipyrromethene 14 (figure 55). A recently developed procedure for selectively is about monocalibre meso-substituted dipyrromethene using EtMgBr and S-pyridyl-substituted of benzothioate (Rao, P.D.; Dhanalekshmi, S.; Littler, B.J.; Lindsey, J.S. J.Org.Chem. submitted). The application of this method monocalibre to the connection 14 leads to the production of a mixture of two regioisomers (10, 16). Attempts to obtain compound 16 as the main product by varying the experimental conditions were unsuccessful. The separation of the two regioisomers is complex and requires extensive use column flash chromatography. Small isomer 16 is obtained, yield 25%. Treatment of compound 16 using 1 equivalent of NBS in THF at -78°C gives compound 17 with the release of 87% in the form of a yellow solid product. All β-substituted 1-bromopyrimidine (11, 13, 17) are somewhat unstable, but remain intact for several weeks when stored at 0°C in argon atmosphere.

Synthesis β-substituted Western half. The synthesis of the Western half, where there are no β-substituents except for pair dimethyl group (1)was previously developed (Strachan, J.P. et al., J.Org.Chem. 2000, 65, 3160-3172). Pyrrol-carboxaldehyde 5, available in quantities of several grams, provides a convenient starting point for the synthesis of new Western half, bearing on himself synthetic handle β -position. β-Substituted Western half in conjunction with β -substituted Eastern half would have made possible the synthesis of components of the blocks based on the chlorine is on, bear two β -Deputy located on opposite sides of the macrocycle. Using the reaction conditions used to obtain 2-(2-nitrovinyl)pyrrole 2-formylpyrazole (Strachan, J.P.; O'shea, D.F.; Balasubramanian, T.; Lindsey, J.S. J.Org.Chem. 2000, 65, 3160-3172), for the reaction of compounds 5 provides, in essence, to extract the source material. After limited research was found that treatment of compound 5 with KOAc and a small excess methylamine-hydrochloride in nitromethane (instead of methanol) as solvent at room temperature for 2 hours instead of 16 hours) gives the desired product 18 aldol-condensation with the release of 89% (figure 56). You may notice that a longer reaction time leads to the formation of product additions by Michael nitromethane on nitroaniline group in the product 18, forming 2 -(1,3-dinitro-2-propyl)-3-(4-itfinal)pyrrole with the release of ˜30%. Recovery of the product 18 with NaBH₄network connection 19, which is subjected to addition by Michael together with mesityloxide in the presence of CsF at 80°C product nitro-hexanone 20, predecessor β-substituted Western half. Although addition Michael is fast compared with the formation of β-unsubstituted mate (the precursor compound 1), the output is slightly lower (42% compared to the 65%). Treatment of compound 20 using NaOMe, and then a buffer solution of TiCl₃network β-substituted Western half 21 with the release of 45-50% in the form of a light green solid product. Output and stability β-substituted LC is larger than the output of the unsubstituted analogue (half 21 has TPL=141 -142°C; 1 represents an oil).

Obtaining chlorine. Previous methods of synthesis of chlorin include: (1) obtaining bromopyrimidine-monocarbonate (2-OH, EP) by restoring the carbonyl group in the precursor VP, (2) acid-catalyzed condensation of VP and OT (1) obtaining dihydropyran-a, and (3) oxidation mediated by metal cyclization of obtaining chlorine (Strachan, J.P.; O'shea, D.F.; Balasubramanian, T.; Lindsey, J.S. J.Org.Chem. 2000, 65, 3160-3172). All three stages are carried out sequentially in the same day. The same procedure is used here except that the conditions of extraction are different because of the labile nature β-substituted precursors PG (11, 13, 17) and the corresponding β-substituted Eastern halves. In a typical reaction, compound 11 is treated with NaBH₄in THF/MeOH (4:1) at room temperature in argon atmosphere. With the disappearance of starting material (analysis by TLC), the product is extracted from the reaction mixture, and the carbinol 11-OH is treated with 1.2 equivalent of the CW at room temperature in CH ₃CN containing TFU. After 25-30 minutes the final dihydropyran-a is obtained by quenching the reaction mixture with aqueous NaHCO₃and retrieve CH₂Cl₂. Add anhydrous toluene and 15 molar equivalents each of AgIO₃, Zn(OAc)₂and of piperidine and the mixture is heated at 80°C for ˜2.5 hours. The reaction mixture is slowly turning from red to green, indicating the formation of chlorine. Filtering the reaction mixture through a layer of oxide of silicon and subsequent column chromatography gives the chlorin Zn-22 with a purity of >90%. Deposition using CH₂Cl₂/hexane yields a pure chlorin (Zn -22) with the release of 18% (figure 57). Similar processing of the Eastern half of the 13-OH and compound 1 gives the zinc chlorin Zn-23 with the release of 22%. The Eastern half (17)carrying β -substituent in position 8, interacts similarly with connection 1, giving the zinc chlorin Zn-24.

Zn-chlorin 22-24 carry one β-Deputy. For the preparation of chlorine, carrying two β-Deputy, 13-OH and the Western half of the 21 react with obtaining the zinc chlorin Zn-25 with the release of 24% (figure 58). This chlorine has itfinally group and ethynylphenyl group β-position on opposite sides of the macrocycle. Porphyrins bearing on himself idfamilia and ethynylphenyl g is uppy in TRANS-orientation, used in the stepwise synthesis of linear multiporphyrin chains (Wagner, R.W.; Lindsey, J.S. SOC. 1994, 116, 9759-9760; Wagner, R.W.; Ciringh, Y.; Clausen, P.C.; Lindsey, J.S. Chem.Mater. 1999, 11, 2974-2983; Lindsey, J.S. et al., Tetrahedron 1994, 50, 8941-8968). Similar linear multicarinata chain can be obtained by using Zn-25. In each of these reactions with the formation of chlorine turns out only one of chlorin product, which indicates the absence of rearrangements in the course of the reaction. This technique is quite General, and outputs 18-24%, obtained for the three β-substituted Eastern halves (11-OH, 13-OH, 17-OH) and β-substituted Western half (21), are noticeably superior ˜10%received for meso-substituted Eastern halves (2-OH) and Western halves (1).

Zn-chlorin demetallised the corresponding chlorins with the free base by treatment with TFU in CH₂Cl₂. In most cases, the crude product is sufficiently pure for analysis, while in other cases the chlorine with the free base optionally is purified by a short column with silica.

Spectral properties of chlorins. Spectra¹H NMR. Available information in NMR spectra relative to the chlorine obtained mainly for natural chlorine, which bear alkyl groups, more just β-provisions.¹H NMR spectra² -substituted chlorins with the free base (22-25) and Zn-chlorin (Zn-22-Zn-25) is easily interpreted and confirm the expected patterns of substitution. 22, two NH protons appear as broad peaks at δ -2,15 and -1,85 ppm, and the signal at lower field strength appears for one of the meso-substituted protons (attributed to C-10) at δ 9,84 M.D.. Restored the ring shows a singlet at δ 2,07 ppm (paired dimethyl group) and another singlet at δ with 4.64 ppm (ring CH₂), which is also observed in meso-substituted chlorins. Other characteristic features include AB Quartet at δ cent to 8.85 ppm (β-pyrrole protons of ring A), two doublet at δ 8,64 and of 8.90 ppm (β-pyrrole protons of ring B), and singlets at δ 8,91 (2H) and 8,99 ppm (two meso-proton at C-15 and C-20, and one β-pyrrole proton ring C). Significant changes for β-substituted Zn-22 represent the absence of signals corresponding to the protons of NH, and small shifts toward the higher field strengths from steam dimethyl group (δ a 2.01 ppm), the ring methylene protons (δ 4,48 ppm) and all meso - and β-pyrrole protons. Similar trends are observed for chlorine free base 23 and the zinc chlorin Zn-23.

Range¹H NMR of chlorin 24 is somewhat different because of differences in the structure of the substitution p is the perimeter of the molecule. Characteristic features in addition to the great values of chemical shifts for the two NH protons include singlet at δ 8,64 ppm (β-pyrrole proton ring (B) and shifted towards lower field strengths the signal δ 9,17 ppm as doublet (one of β-pyrrole protons of ring C). Range¹H NMR of chlorin 25 is simpler. β-Pyrrole protons of ring B appear as two doublets at δ 8,62 and 8,88, and the Quartet AB, appropriate β-pyrrole protons of ring A in the chlorines 22-24, is missing. The remaining meso-protons and β-pyrrole protons give resonance as five singlets. Zn-25 shows a similar structure except for a small shift toward the higher field strengths peaks associated with meso - and β-protons.

The distinctive feature of this set of chlorins is that β-pyrrole protons of ring B are manifested in several large field strengths in comparison with all other pyrrolic protons. This indicates that β -pyrrole double bond of ring B does not participate fully in the socialization of electrons 18π ring chlorin macrocycle.

Absorption spectra. Each of the chlorines with the free base (22-25) shows an intense band, Sore and characterized by a strong band of Q_y. Band, Sore in every the m case demonstrates his shoulder at short wavelengths with significant intensity, that leads to the peak width at half-maximum level within 32-35 nm for 22-25. This feature of the spectrum is observed for the previous set of meso-substituted chlorins with the free base, which was investigated. Band, Sore and slightly shifted to the red side, as the Deputy is moved from position 8 (24) 12 (22, 23), 2 and 12 (25). Significant differences in the position of maximum absorption of Q_yand the intensity of absorption occur depending on the position of substitution of the chlorine. The position of the maximum absorption of Q_yis in the range from 637 to 655 nm and varies in parallel with the red shift of the fringe, Sore. In addition, there is a hyperchromic effect strip Q_ythat accompanies bathochromic shift. Although the exact determination of molar absorption coefficients can be complex, especially in the manipulation of small samples, the ratio of the bands Q_yand, Sore and provides a relative measure of changes in the intensity of bands. The ratio of bands, Sore/Q_yreduced from 4.3 (24) 2.5 (25). These data are listed in table 1. You may notice that the chlorines with itfinally or ethynylphenyl group in position 12 demonstrate approximately the same absorption spectra. For comparison, meso-substituted chlorins with the free base exhibit absorption maxima at 411-414 nm and 640-644 nm.

the each of the zinc-chlorine (Zn-22-Zn-25) shows an intense band, Sore and characterized by a strong band of Q _y. Band, Sore and in each case is narrow (width of the peak at half-maximum level 18-21 nm) with only a very weak shoulder in the region of short wavelengths. Band Q_yundergoes a red shift from 606 nm to 628 nm, since the position of the substituent is changed from 8 (Zn-24) 12 (Zn-22, Zn-23), 2 and 12 (Zn-25). Also, there is a simultaneous increase in the intensity of band Q_y. These results are listed in table 1. In all the investigated chlorines red shift of the band, Sore accompanied by a more pronounced red shift of the band of Q_y. The only inconsistency in this trend occurs when comparing Zn-24 and Zn-22 (or Zn-23). The first one has the shortest wavelength for band Q_y(606 nm), but the band, Sore and 415 nm, compared to 615 nm and 411 nm for them in the latter case. For comparison, meso-substituted zinc chlorins show absorption maxima at 412 nm and 608 nm.

Fluorescence spectra and yields. Like meso-substituted chlorines, chlorins with the free base 22-24 demonstrate the characteristic narrow zone of fluorescence at 640 nm and a weaker emission in the field 660-720 nm. The latter shows two well-resolved peak at approximately 680 and 710 nm. The spectrum of emission of chlorine 25 with the free base is shifted to 660 nm and 726 nm. Zn-chlorin Zn-22 and Zn-23 demonstrate each narrow zone of fluorescence near his summe is zi 620 nm and a weak band at 676 nm, while the emission of Zn-24 appears on 609 and 661 nm. The spectrum of emission of Zn-25 stronger shifted to the red side than it is observed for the form of the free base 25 (635 and 691 nm). Quantum yields of fluorescence determined for those chlorines that are idfamilia substituents (which show a decrease in output due to the heavy-atom effect). Quantum yield of fluorescence for chlorin 23 with the free base is 0.25, while for Zn-23 it is 0.11. These values are consistent with values for other natural or synthetic chlorins.

The conclusions. Synthesis of chlorins, described here, provides the following features: (1) control of the position of the restored ring, (2) maintaining a given level of hydrogenation of chlorine through the use of paired dimethyl groups, (3) placement of a synthetic handles at specified places on the perimeter of the macrocycle, and (4) only chlorin product, thus, easier to clean. The ability to incorporate substituents in different positions (2, 5, 8, 10, or 12) on the perimeter of chlorin reveals a number of fundamental capabilities. When the different structures of the substitution position of the absorption band Q_ycan be changed within 637-655 nm for chlorins with the free base, and 606-628 nm for zinc chlorins, making possible a wider Perek ivanie spectrum. Chlorin bearing synthetic handles in positions 2 and 12 (25), should create the opportunity for integrating the components of the blocks on the basis of chlorin in a linear architecture. The availability of a family of synthetic chlorins, bearing different substituents in a given position, should facilitate systematic studies of the effects of substituents and to expand the scope containing chlorin model systems.

Experimental section

The General part. Spectra¹H and¹³C NMR (300 MHz) receive in CDCl₃if not stated otherwise. Absorption spectra (Cary 3, the intervals between data points is 0.25 nm) and fluorescence spectra (Spex FluoroMax, the intervals between data points 1 nm) measured in routine ways. Chlorins analyze in its original form using mass spectrometry, laser desorption (LD-MS) in the absence of matrix (Fenyo, D. et al., J. Porphyrins Phthalocyanines 1997, 1, 93-99; Srinivasan, N. et al., J. Porphyrins Phthalocyanines 1999, 3, 283-291). Pyrrole distil at atmospheric pressure of CaH₂. The melting temperature is not adjusted. p-Identilied receive from Karl Industries. All other reagents and starting materials receive from Aldrich. The spectral parameters, including the molar absorption coefficients and quantum yields of fluorescence (Φ_f), determined as described previously (Strachan, J.P. et al., J.Org.Chem. 2000, 65, 3160-3172).

The chromatography. ven is operational chromatography is carried out using silica (Baker) or alumina (Fisher A540, 80-200 mesh) and eluting solvents on the basis of hexane, mixed with ethyl acetate or CH₂Cl₂.

The solvents. THF distil from sodium benzophenone of life according to needs. CH₃CN (Fisher certified A.C.S.) distil from CaH₂and keep on powdered molecular sieves. Nitromethane store over CaCl₂. CH₂Cl₂distil from CaH₂. Dry methanol prepared as follows. Magnesium shavings (5 g) and iodine (0.5 g) with 75 ml of methanol is heated up until the iodine will not disappear, and the magnesium is not converted in the methoxide. Add up to 1 l of methanol and heated under reflux for at least 2 hours before collection. Other solvents used in the form as they are received.

Connections 1(Strachan, J.P. et al., J.Org.Chem. 2000, 65, 3160-3172) and 3 (Balasubramanian, T.; Lindsey, J. S. Tetrahedron 1999, 55, 6771-6784) prepared in accordance with the procedures found in the literature.

3-(4-Itfinal)pyrrole (4). Following previously described procedures (Balasubramanian, T.; Lindsey, J.S. Tetrahedron 1999, 55, 6771-6784), a mixture of 3-etoxycarbonyl-4-(4-itfinal)pyrrole (7.20 g, 21.1 mmol) and ethylene glycol (55 ml) in a 100-ml flask of Clausena rinsed with argon for 10 min, and then add powdered NaOH (2.2 g, 55 mmol). The flask is put in an oil bath at 120°C and the oil bath temperature was raised to 160°C. After 2.5 hours the flask was cooled to the room for the Noah temperature and treated with 10% aqueous NaCl solution (100 ml). The aqueous layer was extracted with CH₂Cl₂, the organic layers collected, washed with 10% aqueous NaCl solution, dried (Na₂SO₄), concentrated and recrystallized in ethanol to obtain a light-brown crystals (5,18 g, 91%). TPL 164-165°C;¹H NMR δ 6,51 (m, 1H), 6,83 (m, 1H), was 7.08 (s, 1H), 7,27 (d, J=8.7 Hz, 2H), 7,63 (d, J=8.7 Hz, 2H);¹³C NMR δ 89,9, 106,3, 114,7, 119,1, 123,8, 127,0, 135,2, 137,5; EI-MS observed 268,9702 calculated 268,9702. Analytically calculated for C₁₀H₈IN: C AND 44.6; H, 3,0, N, 5,2. Found: C, A 44.7; H, 3,0, N, 5,1. The synthesis starting from 4-identilied (35 g), monoethyl of malonate, and TosMIC, is carried out with a linear scaling procedures with the receipt of 21.5 g of compound 4.

2-Formyl-3-(4-itfinal)pyrrole (5). A solution of compound 4 (5,15 g of 19.1 mmol) in DMF (6,1 ml) and CH₂Cl₂(140 ml) in an argon atmosphere cooled to 0°C and then add POCl₃(2,11 ml, and 22.6 mmol) dropwise. After 1 hour, the flask is heated to room temperature and stirred over night. The reaction is quenched at 0°C with 2.5 M NaOH (100 ml). The mixture was poured into water (500 ml), extracted with CH₂Cl₂, and the combined organic layers washed with water, saturated salt solution, dried (Na₂SO₄) and the solvent is removed in vacuum.¹H NMR spectroscopy shows two regioisomers with respect ˜6:1. Small isomer shows the signals when the δ ,21 and 7,39 ppm, compared with signals when δ 6.42 per 7,14 and for the main isomer. The signal at the lowest field strength (7,39 ppm) is attributed to the proton adjacent to the formyl group, which is 2-formyl-4-aryl substituted pyrrole. Recrystallization from ethyl acetate gives the orange solid product corresponding to the main aldehyde (2.25 g). The mother liquid is concentrated and purified using flash column-chromatography [silica, hexane/ethyl acetate (3:1)]. The first fraction corresponds to the main aldehyde (1.25 g). Total yield specified in the connection header is 3.50 g (62%): TPL 153-154°C;¹H NMR δ 6.42 per (m, 1H), 7,14 (m, 1H), 7,22 (m, 2H), 7,76 (m, 2H), 9,59 (s, 1H), of 10.72 (user, 1H);¹³C NMR δ 93,5, 104,3, 111,4, 125,8, 128,6, 130,8, 133,1, 137,8, 179,4; FAB-MS observed 296,9663 calculated 296,9651; Analytical calculated for C₁₀H₈INO: C TO 44.5; H, 2.7; THE N, 4,7. Found: C, 44,4; H, 2.7; The N, 4,6.

N-tert-Butoxycarbonyl-2-formyl-3-(4-itfinal)pyrrole (6). Following the standard procedure (Tietze, L. F.; Kettschau, G.; Heitmann, K. Synthesis 1996, 851-857), a sample of NaH (70 mg, about 1.75 mmol, 60% dispersion in mineral oil) in a round bottom flask in an argon atmosphere twice washed with anhydrous pentane (˜5 ml). Add anhydrous THF (14 ml), and then compound 5 (400 mg, 1.35 mmol). After stirring for 30 min at room temperature, add (BOC)₂O (325 mg, 1.5 mmol), and continue premesis the treatment in the next 2 hours. The reaction is quenched with 50% saturated aqueous NH₄Cl (50 ml). The mixture is extracted with simple ether, and the combined organic layers washed with saturated salt solution, dried (Na₂SO₄) and filtered [silica, hexane/ethyl acetate (4:1)] to obtain a viscous oil (535 mg, quantitative).¹H NMR δ of 1.64 (s, 9H), 6,33 (d, J=3.0 Hz, 1H), 7,30 (d, J=8.1 Hz, 2H), 7,46 (d, J=3.0 Hz, 1H), 7,72 (d, J=8.1 Hz, 2H), 10,22 (s, 1H);¹³C NMR δ 27,7, 85,8, 94,2, 113,2, 126,7, 128,5, 131,3, 132,8, 137,0, 137,4, 148,3, 181,6; FAB-MS observed 397,0176 calculated 397,0175 (C₁₆H₁₆INO₃).

N-tert-Butoxycarbonyl-2-hydroxymethyl-3-(4-itfinal)pyrrole (7). A solution of compound 6 (400 mg, 1.0 mmol) in anhydrous THF (12 ml) in an argon atmosphere cooled to -20 to -25°C, and the parts add LiBH₄(55 mg, 2.5 mmol). The reaction is followed by TLC (silica, hexane/ethyl acetate (4:1)), and when it is not detected any source material (20-25 min), the reaction is quenched with cold water (30 ml). The aqueous layer was extracted with CH₂Cl₂and the organic layer dried (Na₂SO₄), concentrated and purified using flash column-chromatography [silica, hexane/ethyl acetate containing 1% Et₃N (3:1)] to obtain resin (330 mg, 82%).¹H NMR δ of 1.62 (s, 9H), 3,61 (user, 1H), 4,66 (d, J=7.2 Hz, 2H), and 6.25 (d, J=3.6 Hz, 1H), 7,18 (d, J=8.1 Hz, 2H), 7,22 (d, J=3.6 Hz, 1H), 7,71 (d, J=8.1 Hz, 2H);¹³C NMR δ 27,8, 55,3, 84,7, 92,4, 111,2, 121,3, 127,9, 130,0, 130,4, 34,1, 137,5, 149,8; FAB-MS observed 399,0336 calculated 399,0331 (C₁₆H₁₈INO₃).

3-(4-Itfinal)-10-N-(tert-butoxycarbonyl)dipyrromethene (8). A solution of compound 7 (1.2 g, 3.0 mmol) and pyrrole (3,36 ml, 48 mmol) in 1,4-dioxane (36 ml) at room temperature, treated with 10% aqueous HCl solution (6.0 ml). The reaction is followed by TLC [silica, hexane/ethyl acetate (4:1)]. After 4 hours, add saturated aqueous solution of NaHCO₃(50 ml) and water (50 ml) and the mixture extracted with CH₂Cl₂. The combined organic layers washed with water, saturated salt solution, dried (Na₂SO₄), concentrated and purified using flash chromatography [silica, hexane/ethyl acetate (4:1)]. Nonpolar product isolated in small quantities (not characterized). The desired product is obtained in the form of a pale brown solid (920 mg, yield 68%): TPL 128 -129°C;¹H NMR δ of 1.57 (s, 9H), 4,18 (s, 2H), by 5.87 (user, 1H), 6,10 (m, 1H), from 6.22 (d, J=3.0 Hz, 1H), only 6.64 (m, 1H), 7,16 (d, J=8.0 Hz, 2H), 7,24 (d, J=3.6 Hz, 1H), 7,71 (d, J=8.0 Hz, 2H), 8,78 (user, 1H);¹³C NMR δ 24,6, 27,8, 84,3, 92,1, 105,8, 107,9, 111,6, 116,3, 121,0, 126,8, 128,5, 130,4, 130,8, 135,0, 137,4, 150,0; FAB-MS observed 448,0659 calculated 448,0648; Analytical calculated for C₂₀H₂₁IN₂O₂: C, UP 53.6; H, 4,7, N, OF 6.3. Found: C, 54,1; H, A 4.9; N, 5,9.

3-(4-Itfinal)-9-(4-methylbenzoyl)-10-N-(tert-butoxycarbonyl)dipyrromethene (9). A solution of compound 8 (448 mg, 1.0 mmol) in betwedn the m THF (15 ml) in an argon atmosphere at 0° C slowly treated with EtMgBr (1 M in THF, 2.5 ml, 2.5 mmol). The mixture is stirred for 30 minutes at 0°C, then slowly add n-toluoyl chloride (200 μl, 1.5 mmol), and stirring is continued for 1 hour at 0°C. the Reaction is quenched with saturated aqueous NH₄Cl and extracted with CH₂Cl₂. The combined organic layers washed with water, saturated salt solution, dried (Na₂SO₄), concentrated, and the product was then purified using column flash chromatography [silica, hexane/ethyl acetate (4:1)]. The product is obtained in the form of a whitish solid (375 mg, 66%): TPL 120-121°C; (because of possible rotamers, data¹H NMR and¹³C NMR are not very clear)¹H NMR δ and 1.56 (s, 9H), 2,42 (s, 3H), 4,29 (s, 2H), 5,95 (m, 1H), of 6.26 (m, 1H), 6,76 (m, 1H), to 7.09 (m, 2H), 7,16 (m, 1H), 7,25 (m, 2H), 7,31 (m, 1H), 7,71 (d, 8.7 Hz, 2H), to 7.77 (d, J=8.1 Hz, 2H), 9,95 (user, 1H);¹³C NMR δ 25,2, 27,8, 31,7, 84,8, 92,3, 109,3, 111,5, 119,6, 121,5, 125,8, 126,3, 128,9, 129,0, 130,2, 130,6, 134,7, 135,8, 137,5, 138,6, 142,0, 149,7, 183,8; Analytically calculated for C₂₈H₂₇IN₂O₃: C, TO 59.4; H, 4,8, N, 5,0. Found: C, To 59.4; H, 4,6, N, 5,1.

3-(4-Itfinal)-9-(4-methylbenzoyl)dipyrromethene (10). Following the standard way to remove the protection with BOC-protected pyrrole (Hasan, I. et al., J.Org.Chem. 1981, 46, 157-164), a solution of compound (9) (328 mg, of 0.58 mmol) in anhydrous THF (4 ml) in an argon atmosphere at room temperature is treated with methanol is astora NaOMe (0.7 ml, prepare by dissolving 200 mg of NaOMe in 1.0 ml MeOH). After 20-25 minutes the reaction is quenched with a mixture of hexane and water (20 ml, 1:1) and extracted with ethyl acetate. The combined organic layers washed with water, saturated salt solution, dried (Na₂SO₄) and purified using column flash chromatography [silica, hexane/ethyl acetate (3:1)] to obtain a pale brown solid product (216 mg, 80%): TPL 185-186°C;¹H NMR δ 2,43 (s, 3H), 4,17 (s, 2H), x 6.15 (m, 1H), 6,56 (m, 1H), 6,85 (m, 1H), 7,17 (m, 2H), 7,28 (m, 2H), 7,69 (m, 2H), to 7.77 (d, J=7.8 Hz, 2H), 9,43 (user, 1H), 10,88 (user, 1H);¹³C NMR δ 21,6, 25,2, 90,6, 108,6, 110,3, 117,4, 121,1, 122,3, 123,9, 129,0, 129,1, 130,0, 130,7, 135,5, 136,2, 137,4, 139,4, 142,6, 185,2; FAB-MS observed 466,0561 calculated 466,0542; Analytical calculated for C₂₃H₁₉IN₂O: C, A 59.2; H, 4,1; N, 6,0. Found: C, Of 59.3; H, 4,2; N, 5,9.

1-Bromo-3-(4-itfinal)-9-(4-methylbenzoyl)dipyrromethene (11). Following previously described procedures (Strachan, J.P. et al., J.Org.Chem. 2000, 65, 3160-3172), compound 10 (120 mg, 0.26 mmol) dissolved in anhydrous THF (6 ml) and cooled to -78°C in argon atmosphere. add recrystallized NBS (46 mg, 0.26 mmol) and the reaction mixture is stirred for 1 hour (-78°C)and then quenched with a mixture of hexane and water (20 ml, 1:1), and enable her to warm up to 0°C. the Aqueous portion is extracted with ether chemical purity and the combined organic layers dried over K₂CO₃. The solvent is evaporated vacuume at room temperature. Purification using flash column-chromatography [silica, hexane/simple ether (2:1)] to give a yellow solid product (120 mg, 85%). Bromopyrimidine is unstable, but can be stored for several weeks at 0°C. TPL 160°C (decomp.);¹H NMR δ of 2.44 (s, 3H), 4.09 to (s, 2H), 6,12 (d, J=3.0 Hz, 1H), 6,16 (m, 1H), 6.89 in (m, 1H), 7,14 (d, J=7.8 Hz, 2H), 7,30 (d, J=7.8 Hz, 2H), 7,71 (d, J=8.1 Hz, 2H), 7,80 (d, J=8.1 Hz, 2H), 10,33 (user, 1H), 11,59 (user, 1H);¹³C NMR δ 21,6, 24,9, 91,1, 97,9, 110,2, 110,5, 122,8, 123,5, 125,4, 129,2, 130,2, 130,0, 130,8, 135,2, 135,4, 137,5, 139,9, 142,8, 186,1; FAB-MS observed 543,9642 calculated 543,9647; Analytical calculated for C₂₃H₁₈BrIN₂O: C, AT 50.7; H, 3,3, N, 5,1. Found: C, A 51.3; H, 3,5, N, 5,2.

3-[4-(Trimethylsilylethynyl)phenyl]-9-(4-methylbenzoyl) dipyrromethene (12). Samples of compound 10 (279 mg, 0,599 mmol), Pd₂(dba)₃(42 mg, 0.046 mmol), Ph₃As (113 mg, 0,369 mmol) and CuI (9 mg, 0,047 mmol) is added to 25-ml flask, Selenka. The flask was pumped and rinsed three times with argon. Then add deaerated anhydrous THF/Et₃N (6 ml, 1:1), and then trimethylsilylacetamide (127 μl, 0.90 mmol). The flask is sealed, immersed in an oil bath (37°C), and the mixture is stirred over night. Then add CH₂Cl₂(20 ml)and the mixture filtered through a pad of Celite, washed several times with CH₂Cl₂, concentrated and the residue purified using column flash chromatography [silica, hexane/e is ylacetic (3:1)] to obtain a yellow solid product (262 mg, quantitatively): TPL 126-127°C;¹H NMR δ of 0.26 (s, 9H), 2,43 (s, 3H), 4,19 (s, 2H), 6,16 (m, 1H), 6,28 (m, 1H), 6,55 (m, 1H), 6,85 (m, 1H), 7,28 (d, J=8.7 Hz, 2H), 7,38 (d, J=8.1 Hz, 2H), 7,49 (d, J=8.7 Hz, 2H), to 7.77 (d, J=8,1 Hz, 2H), 9,51 (user, 1H), 10,96 (user, 1H);¹³C NMR δ 0,0, 21,5, 25,3, 105,4, 108,6, 110,3, 117,4, 119,9, 121,5, 122,3, 124,1, 127,6, 129,0, 129,1, 130,7, 132,0, 135,5, 137,0, 139,5, 142,6, 185,2; FAB-MS observed 436,1972 calculated 436,1971; Analytical calculated for C₂₈H₂₈N₂OSi: C, 77,0; H, 6.5; The N, 6,4. Found: C, To 76.3; H, 6,3; N, 6,3.

1-Bromo-3-[4-(trimethylsilylethynyl)phenyl]-9-(4-methylbenzoyl)dipyrromethene (13). Following the procedure for the synthesis of compound (11), the treating compound 12 (150 mg, 0.34 mmol) with NBS (60 mg, 0.34 mmol) to give a pale yellow solid product (160 mg, 91%): TPL 140°C (decomp.);¹H NMR δ of 0.26 (s, 9H), is 2.44 (s, 3H), of 4.12 (s, 2H), 6,17 (m, 2H), 6.89 in (m, 1H), 7,31 (m, 4H), 7,50 (d, J=9.0 Hz, 2H), 7,80 (d, J=8.1 Hz, 2H), 10,16 (user, 1H), 11,42 (user, 1H);¹³C NMR δ 0,0, 21,5, 25,0, 94,1, 97,9, 105,2, 110,3, 110,5, 120,4, 123,3, 125,5, 127,7, 129,2, 130,7, 132,1, 135,4, 135,9, 139,7, 142,8, 185,9; FAB-MS observed 514,1079 calculated 514,1076; Analytical calculated for C₂₈H₂₇BrN₂OSi: C, To 65.2; H, 5,3, N, 5,4. Found: C, A Total Of 65.1; H, 5,2, N, 5,3.

3-(4-Itfinal)dipyrromethene (14). Following the procedure of removing the protection used for the preparation of compound 10, a sample of compound 8 (225 mg, 0.50 mmol) in anhydrous THF (4 ml) in an argon atmosphere at room temperature is treated with a methanol solution of NaOMe (0.6 ml, prepared by dissolving 200 mg NaOM in 1.0 ml MeOH). After 15 min the reaction is quenched with a mixture of hexane and water (14 ml, 1:1), extracted with ethyl acetate and the combined organic layers washed with water, saturated salt solution, then dried over Na₂SO₄. The residue is passed through a filtration column to obtain a light brown solid (160 mg, 92%). Analytical data are in accordance with literature data (Balasubramanian, T.; Lindsey, J. S. Tetrahedron 1999, 55, 6771 -6784).

3-(4-Itfinal)-1-(4-methylbenzoyl)dipyrromethene (16). Following the General procedure monocalibre for unprotected dipyrromethene (Rao, P.D. et al., J.Org.Chem. 2000, 65, 1084-1092,), EtMgBr (1 M solution in THF, 2.2 ml, 2.2 mmol) are added to a solution of compound 14 (385 mg, 1.1 mmol) in anhydrous THF (14 ml). After stirring for 10 min the flask was cooled to -78°C and slowly add a solution piridinovogo of tiefer 15 (255 mg, 1.1 mmol) in anhydrous THF (3 ml). After a few minutes the cooling bath is removed, and stirring is continued for 1 hour, then the mixture is quenched with saturated aqueous NH₄Cl, water, and then extracted with CH₂Cl₂. The combined organic layers washed with water, saturated salt solution, dried (Na₂SO₄) and concentrate. Two of the resulting regioisomer purified by two successive flash column [silica, hexane/ethyl acetate (3:1)] to obtain small isomer 16 (130 mg, 25%) and heads of the CSOs isomer 10 (270 mg, 53%). Data for 16: TPL 190°C (decomp.);¹H NMR δ 2,43 (s, 3H), 4,15 (s, 2H), equal to 6.05 (m, 1H), 6,13 (m, 1H), return of 6.58 (m, 1H), 6,94 (m, 1H), 7,19 (d, J=8.7 Hz, 2H), 7,28 (d, J=8.1 Hz, 2H), 7,73 (d, J=8.7 Hz, 2H), 7,78 (d, J=8.1 Hz, 2H), 9,17 (user, 1H), 10,83 (user, 1H);¹³C NMR δ 21,6, 25,2, 91,8, 106,8, 108,3, 117,8, 121,1, 124,3, 127,2, 129,1, 129,2, 129,7, 130,2, 134,6, 135,4, 136,3, 137,6, 142,9, 185,4; FAB-MS observed 466,0573 calculated 466,0542; Analytical calculated for C₂₃H₁₉IN₂O: C, A 59.2; H, 4,1; N, 6,0. Found: C, To 59.1; H, 4,2, N, 5,8.

9-Bromo-3-(4-itfinal)-1-(4-methylbenzoyl)dipyrromethene (17). Following the procedure for the synthesis of compound (11), treatment of compound 16 (186 mg, 0.400 mmol) with NBS (72 mg, 0,405 mmol) gives a pale yellow solid product (189 mg, 87%): TPL 140°C (decomp.);¹H NMR δ 2,43 (s, 3H), 4,08 (s, 2H), 5,94 (m, 1H), 6,00 (m, 1H), of 6.96 (d, J=2.1 Hz, 1H), 7,18 (d, J=8.7 Hz, 2H), 7,29 (d, J=8.1 Hz, 2H), 7,74 (d, J=8.7 Hz, 2H), 7,80 (d, J=8.1 Hz, 2H), 9,80 (user, 1H), 11,53 (user, 1H); an attempt is made measurements¹³C NMR in CDCl₃but the connection is decomposed with long-term data. FAB-MS observed 543,9628 calculated 543,9647; Analytical calculated for C₂₃H₁₉IN₂O: C, AT 50.7; H, 3,3, N, 5,1. Found: C, A 51.2; H, 3,4; N, 5,0.

2-(2-TRANS-Nitrovinyl)-3-(4-itfinal)pyrrole (18). A mixture of compound 5 (of 1.485 g, 5.00 mmol), KOAc (492 mg, free 5.01 mmol), methylamine-hydrochloride (402 mg, 5,95 mmol) and nitromethane (45 ml) in an argon atmosphere was stirred at room temperature. The mixture is slowly becoming orange and gives a reddish-orange is the new sediment. The reaction is followed by TLC, and after stirring for 2 h TLC shows the appearance of a new component and the disappearance of compound 5. (Longer reaction time (10 h) leads to the formation of product additions by Michael, 2-(1,3-dinitro-2-propyl)-3-(4-itfinal)pyrrole, with the release of ˜30%.) The reaction is quenched with saturated salt solution, extracted with ethyl acetate and the organic layers dried (Na₂SO₄) and concentrate. The residue is treated with hot ethyl acetate and filtered, then concentrated and dissolved in hot CH₂Cl₂with the subsequent deposition of adding cold hexane and obtain orange solid product (1.52 g, 89%): TPL 217-218°C (decomp.);¹H NMR (acetone-d₆) δ 6,56 (d, J=2.1 Hz, 1H), 7,32 (d, J=8,2 Hz, 2H), 7,35 (m, 1H), 7,81 (d, J=13.5 Hz, 1H), of 7.90 (d, J=8,3 Hz, 2H), to 7.99 (d, J=a 13.4 Hz, 1H);¹³C NMR (acetone-d₆) δ 93,4, 112,5, 121,3, 127,1, 127,2, 128,4, 131,8, 132,8, 135,4, 138,9; FAB-MS observed 339,9720 calculated 339,9709. Analytically calculated for C₁₂H₉IN₂O₂: C, 42,4; H, 2.7; THE N, 8,2. Found: C, compared with 41.8; H, 2,6, N, 7,9; λ_abs(toluene) 395 nm.

2-(2-Nitroethyl)-3-(4-itfinal)pyrrole (19). Following the procedure for β-unsubstituted pyrrole (Strachan, J.P. et al., J.Org.Chem. 2000, 65, 3160-3172), a sample of compound 18 (1,36 g, 4.00 mmol) dissolved in anhydrous THF/MeOH (40 ml, 9:1) in an argon atmosphere at 0°C. the parts added NaBH₄(605 mg, 16,00 mmol and stirring is continued for 1 hour at 0° C. the mixture is Then stirred for 2 hours at room temperature. The reaction mixture is neutralized with acetic acid (pH 7), then add water (50 ml) and the mixture extracted with ethyl acetate. The combined organic layers washed with water, saturated salt solution, dried (Na₂SO₄), concentrated and purified by passing through a short column [silica, hexane/ethyl acetate (3:1)] to obtain a whitish solid (1.2 g, 88%): TPL 88-89°C;¹H NMR δ to 3.41 (t, J=6.6 Hz, 2H), to 4.52 (t, J=6.6 Hz, 2H), of 6.26 (s, 1H), 6,74 (s, 1H), 7,07 (d, J=8.1 Hz, 2H), 7,69 (d, J=8.1 Hz, 2H), 8,33 (user, 1H);¹³C NMR δ 24,0, 75,0, 91,1, 109,3, 117,8, 122,1, 122,2, 129,8, 135,7, 137,7; FAB-MS observed 341,9877 calculated 341,9865; Analytical calculated for C₁₂H₁₁IN₂O₂: C, 42,1; H, 3,2, N, 8,2. Found: C, Of 42.3; H, 3,3, N, 8,1.

1-[3-(4-Itfinal)Pirro-2-yl]-2-nitro-3,3-dimethyl-5-hexanol (20). Following the procedure for β-unsubstituted pyrrole (Strachan, J.P. et al., J.Org.Chem. 2000, 65, 3160-3172), a mixture of compound 19 (of 1.03 g, 3.0 mmol), CsF (2.28 g, 15.0 mmol) and mesityl oxide (1,72 ml, 15.0 mmol) in anhydrous acetonitrile (22.5 ml) is heated at 80°C for 2.5 - 3 hours, during which time the mixture turned from colorless to brown and then to dark red. Analysis by TLC confirms the absence of starting material. The solvent is evaporated in vacuum, the residue is extracted with ethyl acetate and filtered through a pad of Oka and silica using ethyl acetate as eluent. The solvent is evaporated in vacuum and the product purified by gravity column [alumina, hexane/ethyl acetate (2:1)] followed by recrystallization from CH₂Cl₂/hexane and obtain brown crystals (550 mg, 42%): TPL 124-125°C;¹H NMR δ a 1.08 (s, 3H), 1,19 (s, 3H), 2,11 (s, 3H), 2,37 (d, J=17,4 Hz, 1H), 2,56 (d, J=17,4 Hz, 1H), 3.15 in (m, 1H), 3,39 (m, 1H), 5,20 (m, 1H), 6,21 (m, 1H), of 6.68 (m, 1H), 7,10 (m, 2H), of 7.70 (m, 2H), by 8.22 (user, 1H);¹³C NMR δ 23,9, 24,2, 24,8, 31,6, 36,8, 51,2, 91,1, 94,2, 109,1, 117,8, 122,2, 122,4, 130,1, 135,9, 137,5, 206,7; FAB-MS observed 440,0605 calculated 440,0597; Analytical calculated for C₁₈H₂₁IN₂O₃: C, 49,1; H, 4,8; N, 6,4. Found: C, 49,1; H, 4,7, N, 6,3.

1,3 .3m-Trimethyl-7-(4-itfinal)-2,3-dihydropyridin (21). Following the procedure for β-unsubstituted pyrrole (Strachan, J.P. et al., J.Org.Chem. 2000, 65, 3160-3172), a solution of compound 20 (220 mg, 0.50 mmol) in anhydrous THF (5.0 ml) in an argon atmosphere is treated with NaOMe (135 mg, 2.5 mmol) and the mixture is stirred for 1 hour at room temperature (flask). In the second flask combine TiCl₃(8.6 wt.% TiCl₃28 wt.% HCl, and 3.8 ml, 2.5 mmol, of 5.0 molar equivalents) and H₂O (20 ml), NH₄OAc (˜15 g) is added as a buffer to bring the pH to 6.0, and then add THF (5 ml). Nitronates the anion of compound 20, formed in the first flask, transferred via cannula into a solution of TiCl₃with the buffer in the second flask. Additional THF (3 is l) is added to the flask with nitronate anion, and also supernatant is transferred into a solution of TiCl₃with the buffer. The resulting mixture was stirred at room temperature for 6 hours in an argon atmosphere. The mixture is then extracted with ethyl acetate and the combined organic layers washed with saturated aqueous NaHCO₃, water, saturated salt solution, and then dried (MgSO₄). The solvent is removed under reduced pressure at room temperature. The crude product was passed through a short column [alumina, hexane/ethyl acetate (2:1)] to obtain a light green solid product (80-92 mg, 45 -50%): TPL 140-142°C;¹H NMR δ of 1.18 (s, 6H), 2,22 (s, 3H), 2,52 (s, 2H), of 5.89 (s, 1H), of 6.26 (m, 1H), 6,85 (m, 1H), 7,19 (m, 2H), 7,69 (m, 2H), 11,09 (user, 1H);¹³C NMR δ 20,7, 29,1, 29,7, 41,2, 53,7, 90,3, 102,3, 108,6, 118,5, 122,2, 127,5, 130,4, 136,8, 137,4, 161,9, 177,2; FAB-MS observed 390,0595 calculated 390,0593 (C₁₈H₁₉IN₂); λ_abs(toluene) 352 nm.

The General procedure for obtaining chlorine: Zn(II)-17,18-Dihydro-18,18-dimethyl-5-(4-were)-12-(4-itfinal)porphyrin (Zn-22). Following the General procedure (Strachan, J.P. et al., J.Org.Chem. 2000, 65, 3160-3172), to a solution of compound 11 (110 mg, 0.20 mmol) in 7.5 ml of anhydrous THF/MeOH (4:1) at room temperature in small portions add excess NaBH₄(100 mg, 2.6 mmol). The reaction is followed by TLC [alumina, hexane/ethyl acetate (3:1)], and at its completion, the mixture was quenched with cold water (˜10 ml), then extrage the comfort distilled CH ₂Cl₂(C ml). The combined organic layers washed with saturated salt solution (50 ml), dried (K₂CO₃within 2-3 min and concentrated in vacuo at room temperature to leave the resulting carbinol 11-OH ˜1-2 ml of CH₂Cl₂. RR 1 (45 mg, 0.24 mmol) is dissolved in a few ml of anhydrous CH₃CN and unite with 11-OH, then add additional anhydrous CH₃CN with obtaining overall, 22 ml of CH₃CN. The solution was stirred at room temperature in an argon atmosphere and add TFU (20 μl, 0.26 mmol). The reaction is followed by TLC [alumina, hexane/ethyl acetate (3:1)], which after 25-30 minutes demonstrates the disappearance of the EAP and the appearance of bright spots just under the LC. The reaction mixture was quenched with a 10% aqueous solution of NaHCO₃and extracted with distilled CH₂Cl₂(C ml). The combined organic layers washed with water, saturated salt solution, dried (Na₂SO₄) and the solvent is removed in vacuum at room temperature. The residue is dissolved in 14 ml of anhydrous toluene in an argon atmosphere, and then add AgIO₃(848 mg, 3.0 mmol), piperidine (300 μl, 3.0 mmol) and Zn(OAc)₂(550 mg, 3.0 mmol). The resulting mixture is heated at 80°C for 2.5 hours. The reaction is followed by TLC [silica, hexane/CH₂Cl₂, (1:1); shows one individual p is taken green spot] and absorption spectroscopy (bands at ˜ 410 nm and ˜610 nm). The color change of the reaction mixture from red to green indicates the formation of chlorine. The reaction mixture is cooled to room temperature, and then passed through a short column (silica, CH₂Cl₂). The main fraction concentrate and again subjected to chromatography [silica, hexane/CH₂Cl₂(2:1, then 1:1)]. The obtained blue-green solid product is dissolved in a minimum amount of CH₂Cl₂and precipitated by adding hexane to obtain a green-blue solid (25 mg, 18%).¹H NMR δ a 2.01 (s, 6H), to 2.67 (s, 3H), 4,48 (s, 2H), 7,50 (d, J=7.2 Hz, 2H), to $ 7.91 (d, J=7.2 Hz, 2H), 7,95 (d, J=8.1 Hz, 2H), of 8.09 (d, J=8.1 Hz, 2H), 8,51 (d, J=4,2 Hz, 1H), 8,67 (m, 5H), 8,78 (d, J=of 4.2 Hz, 1H), of 9.56 (s, 1H); LD-MS observed 693,78; FAB-MS observed 694,0580 calculated 694,0572 (C₃₅H₂₇IN₄Zn); λ_abs(toluene)/411 nm (log ε=5,33, the width of the peak at half-maximum level = 18 nm), 616 (4,76), λ_em619, 674 nm.

Comments on get chlorine: (1) the Full recovery of the carbonyl in the predecessor of the EAP to the corresponding carbinol sometimes requires additional NaBH₄. The recovery must be completed before carrying out the reaction of obtaining chlorine. (2) When removing the EAP organic layers dried in K₂CO₃(carbinol decomposes quickly when drying over Na₂SO₄or MgSO₄). Is the most important not to bring the solution EAP before drying, because the EAP in the dried form is absolutely unstable. (3) the EAP when removing and condensing the solution, giving dihydropyran-a, as a rule, are either yellow or bright red; these solutions lead to the obtaining of chlorins with a good yield. In some cases there is additional darkening, in this case, get low outputs of chlorines.

General conditions for metallation. 17,18-Dihydro-18,18-dimethyl-5-(4-were)-12-(4-itfinal)porphyrin (22). To a solution of Zn-22 (10 mg, 14.4 mmol) in anhydrous CH₂Cl₂(5 ml) is added TFU (58 mmol, 0.75 mmol). After stirring for 30 min at room temperature (monitored by TLC and UV-visible spectroscopy) the reaction is quenched with a 10% aqueous solution of NaHCO₃(20 ml) and extracted with CH₂Cl₂. The combined organic layers washed with water, dried (Na₂SO₄) and concentrate. Extra cleaning (if necessary) is achieved by chromatography in a short column [silica, hexane/CH₂Cl₂(1:1 then 1:2)], to obtain a green solid (8.0 mg, 88%).¹H NMR δ -2,15 (user, 1H), -1,85 (user, 1H), 2,07 (s, 6H), 2,69 (s, 3H), with 4.64 (s, 2H), 7,54 (d, J=7.5 Hz, 2H), 8,04 (m, 4H), 8,16 (d, J=8.1 Hz, 2H), 8,64 (d, J=4.5 Hz, 1H), cent to 8.85 (AB Quartet, J=4.5 Hz, 2H), 8,90 (m, 3H), 8,99 (s, 1H), 9,84 (s, 1H); LD-MS observed 633,88; FAB-MS observed 632,1434 calculated 632,1437 (C₃₅H₂₉IN₄); λ (toluene)/414 nm (log ε=5,13, the width of the peak at half-maximum level = 34 nm), 505 (4,12), 643 (4,65); λ_em646, 682 nm.

Zn(II)-17,18-Dihydro-18,18-dimethyl-5-(4-were)-12-{4-[2-(trimethylsilyl)ethinyl]phenyl}porphyrin (Zn-23). Following the General procedure for obtaining chlorine, the reaction of 13-OH [prepared from 13 (130 mg, 0.25 mmol)and compound 1 (57 mg, 0.30 mmol) gives the blue solid product (36 mg, 22%).¹H NMR δ of 0.35 (s, 9H), 2,03 (s, 6H), to 2.67 (s, 3H), of 4.54 (s, 2H), 7,50 (d, J=8.1 Hz, 2H), 7,86 (d, J=8.1 Hz, 2H), of 7.96 (d, J=7.5 Hz, 2H), 8,16 (d, J=8.1 Hz, 2H), 8,53 (d, J=4.5 Hz, 1H), at 8.60 (s, 1H), 8,68 (m, 2H), 8,73 (d, J=4.5 Hz, 1H), up 8.75 (s, 1H), 8,80 (d, J=4.5 Hz, 1H), 9,63 (s, 1H); LD-MS observed 665,74; FAB-MS observed 664,2007 calculated 664,2001; (C₄₀H₃₆IN₄SiZn); λ_abs(toluene)/413 nm (log ε=5,31, the width of the peak at half-maximum level = 21 nm), 618 (4,77), λ_em622, 676 nm (Φ_f=0,11).

17,18-Dihydro-18,18-dimethyl-5-(4-were)-12-{4-[2-(trimethylsilyl)ethinyl]phenyl}porphyrin (23). Following the General procedure demetilirovania, sample Zn-23 (10 mg, 15 µmol) of green solid product (8.0 mg, 89%).¹H NMR δ -2,15 (user, 1H), -1,85 (user, 1H), 0,35 (s, 9H), 2,07 (s, 6H), 2,69 (s, 3H), with 4.64 (s, 2H), 7,53 (d, J=7.5 Hz, 2H), to $ 7.91 (d, J=8.1 Hz, 2H), 8,03 (d, J=8.1 Hz, 2H), of 8.27 (d, J=8.1 Hz, 2H), 8,64 (d, J=4.5 Hz, 1H), 8,84 (AB Quartet, J=4.5 Hz, 2H), 8,89 (m, 2H), 8,93 (s, 1H), 8,99 (s, 1H), 9,86 (s, 1H); LD-MS observed 604,31; FAB-MS observed 602,2880 calculated 602,2866 (C₄₀H₃₈IN₄Si); λ_abs(toluene)/415 nm (log ε=equal to 4.97, the width of the peak at the level at which maximum = 36 nm), 506 (3,96), 647 (4,49); λ_em648, 685, 715 nm (Φ_f=0,25).

Zn(II)-17,18-Dihydro-18,18-dimethyl-5-(4-were)-8-(4-itfinal)porphyrin (Zn-24). Following the General procedure for obtaining chlorine, the reaction of the 17-OH [prepared from compound 17 (110 mg, 0.20 mmol)and compound 1 (45 mg, 0.24 mmol) gives the blue solid product (30 mg, 24%).¹H NMR δ 2,03 (s, 6H), to 2.67 (s, 3H), 4,51 (s, 2H), 7,50 (d, J=8.1 Hz, 2H), 7,86 (d, J=8.1 Hz, 2H), of 7.97 (d, J=8.1 Hz, 2H), 8,02 (d, J=8.1 Hz, 2H), 8,54 (s, 1H), at 8.60 (s, 1H), 8,69 (m, 4H), 8,97 (d, J=4,2 Hz, 1H), being 9.61 (s, 1H); LD-MS observed 696,39; FAB-MS observed 694,0607 calculated 694,0572 (C₃₅H₂₇IN₄Zn); λ_abs(toluene)/416 nm (log ε=5,13, the width of the peak at half-maximum level = 18 nm), 607 (4,49); λ_em609,661 nm.

17,18-Dihydro-18,18-dimethyl-5-(4-were)-8-(4-itfinal)porphyrin (24). Following the General procedure demetilirovania, sample Zn-24 (10 mg, 14.4 μmol) of green solid product (7.5 mg, 83%).¹H NMR δ -2,20 (user, 1H), -1,96 (user, 1H), 2,07 (s, 6H), 2,68 (s, 3H), 4,63 (s, 2H), 7,53 (d, J=8.1 Hz, 2H), 7,86 (d, J=8.7 Hz, 2H), 8,03 (m, 4H), 8,64 (s, 1H), cent to 8.85 (m, 3H), 8,91 (s, 1H), 8,99 (s, 1H), 9,17 (d, J=4.5 Hz, 1H), 9,83 (s, 1H); LD-MS observed 631,58; FAB-MS observed 632,1454 calculated 632,1437 (C₃₅H₂₉IN₄); λ_abs(toluene)/410 nm (log ε=5,11, the width of the peak at half-maximum level = 32 nm), 504 (4,01), 638 (4,48); λ_em639, 679, 702 nm.

Zn(II)-17,18-Dihydro-18,18-dimethyl-2-(4-itfinal)-5-(4-were)-12-{4-[2-(trimethylsilyl)ethinyl]phenyl}porphyrin (Zn -25). Following the General process is ur to obtain chlorine, the reaction of 13-OH [prepared from compound 13 (103 mg, 0.20 mmol)and compound 21 (86 mg, 0.22 mmol) gives the blue solid product (42 mg, 24%).¹H NMR δ of 0.36 (s, 9H), to 1.96 (s, 6H), to 2.67 (s, 3H), 4,48 (s, 1H), 7,50 (d, J=7.5 Hz, 2H), 7,82 (d, J=8.7 Hz, 2H), 7,86 (d, J=8.1 Hz, 2H), of 7.97 (d, J=8.1 Hz, 2H), 8,02 (d, J=8.1 Hz, 2H), 8,13 (d, J=7,8 Hz, 2H), 8,51 (d, J=4,2 Hz, 1H), 8,63 (s, 1H), 8,67 (s, 1H), 8,70 (s, 2H), 8,78 (d, J=4,2 Hz, 1H), 9,58 (s, 1H); LD-MS 866,34; FAB-MS observed 866,1257 calculated 866,1280 (C₄₆H₃₉IN₄SiZn); λ_abs(toluene)/417 nm (log ε=5,32, the width of the peak at half-maximum level = 21 nm), 629 (4,90); λ_em635, 691 nm.

17,18-Dihydro-18,18-dimethyl-2-(4-itfinal)-5-(4-were)-12-{4-[2-(trimethylsilyl)ethinyl]phenyl}porphyrin (25). Following the General procedure demetilirovania, sample Zn-25 (11.0 mg, 13.7 mmol) to give a green solid (8.0 mg, 78%).¹H NMR δ -1,95 (user, 1H), -1,70 (user, 1H), 0,36 (s, 9H), 2,0 (s, 6H), 2,68 (s, 3H), 4,60 (s, 2H), 7,53 (d, J=8.1 Hz, 2H), to $ 7.91 (d, J=8.1 Hz, 2H), 8,03 (d, J=8.1 Hz, 2H), 8,07 (d, J=8.1 Hz, 2H), compared to 8.26 (d, J=8.1 Hz, 2H), to 8.62 (d, J=4,2 Hz, 1H), 8,81 (s, 1H), 8,88 (d, J=4,2 Hz, 1H), 8,91 (s, 1H), of 8.95 (s, 1H), 8,96 (s, 1H), 9,84 (s, 1H); LD-MS 804,02; FAB-MS observed 804,2157 calculated 804,2145 (C₄₆H₄₁IN₄Si); λ_abs(toluene)/422 nm (log ε=5,09, the width of the peak at half-maximum level = 34 nm), 509 (4,08), 655 (4,68); λ_em660, 726 nm.

An alternative approach to chlorins, which bear a pair of dimethyl castle, eliminate the side with ligerie meso - and β -substituents and can be used in model systems, including the interaction tierralinda complex pyrrole, functionalized for subsequent processing (Montfortc, F.-P.; Kutzki, O. Angew. Chem. Int. Ed. 2000, 39, 599-601; Abel, and Montfortc, F.-P. Tetrahedron Lett. 1997, 38, 1745-1748: Schmidt, W.; Montfortc, F.-P. Synlett 1997, 903-904).

All of the above is an illustration of the present invention, and should not be construed as a limitation. Scope of the present invention is defined by the following further claims, with equivalents of the claims should be included in it.

1. Solar cell containing

(a) a first substrate containing a first electrode;

(b) a second substrate containing a second electrode, the first and second substrates arranged to form a space between them, and at least one item from (i) of the first substrate and the first electrode and (ii) of the second substrate and the second electrode is transparent;

(c) the layer of rods for the accumulation of light, is electrically connected with a first electrode, and each of these rods for the accumulation of light contains a polymer of the formula I

where m is at least 1;

X¹represents a group is split charge having an excited state with energy equal to or lower than the X²;

X²-X^m+1represent the chromophores;

X¹electrically connected with a first electrode;

and this solar cell further comprises (d) an electrolyte in the specified space between the first and second substrates.

2. The solar cell according to claim 1, additionally containing mobile charge carrier in the specified electrolyte.

3. Solar cell containing

(a) a first substrate containing a first electrode;

(b) a second substrate containing a second electrode, the first and second substrates arranged to form a space between them, and at least one item from (i) of the first substrate and the first electrode and (ii) of the second substrate and the second electrode is transparent;

(c) the layer of rods for the accumulation of light, is electrically connected with a first electrode, and each of these rods for the accumulation of light contains a polymer of the formula I

where m is at least 1;

X¹is a group of charge separation, with an excited state with energy equal to or lower h the m a X ²;

X²-X^m+1represent the chromophores;

X¹electrically connected with a first electrode; and

X¹-X^m+1chosen in such a way that with injection of either electrons or holes of X¹in the first electrode, the corresponding hole or electron from X¹tolerated at least to X²;

specified solar cell further comprises (d) an electrolyte in the specified space between the first and second substrates and

(e) a mobile charge carrier in the specified electrolyte.

4. The solar cell according to claim 3, where X^m+1associated with the specified second electrode.

5. Solar cell containing

(a) a first substrate containing a first electrode;

(b) a second substrate containing a second electrode, with alasannya the first and second substrates arranged to form a space between them and at least one item from (i) of the first substrate and the first electrode and (ii) of the second substrate and the second electrode is transparent;

(c) the layer of rods for the accumulation of light, is electrically connected with a first electrode, and each of these rods for the accumulation of light contains a polymer of the formula I

where m is at least 1;

X¹is a group of charge separation, with an excited state with energy equal to or lower than the X²;

X²-X^m+1represent the chromophores;

X¹electrically connected with a first electrode and

X^m+1electrically connected to the specified second electrode;

and this solar cell further comprises (d) an electrolyte in the specified space between the first and second substrates.

6. The solar cell according to claim 3 or 5, where X¹-X^m+1chosen so that during the injection of electron from the X¹in the first electrode, the corresponding hole of the X¹transferred to X^m+1.

7. The solar cell according to any one of paragraphs. 1 and 3, or 5, where X¹-X^m+1contain porphyrin macrocycles.

8. The solar cell according to any one of claims 1 and 3, or 5, where the specified electrolyte contains an aqueous electrolyte.

9. The solar cell according to any one of paragraphs. 1 and 3, or 5, where the specified electrolyte contains a nonaqueous electrolyte.

10. The solar cell according to any one of claims 1 and 3, or 5, where the specified electrolyte contains a polymer electrolyte.

11. The solar cell according to any one of claims 1 and 3, or 5, where the specified electrolyte comprises a solid body.

12. The solar cell is about any one of claims 1 and 3, or 5, where specified, a solar cell-free fluid in the specified space between the first and second substrates.

13. The solar cell according to any one of claims 1 and 3, or 5, where the X¹split charge is a bunk sandwich the connection.

14. The solar cell according to any one of claims 1 and 3, or 5, where these rods for the accumulation of light is oriented essentially perpendicularly to the second electrode.

15. The solar cell according to any one of claims 1 and 3, or 5, where these rods for the accumulation of light are linear.

16. The solar cell according to any one of claims 1 and 3, or 5, where these rods for the accumulation of light have a length of not more than 500 nm.

17. The solar cell according to any one of claims 1 and 3, or 5, where X¹-X^m+1each independently contains porphyrin macrocycle selected from the group consisting of formula X, formula XI, formula XII, formula XIII, formula XIV, formula XV, formula XVI and formula XVII

where M is selected from the group consisting of Zn, Mg, Pd, Sn and Al, or M is absent;

To¹- ⁸independently selected from the group consisting of N, O, S, Se, Te, and CH;

S¹- S¹⁶each independently selected from the group consisting of H, aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perftoran the La, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido and carbamoyl, and where each pair of S¹and S²S³and S⁴S⁵and S⁶S⁷and S⁸may independently form a ring arenas, and this ring arenas can, in turn, being unsubstituted or substituted one or more times by Deputy selected from the group consisting of H, aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perforare, pyridyl, cyano, thiocyanato, nitro, amino, alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido and carbamoyl; and where S¹-S¹⁶may contain a bridging group, covalently linked to adjacent the porphyrin macrocycle X¹-X^m+1or a bridging group, covalently linked with a first electrode.

18. The solar cell according to any one of claims 1 and 3, or 5, where these rods for the accumulation of light are internal rectifiers energy of the excited state.

19. The solar cell according to any one of claims 1 and 3, or 5, where these rods for the accumulation of light are internal rectifiers for holes.

20. The solar cell according to any one of claims 1 to 19, where each of these rods for the accumulation of light contains the polymer of formula I with the main chain of connected edges monomial is the moat discoid shape.

21. The solar cell according to any one of claims 1 to 20, where m is at least 2, and these rods for the accumulation of light are internal rectifiers energy of the excited state.

22. The solar cell according to any one of claims 1 to 21, where these rods for the accumulation of light are chemically bound with the specified electrode.

23. The solar cell according to any one of claims 1 to 22, where these rods for the accumulation of light is oriented essentially perpendicularly to the first electrode.

24. Electrical device that contain

(a) a solar cell according to any one of claims 1 and 3 or 5 and

(b) a circuit electrically connected with the solar specified element.

25. Electrical device according to paragraph 24, where said chain contains a resistive load.