Macromolecular compounds with nucleus-shell structure, synthesis method thereof, use thereof as semiconductors in electronic functional element and as electronic functional element

FIELD: chemistry.

SUBSTANCE: invention relates to macromolecular compounds with a nucleus-shell structure. The invention discloses macromolecular compounds with a nucleus-shell structure, whereby the nucleus has a macromolecular dendritic and hyperbranched structure based on carbon or based on silicon and carbon is bonded to at least three, in particular at least six external atoms through a carbon-based coupling chain (V) which is selected from a group consisting of straight and branched alkylene chains with 2-20 carbon atoms, straight or branched polyoxyalkylene chains, straight or branched siloxane chains or straight or branched carbosilane chains, with straight chains based on carbon oligomeric chains (L) with conjugated double bonds on the entire length. Conjugated chains (L) in each separate case are bonded at the end opposite the coupling chain (V) to one more, specifically, aliphatic, arylaliphatic or oxyaliphatic chain (R) without conjugated double bonds. The chains (V), (L) and (R) form the shell. The invention also discloses a method for synthesis of the said compounds.

EFFECT: novel organic compounds which can be synthesised using conventional solvents and have good semiconductor properties.

16 cl, 2 ex

 

The invention relates to the field of semiconductors for electronic functional elements, in particular macromolecular compounds with nuclear shell structure, method of production thereof, their use as semiconductors in electronic functional element and as an electronic functional element.

The field of molecular electronics has been evolving rapidly in the last 15 years with the opening of the organic conducting and semiconducting compounds. At this time, we found a large number of compounds which have electro-optical properties and properties of semiconductors. It is clear to all that molecular electronics is not intended to displace conventional semiconductor electronic component on the basis of silicon. Instead, assume that molecular electronic components will discover new applications, they can be used for application on large surfaces where desired structural flexibility, the possibility of processing at low temperatures and low cost. Currently, semiconductor organic compounds are being developed for such applications as organic field-effect transistors, organic luminescent diodes, sensors, and photovoltaic elements. Due to the simplicity of structure and integration of the radio field-effect transistors in integrated organic semiconductor circuits become possible low-cost solutions for smart cards or tags, who until recently it was impossible to implement based on silicon technology due to cost and lack of flexibility of the silicon functional elements. Similarly, organic field-effect transistors can be used as switching elements in a flexible matrix screens with a large surface. Overview on organic semiconductors, semiconductor integrated circuits and other applications, for example, in Electronics, 2002, Vol 15, ñ.38.

Field-effect transistor is a three-electrode element, in which the conductance of the thin conductive channel between the two electrodes (called "source" and "drain") is controlled by a third electrode (it is called "shutter"), separated by a thin dielectric layer from the conducting channel. The most important characteristic properties of a field-effect transistor is represented by the mobility of charge carriers, which decisively determine the speed of the switching transistor, and the ratio between the currents in the on and off state, the so-called "on/off" - attitude.

In organic field-effect transistors to date has used two large class of compounds. All these connections have an associated structural units in the long chain of the pair, and they are subdivided on the basis of molecular mA the son and of the structure on conjugate polymers and conjugated oligomers.

The oligomers have a generally uniform molecular structure and molecular weight of less than 10,000 daltons. The polymers are generally made up of chains with the same recurring structural units and with a certain distribution of molecular masses. However, the transition from oligomers to polymers not marked clearly.

Often the difference between oligomers and polymers is reflected in the fact that these compounds are fundamentally different ways of processing. The oligomers is usually possible to vaporize, and is applied to the substrate by methods that use the evaporation process. The polymer is usually compounds that, regardless of their molecular weight, it is impossible to translate into the vapor state and are therefore applied in other ways. If we are talking about polymers, as a rule, strive to ensure that they represented compounds soluble in the liquid medium, for example in organic solvents, and then they might be able to use appropriate methods of application. Very widely distributed, for example, a spraying method using centrifugal force ("Spin-Coating"). A particularly elegant method presents the application of semiconductor compounds using the technique of inkjet printers. In accordance with this method the solution of semiconductor compounds is applied to su the strata in the form of fine droplets and dried. This method allows for the structuring during application. The description of this method of applying a semiconductor compounds can be found, for example, in Nature, Vol 401, s.

In General liquid chemical methods attributed to the wide range of possibilities in regard to the simplicity and accessibility of the organic semiconductor integrated circuits.

An important prerequisite for obtaining high-quality organic semiconductor circuits is extremely high purity compounds. In semiconductors, the order phenomena play an important role. Complications in the uniformity of the orientation of the connections and boundary contours of the particles lead to a sharp deterioration of the properties of semiconductors, resulting organic semiconductor circuits that have been built using compounds with insufficient high degree of purity, are generally unhealthy. The remaining impurities can, for example, to enter the charges in the semiconductor connection (doping) and reduce thus the ratio between the currents in the on and off or they can become traps for charges and result in a sharp decrease in mobility. In addition, contamination can trigger the reaction semiconductor compounds with oxygen, and the boot is of the view with the properties of the oxidant can oxidize semiconductor compounds and can thus lead to a reduction of their storage periods, the possibility of processing and operation.

Typically, the purity requirements are so high that achieving it through such well-known in polymer chemistry methods, as hillshade, pereosazhdeniya and extraction, usually becomes impossible. In contrast, the oligomers representing molecular homogeneous and often volatile compounds, can be relatively easily purified by sublimation or chromatography.

The following are some important representatives of semiconducting polymers. For polyfluorenes and fluorenone copolymers, such as polymer based on 9,9-dioctylfluorenyl and bithiophene (I)

achieved values of mobility of charges (hereinafter also abbreviated mobility) to 0.02 cm2/·With (Science, 2000, Vol 290, s), and regioregular poly(3-hexyl-thiophene-2,5-diele) (II)

even up to 0.1 cm2/·With (Science, 1998, Vol 280, s). Polyfluorene, polyfluorene copolymers and poly(3-hexylthiophene-2,5-diyl) after application of the solution form, as almost all long-chain polymers, good films, so they are easily recycled. But they, being of high molecular weight polymers with the distribution of molecular masses, cannot be purified by vacuum sublimation and poorly purified using chromatography.

Important PR is by some members of the Swiss oligomeric semiconductor compounds are, for example, oligothiophenes, in particular the oligothiophenes with alkyl substituents in the quality of end groups in accordance with the formula (III)

where n means the number from four to six and Rxmeans alkyl group, or alkoxygroup,

and pentacene (IV)

Typical mobility, for example, α,α'-vexilar-, -quinque and-sexithiophene are in the range from 0.05 to 0.1 cm2/·C.

Mesophases, in particular liquid crystal phase, is likely to play a special role in the semiconductor organic compounds, but so far in this regard, specialists have no full understanding. For example, it was reported that the maximum achieved to date, the mobility obtained on crystals of α,α'-dihexylfluorene (Chem. Mater., 1998, Volume 10, s), and these crystals at a temperature of 80°C while crystallize from the liquid crystal phase (Synth. Met., 1999, Volume 101, s). Especially high mobility can be obtained by using single crystals, for example, describes the mobility equal to 1.1 cm2/·For single crystals of α,α'-sexithiophene (Science, 2000, Vol 290, s). If the oligomer is applied from a solution, the values of mobility are often dramatically reduced. As a rule, the lower semiconductor properties when processors is ke oligomeric compounds from solution explain the moderate solubility and a low tendency to form films of oligomeric compounds. For example, the emergence of inhomogeneity explain deposition from solution during drying (Chem. Mater., 1998, Volume 10, s).

In accordance with this experiments conducted on the Association properties of semiconducting polymers, which are well processed and easily form a film with properties of semiconducting oligomers. In U.S. patent No. 6025462 described conducting polymers with star-shaped structure consisting of a branched core and shell of the conjugated side groups. However, they are not free from some drawbacks. If the side groups are formed adjacent structures without departing from the substituents, the compounds formed are poorly soluble or completely insoluble and not processed. Substitution of paired units side groups, of course, is accompanied by increased solubility, but the side groups create steric hindrance, making internal disorder and morphological abnormalities, which have a negative impact on the semiconducting properties of these compounds.

Application for international patent No. 02/26859 A1 relates to polymers in the form of paired back wheel is attached to an aromatic conjugated chain. These polymers have diarylamino side groups, which allow electronic conduction. However, these connections do not godets is the role of semiconductors due to diarylamino side groups.

In the application for the European patent No. 1398341 described semiconductor dendrimers, which can be processed from solutions.

However, there is a need for other improved compounds in which the United semiconducting properties known oligomers with the ability to process and to the formation of good films that are characteristic of known polymers.

The objective of the invention is to develop other organic compounds, which can be recycled using conventional solvents and which have good semiconducting properties. Such organic semiconductor compounds can be successfully used for application on large surfaces.

In particular, it would be desirable that these compounds form a high-quality coating thickness and morphology and were suitable for use in electronics.

It was unexpectedly found that organic compounds exhibit the desired properties in cases where they have nuclear shell structure and include a kernel built from multi-functional structural units, and a sheath of connective circuits and linear conjugated oligomeric chains, which are in each case attached to the terminal point link through a flexible unpaired chain.

The object from which retene are macromolecular compounds with nuclear shell structure, moreover, the kernel (K) with basic macromolecular structure based on silicon and/or carbon connected to at least three, in particular at least six, external atoms through the connecting circuit (V) carbon-based linear, carbon-based oligomeric chains (L) passing through the entire length of the conjugated double bonds and conjugated chain (L) in each case connected on opposing connecting chain (V) end with another, especially aliphatic, arylaliphatic or oxyaliphatic chain (R), not containing conjugated double bonds.

In a preferred embodiment, the organic macromolecular compounds can be oligomers or polymers. In the framework of the invention, the term oligomer refers to compounds with an average molecular weight of less than 1000 daltons, the term polymer refers to compounds with an average molecular weight of 1000 daltons or more. Depending on the method of determination of average molecular mass can be srednecenovogo molecular mass (Mnor the mass-average molecular mass (Mw). In this case we are talking about srednetsenovoj molecular mass (Mn).

In the framework of the invention the concept of nuclear shell structure refers to the structure at the molecular level, that is, about what about relates to the structure of the molecule itself.

The concept of the end point of joining the linear conjugated oligomeric chain refers to the point on the terminal structural unit of linear oligomeric chains with conjugated double bonds, through which it is already impossible one connection to another structural unit. The meaning of the concept "leaf" refers to the most remote from the core. Linear oligomeric chain with spaced along its length conjugated double bonds hereinafter will be also abbreviated to be called the linear conjugated oligomeric chain.

In a preferred embodiment, the new compounds have the nuclear shell structure of the General formula (Z)

where K is an n-functional core,

V means connecting chain

L means linear conjugated oligomeric chain,

R denotes a linear or branched alkyl residues with the number of carbon atoms ranging from two to twenty, one - or multi-unsaturated alkeneamine remains with the number of carbon atoms ranging from two to twenty, CNS remains with the number of carbon atoms ranging from two to twenty, arylalkyl remains with the number of carbon atoms ranging from two to twenty, or oligoamine remains with the number of carbon atoms ranging from two to twenty or polyester residues with the number of carbon atoms ranging from two to twenty,

n means an integer equal to three or more is three, in the preferred case is equal to six or more than six.

When this sheath of new compounds, which are preferred, consists of n units-V-L-R, each of which is attached to the kernel.

As examples for n equal to three, or n is equal to six, presents the structure of formula (Z-3) or (Z-6)

where K, V, L and R have the above significance.

Such compounds are designed so that turned out to be United together composed of multifunctional structural units, that is branched, the core, the connecting chain, linear conjugated oligomeric chains and unpaired chain.

Composed of multi-functional structural units of the core in the preferred case has a dendritic or hyperbranched structure.

Hyperbranched structures and their receipt of specialists known. Hyperbranched polymers or oligomers are particularly structure, which is determined by the structure of the original monomers. As monomers used the so-called ABnthe monomers, i.e. monomers containing different functional groups a and B. one Of them functional group (A) part of the molecule only once, while the other functional group (C) is found in it several times (n times). Both functional the groups a and b can be linked together by chemical bonding, for example, in the polymerization. As a consequence of the structure of the monomers during polymerization are formed branched polymers with a tree structure, the so-called hyperbranched polymers. The point of branching in hyperbranched polymers are irregular, they do not rings, and the ends of the chains they are almost exclusively functional group Century Hyperbranched polymers, their structure, issues related to the formation of branches, and their nomenclature is described on the example of hyperbranched polymers on the basis of silicones in the work L.J.Mathias, T.W.Carothers, Adv. Dendritic Macromol. (1995), 2, 101-121, and cited in the literature.

In the framework of the present invention the preferred hyperbranched structures are hyperbranched polymers.

In fact the invention of the dendritic structures are synthetic macromolecular structures that are formed by sequential joining of two or more monomers to each of the already-attached monomers, resulting at each stage of the exponential growth in the number of monomer end groups and eventually formed a spherical tree structure. As a result of this form of three-dimensional macromolecular structure with groups that have branching points and thus with p is irregular regularity grow from the center to the periphery. Typically, the building of such structures is well-known specialist ways from layer to layer. The number of layers is usually called generations. The number of branches in each of the layers, and the number of end groups is increased in each subsequent generation. Due to their regular structure of the dendritic structure can have special benefits. Dendritic structures, methods for their preparation and nomenclature specialist known, and are described, for example, G.R.Newkome and others, Dendrimers and Dendrons, Wiley-VCH, Weinheim, 2001.

Built from dendritic or hyperbranched structures core next will be abbreviated to be called dendritic or hyperbranched core, can be used in the structure described, for example, in U.S. patent No. 6025462. For example, these hyperbranched structure, as Polyphenylene, polyether ketones, polyether described, for example, in U.S. patent No. 5183862, No. 5225522, and No. 5270402, aramids such as, for example, described in U.S. patent No. 5264543 such polyamides, such as described in U.S. patent No. 5346984, such polycarbosilane or polycarbosilane, as, for example, described in U.S. patent No. 6384172, or such polyarylene, as, for example, described in U.S. patent No. 5070183 or No. 5145930, or dendritic patterns, as, for example, polyarylene, polyester polyarylene or polyamidoamine described in patents school is No. 4435548 and No. 4507466, as well as such polyethylenimine, as, for example, described in U.S. patent No. 4631337.

However, to build a dendritic or hyperbranched core can be used and other structural units. The role of dendritic or hyperbranched core consists predominantly to carry a range of functional groups and thus serve a matrix, which is applied to the connecting chain with linear conjugated oligomeric chains, so that they can form nuclear shell structure. Linear conjugated oligomeric chain through accession to the matrix is already in the ordered state, which increases their efficiency.

Dendritic or hyperbranched core carries a number of functional groups, which are the attachment points that can be used to link through the connecting circuit with linear conjugated oligomeric chains. In particular, dendritic core, as the core, built of hyperbranched structures, shall be not less than three, but in the preferred case, at least six functional groups.

In dendritic or hyperbranched core preferred 1,3,5-phenylene the first structural units (formula V-a) and structural units of formula (V-b) to (V-e), with several identical or different structural units of the t (V-a) to (V-e) connected

moreover, in the structural units of the formulas (V-e) and (V-d) a, b, C and d independently of one another denote 0, 1, 2, or 3.

Marked with*provisions in formulas (V-a) to (V-e)and the following formulas represent the attachment point. The structural unit (V-a) to (V-e) communicate through them with each other or through a connecting chain with linear conjugated oligomeric chains (L).

The following are examples of dendritic cores (k), constructed from the structural units (V-a).

In marked*provisions are bound through the connecting circuit (V) with linear conjugated oligomeric chains (L).

The shell of the new compounds consists of connecting circuits, linear conjugated oligomeric chains and unpaired chains.

In the preferred case, the connecting circuit (V) have high flexibility, i.e. they are characterized by high (inside)molecular mobility, and because of this affect the geometrical arrangement of the segments L-R around the nucleus as In the framework of the invention the concept of flexibility refers to the (inside)molecular mobility.

The role of the connecting circuits are suitable in the General case of a linear or branched chains, which are characterized by the following structural attributes:

carbon atoms, United simple bonds with carbon atoms,

- hydrogen atoms connected to carbon atoms,

- oxygen atoms, the United simple bonds with carbon atoms,

the silicon atoms, the United simple bonds with atoms of carbon and/or

the silicon atoms, the United simple bonds with oxygen atoms,

and which in the preferred case, contain in the amount of from six to sixty atoms, and which in the preferred case does not contain ring structures.

Suitable coupling circuit in a particularly preferred case are linear or branched alkylene chain with the number of carbon atoms ranging from two to twenty, as, for example, ethylene, n-butylene, n-hexylene, n-octylaniline and n-dodecylamine chain, linear or branched polyoxyalkylene chain, for example oligoamine chain containing segments-OCH2-, -Och(CH3)- or-O-(CH2)4-, linear or branched siloxane chain, such as chain dimethylsiloxane structural units, and/or linear or branched carbosilane circuit, i.e. a circuit in which there is a simple relationship between silicon atoms and carbon atoms, the silicon atoms and the carbon chains may be arranged alternately in the statistical or block order, for example, it can be structureagency-SiR 2-CH2-CH2-CH2-SiR2-.

The role of the linear conjugated oligomeric chains in principle fit all chains, which are the structural units that constitute themselves electrically conductive or semiconductive oligomers or polymers. They represent, for example, unsubstituted or substituted polyaniline, polythiophene, polyethyleneoxide, Polyphenylene, polypyrrole, polyacetylenes, polyazomethine, polyphenylenevinylene, polyfluorene, which can be used in the form of homopolymers, or homologoumena, or in the form of copolymers or cooligomers. Examples of such structures, which in the preferred case can be used as linear conjugated oligomeric chains are chains consisting of structural units of General formula (VI-a) to (VI-e) in the amount of from two to ten, in the preferred case from two to seven

thus R1, R2and R3may be the same or different and mean a hydrogen atom, a linear or branched alkyl group with the number of carbon atoms from one to twenty, or alkoxygroup with the number of carbon atoms from one to twenty, in the preferred case, they are the same and signify a hydrogen atom,

R4may be the same or different and mean atom odor is Yes, linear or branched alkyl group with the number of carbon atoms from one to twenty or alkoxygroup with the number of carbon atoms from one to twenty, in the preferred case, they represent a hydrogen atom or alkyl group with carbon atoms from six to twelve and

R5means a hydrogen atom or a methyl or ethyl group, in the preferred case mean a hydrogen atom.

Sign*in formulas (VI-a) to (VI-e) denotes the attachment point through which the structural unit (VI-a) to (VI-e) are related to each other in the linear conjugated oligomeric chains or, respectively, through which the ends of the chains associated with the kernel or with unpaired chain.

Particular preference is given paired linear oligomeric chains comprising structural units of the unsubstituted or substituted 2,5-thiophenol (VI-a) or (VI-b), or unsubstituted or substituted 1,4-fenelonov (VI-e). Set at the beginning of names, numbers, 2,5 - or 1,4 - point position, through which the connection of the structural units.

Hereinafter, the term "substituted", unless otherwise specified, refers to the substitution of alkyl groups, particularly alkyl groups with carbon atoms of from one to twenty, or alkoxygroup, in particular alkoxygroup with the number of carbon atoms is kind of from one to twenty.

Particular preference is given paired linear oligomeric chains with structural units of the unsubstituted 2,5-thiophenol (VI-a) or 2,5-(3,4-ethylenedioxythiophene) (VI-b).

Linear conjugated oligomeric chain, in the General formula (Z) is indicated by the symbol L on the terminal connection points are in each case associated with the non-coupled circuit (R). Preferably, when unpaired chains have a high degree of flexibility, i.e. they have a high (inside)molecular mobility, due to this they interact with the solvent molecules and provide increased solubility. In the framework of the invention, the flexibility should be understood as (inside)molecular mobility. Unpaired chains, which end position is connected with the linear conjugated oligomeric chains, represent a linear or branched aliphatic, unsaturated or arylaliphatic chain with the number of carbon atoms ranging from two to twenty, in the preferred case from six to twenty, in which can be embedded atoms of oxygen. Preference is given to aliphatic and oxyaliphatic groups, i.e. alkoxygroup, or a linear or branched aliphatic groups, which have built-in oxygen atoms, such as groups based on a simple oligoesters or polyesters. Special preference from the W unbranched alkyl groups with carbon atoms from two to twenty or alkoxygroup with the number of carbon atoms ranging from two to twenty. Examples of suitable circuits are such alkyl groups as n-exilda, n-heptylene, n-aktiline, n-nanlina, n-decile and n-Godzilla group, or such alkoxygroup as n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-dellarciprete and n-dodecyloxy.

Examples of the structural elements of L-R, consisting of linear conjugated oligomeric chains, which are in each case connected at the terminal point of connection with unpaired chain, are the structural elements of the General formulae (VI-a-R) and (VI-b-R):

where R has the above for the General formula (Z) value, and

p means an integer from 2 to 10, in the preferred case from 2 to 7.

Preferred implementations of the present invention is represented by compounds with structures that dendritic core contain siloxane and/or carbosilane structural units, as the connecting chain is a linear, unbranched alkylene group, as linear conjugated oligomeric chains - unsubstituted oligothiophene chain and oligo(3,4-ethylenedioxythiophene) chain comprising from 2 to 4 thiophene or, respectively, (3,4-ethylenedioxythiophene) structural units, as well as alkyl groups with carbon atoms from six to twelve as the flexible unpaired chains.

As relevant examples are the following compounds of the formula (Z-4-a) and (Z-X-a):

,

and (Z-X-a) n, m and p may be the same or different, independently from each other, they represent an integer from 1 to 100, in the preferred case from 3 to 20, in a particularly preferred case from 4 to 12. In preferred embodiments of relevant to the invention of compounds of at least two of the variables n, m and p are identical, and in most preferred embodiments, the same n, m, and R.

Preferably, when new connections are conductors or semiconductors. In a particularly preferred case, the objects of the invention are semiconductor compounds. Particular preference is given to such compounds, in which the mobility of charge carriers is not less than 10-4cm2/·C. the charge Carriers are, for example, a positive hole charges.

Corresponding to the invention of the macromolecular compounds are usually soluble in ordinary solvents, such as chloroform, toluene, benzene, diethyl ether, dichloromethane or tetrahydrofuran, and therefore they are very well suited for processing in the form of solutions. In particular, it was unexpectedly found that even new special is connected to the I with the unsubstituted thiophene or accordingly, 3,4-ethylenedioxythiophene structural units in the linear conjugated oligomeric chains show very good solubility and steric difficult side chains do not violate the internal order or morphology. In accordance with these new connections are good semiconducting properties and, in addition, they are characterized by an outstanding ability to form films. So they are very well suited for coating large areas. In addition, corresponding to the invention of semiconductor compounds show excellent thermal stability and showed himself well against aging.

The advantage of corresponding to the invention of compounds, for example in comparison with the known semiconductor dendrimers on the application for European patent No. 1398341, also lies in the fact that due to the increased flexibility due to the additional coupling circuits in the shell can be achieved a higher order in the semiconductor layer corresponding to the invention compounds. This can have a positive impact on the properties of the final product.

In principle, to obtain the corresponding invention compounds can be used in different ways.

For example, the first can be p the obtained structural elements V-L-R and then held their accession to the kernel (K). Also, however, for the case of the dendritic core of the finished structural element V-L-R or part of its structure can be first attached, for example, a structural unit called monterona, and at the next stage, several such mantendremos can be combined into a final structure. Mantendremos referred to as structural unit, which includes part of the dendritic structure and which can be used for the Assembly of dendritic structure.

In principle, the method of obtaining does not have a decisive influence on the properties relevant to the invention compounds. In the framework of the described synthetic routes can be implemented a number of options. For example, there is a possibility to change the sequence of separate stages of obtaining, when, for example, unpaired flexible circuit attached to the paired linear oligomeric chains at the last stage of receipt.

Depending on the resulting structure may, for example, be expedient accession unpaired flexible chains (R) conjugate to a linear oligomeric chains (L) at an earlier stage, because the flexible circuit (R) increase the solubility of the starting materials and ease thanks to this, obtaining relevant to the invention of compounds.

To build the kernel, consisting of multifunctional structural units, to bind it is with connecting circuits (V), for linking the connecting circuits (V) with linear conjugated oligomeric chains (L) and to join him unpaired flexible chains (R) can be used a number of chemical reactions, which, in principle, known to the specialist. In the preferred case, these chemical reactions are represented by reactions of ORGANOMETALLIC compounds. Their advantage is that they usually occur in mild reaction conditions and with high selectivity, and in this case, using them can be achieved and high outputs.

Corresponding to the invention compounds can be obtained and so that the accession process was first formed separate structural elements K, V, L and R, and that they were in original compounds, should join together in a reaction only in the form of incomplete structures or in functionalized form.

So, for example, linear oligomeric chain (L) may be formed only in the process of joining two correspondingly functionalized for such a connection areas of the circuit. With this method of holding the Assembly corresponding to the invention of compounds, preference is also given to chemical reactions involving ORGANOMETALLIC reagents.

In addition, the object of the invention is a method for retrieving relevant to the invention connected to the deposits, characterized in that get them involving ORGANOMETALLIC reagents.

For ORGANOMETALLIC reactions may be necessary in the introduction of the relevant functional groups in the dendritic or hyperbranched core, in the connection chain, linear conjugated oligomeric chains and flexible unpaired chain and after that it will be possible to join them.

Such functional groups are, for example, alkeline group, a halogen group such as chlorine, bromine and iodine group, in the preferred case of the bromine groups, such ORGANOTIN groups, such as trimethyl - or triethylamine group, such organosilicon groups, as, for example, trimethylsilyl or triethylsilyl group, or organoboron groups, as, for example, boranova acid.

Among ORGANOMETALLIC reactions for a combination of individual structural elements relevant to the invention of compounds of particular preference is the combination of reaction Comedy, which is a combination of two bromine groups via Grignard reagents with participation of such palladium catalysts, such as dichloride, 1,1-bis(diphenylphosphino)ferienparadies(II), and the combination of the Suzuki reaction, during which the boron-containing group combines the bromine groups in basic medium in the presence of palladium catalysts. The ways these two reactions combination of specialist known. The hydrosilation alkenyl groups also constitute a preferred ORGANOMETALLIC reaction to connect the individual structural elements in obtaining relevant to the invention compounds. How hydrosilation also known specialist.

Examples of implementation relevant to the invention methods are described in the examples received.

Preferably, when the intermediate products between the individual stages of obtaining and end connections are cleaned. This can be used such known methods as distillation, sublimation, recrystallization, extraction, pereosazhdeniya, flushing or chromatography. In the preferred case, the intermediate products and the final connection is cleaned by distillation, sublimation and chromatography, as in this case can be obtained the maximum degree of purification.

This has the advantage compared to the known semiconductor polymers, because with a simple and affordable cleaning methods relevant to the invention compounds can be obtained with a high degree of purity and, as such, they become suitable for use in semiconductor applications.

Suitable the e to the invention compounds can form mesophases (mesomorphic phase) that is, they form a physical phase between the solid and liquid state. They are also known as liquid crystal phases, and they determine the destination corresponding to the invention of compounds. In the preferred case, corresponding to the invention the compounds form a liquid crystal phase in a range from 50°C to 300°C, in a particularly preferred case in the range from 80°C to 180°C.

Corresponding to the invention of compounds soluble in the usual solvents, such as chloroform, toluene, benzene, diethyl ether, dichloromethane or tetrahydrofuran, to form solutions with a concentration of not less than 0.1%, in the preferred case, at least 1%, in the most preferred case, not less than 5%.

During the evaporation of their solutions corresponding to the invention compounds can form high-quality layers of uniform thickness and morphology and, therefore, suitable for use in electronics.

And, finally, the object of the invention is also the application of the relevant invention compounds as semiconductor in such electronic functional elements, such as field-effect transistors, light-emitting elements of the devices, for example organic luminescent diodes or photovoltaic cells, lasers and sensors.

In the preferred case, corresponding to the invention compounds are used for the peaceful purposes in the form of layers.

In order corresponding to the invention compounds can fully ensure their functioning in the role of semiconductors, they must have sufficient mobility, for example not less than 10-4cm2/·C. the Mobility of the charges may be, for example, determined according to the method described in Mrore and C.E.Swenberg, Electronic Processes in Organic Crystals and Polymers, 2nd ed., s-713 (Oxford University Press, new York, Oxford, 1999).

In the practical use of the compounds applied to the intended substrate, such as an electrical or electronic structures of silicon substrates, polymer films or glass plates. In principle, the application can be used by any means. In the preferred case, corresponding to the invention of compounds is applied from the liquid phase, i.e. from the solution, and then evaporated the solvent. Application of the solution can be conducted by known methods, for example by means of a spray, dipping, stamping and screen printing. In particular, preference is given to application by using centrifugal force and by the way inkjet printing.

After applying the layers relevant to the invention compounds can be further modified, for example, by heat treatment, for example, by passing through the liquid crystal phase, and the and by structuring for example, laser ablation.

In addition, the object of the invention is electronic functional elements containing relevant to the invention substances as semiconductors.

Examples

5-(10-Undecenyl)-2,2'-Bethoven get known method (Synthesis, 1993, s, J.Mater. Chem. 2003, Volume 13, s). Synthesis carbosilane dendrimers G5 (All) 128 (see example 2A) and hyperbranched carbosilane polymers Si-Hyper-Allyl (see example 2B) described in Polym. Sci., ser. A, 1998, Vol 40, s and in J. Polym. Sci., part a, 2000, Vol. 38, S. 741. The entire reaction apparatus before using heated using conventional techniques in an atmosphere of inert gas and washed with nitrogen.

Example 1. The connection is obtained with V-L-R-structure

Example 1A. Getting 4,4,5,5-tetramethyl-2-[5'-(10-undecenyl)-2,2'-beteen-5-yl]-1,3,2-dioxaborolane (Und-2T-Bor)

In a dry nitrogen-filled flask of 500 ml, equipped with a mechanical stirrer, cooled acetone with dry ice and 100 ml of anhydrous tetrahydrofuran to -75°C. are Added dropwise to 6.4 ml of 2.5 M solution of utility in hexane and continue stirring for 20 minutes. Then for 1.5 hours added dropwise a solution of 5-undecenyl-2,2-bithiophene (5.10 g, 16.0 mmol) in 120 ml of anhydrous tetrahydrofuran and stirred for further 30 minutes at -75°C. then for 1 hour, warmed to 0°C INOVA cool light yellow solution to -75°C. Portions add 3,91 g isopropoxyaniline so that the solution temperature did not rise above -72°C., and after completion of the addition, continue stirring at -72°C for 30 minutes. Without stopping the stirring, remove the cooling bath and allow the reaction mixture to slowly warm up. After 3 hours the reaction mixture was added to 500 ml of diethyl ether, is added a mixture of 200 ml of ice water and 16 ml of 1 N. hydrochloric acid, shaken and separated phases. The organic phase is twice washed with water to 200 ml, dried with anhydrous sodium sulfate, filter and remove the solvent. Get to 7.35 g of product as a solid blue color.

1H NMR (deuterochloroform, tetramethylsilane was/ppm): 1,22-1,45 (overlapping peaks with a maximum at 1,283, 14N). 1,345 (C., 12 H), 1,672 (m, J=7.5 Hz, M=5, 2H), 2,037 (sq, J=7.2 Hz, 2H), 2,781 (t, J=7,3 Hz, 2H), 4,928 (D., J=10.3 Hz, 1H), 4,991 (D., J=17,1 Hz, 1H), 5,811 (m. 1H), 6,676 (D., J=3,4 Hz, 1H), 7,037 (D., J=3,9 Hz, 1H), 7,152 (D., J=3,9 Hz, 1H), 7,496 (D., J=3,4 Hz, 1H).

Example 1B. Getting 5-hexyl-5'-undec-10-EN-1-yl-2,2':5',2":5",2"'-quadrati-dryer (Und-4T-Hex)

In a dry nitrogen-filled device, consisting of a three-neck flask with a volume of 250 ml with a magnetic stirrer, reflux condenser and enter the Septum, download 4.61 in g of 2-hexyl-5-bromothiophene, saturated with nitrogen and a nitrogen atmosphere are added 0,090 g of tetrakis(triphenylphosphine)p is lady. Then through the system enter the Septum using a syringe sequentially added a solution of 7.35 g of compound from example 1A, 120 ml of toluene under nitrogen and 21 ml of 2 M solution of sodium carbonate under nitrogen and left overnight while boiling under reflux. After cooling, the reaction mixture was added to a mixture of 200 ml of ice water, 45 ml of 1 N. hydrochloric acid and 300 ml of toluene, shaken and twice washed with water to 200 ml of the Resulting yellow precipitate is filtered off, dissolved in 350 ml of toluene, dried over magnesium sulfate, filter and remove the solvent. Obtain 1.28 g solid yellow (Und-4T-Hex)1.

Liquid organic phase is dried over magnesium sulfate, filtered, remove the solvent and the residue is recrystallized from 900 ml of n-hexane. Obtain 5.8 g of a solid substance brown-yellow (Und-4T-Hex)2. After repeated recrystallization from toluene get to 4.81 g of yellow powder, which according to the analysis consists of (Und-4T-Hex) and triphenylphosphine. The output of 1.28+4,81=6,09 g (77% of theory).

Mass spectrum (Und-4T-Hex)1: m/z=566 (M·+)+traces and 634 582.

1H NMR ((Und-4T-Hex)1, deuterochloroform, tetramethylsilane was/ppm): 0,896 (t, J=6,9, MN), 1,23-1,44 (overlapping peaks with a maximum at 1,289, 18 H), 1,682 (m, J=7,3, M=5, 4H), 2,040 (sq, J=7,0, 2H), 2,791 (t, J=7,6, 4H), 2,840 (sq, J=7,2, 2H), 4,931 (D., J=9,8,1H), 4,989 (D., J=17.1 to,1H), 5,814 (m, 1H), 6,681 (D., J=3,9. 2H), 6,975 (D., J=,4,2H), 6,988 (D., J=3,9,2H), 7,029 (D., J=3,9,2H).

Example 1B: Obtain 1-[11-(5"'-hexyl-2,2':5',2":5",2"'-quatation-5-yl)undecyl]-1,1,3,3-tetramethyldisiloxane(HSi-Und-4T-Hex)

In a dry nitrogen-filled three-neck flask with a volume of 250 ml with a magnetic stirrer, reflux condenser, a tube for input of nitrogen and a thermometer load of 1.25 g of compound from example 1B (Und-4T-Hex) and 40 ml of anhydrous toluene, the solution is saturated with nitrogen and heated to 70°C. To the clear solution was added 16 ml (12.0 g) tetramethyldisiloxane and 10 μl of a platinum complex with cycloisomerisation in cycloisomerisation (content of platinum 3-3,5%) (produced by ABCR, Karlsruhe) and stirred for 21 hours. After removal of the solvent receive 2,59 g solid yellow color, which is dissolved in hot methanol and chromatographic on silica gel at 50°C. Receive 1,365 g (87% of theory) of a solid yellow color.

Mass spectrum, field desorption: the main peak with m/z=700 (M•+), fewer with m/z=566 and traces of m/z=714, 774 and 903.

1H NMR (deuterochloroform, tetramethylsilane was/ppm): 0,056 (C., 6N), 0,160 (D., J=2,5 Hz, 6N), 0,526 (t, J=7,6 Hz, 2H), 0,896 (t, J=6,85, 3H), 1,21-1,44 (overlapping peaks with a maximum at were 1,268, 22 H), 1,681 (m, J=7,5, M=5, 4H), 2,789 (t, J=7,6 Hz, 4H), 4,676 (m, J=2,8 Hz, M=7,1H), 6,680 (D., J=3,9,2H), 6,974 (D., J=3,4, 2H), 6,987 (D., J=3,9,2H), 7,028 (D., J=3,4,2H).

Example 2. Obtaining according to the current invention compounds with K-(V-L-R) n-structure

Example 2A. Gaining relevant to the invention connection with dendritic core and C-(V-L-R)n-structure

In a dry nitrogen-filled three-neck flask with a volume of 100 ml with a magnetic stirrer, reflux condenser, a tube for input of nitrogen and a thermometer download 702 mg (1.0 mmol) of the compound from example 1B (HSi-Und-4T-Hex), saturated with nitrogen, and was added 1.3 ml (82 mg solids) solution of dendrimer G5(A11)128. The solvent is removed in vacuum, the flask with nitrogen. Add 17 ml of anhydrous toluene and saturate the solution with nitrogen. The mixture is heated to 60°C. to the clear solution add 10 ál of platinum divinyltetramethyldisiloxane complex in xylene (manufactured by ABCR, Karlsruhe) with the content of platinum 2-2,4% and 20 hours heat the solution at 80°C. After that, add 70 ml of ethanol, 4 hours, refluxed, the resulting suspension is filtered while hot and dried the filter residue in high vacuum (625 mg solid yellow (Z-4-a)1). From the filtrate the solvent is distilled off (at residue 216 mg).

(Z-4-a)1dissolved in 15 ml of toluene at 80°C and added dropwise to 70 ml of ethanol. Formed suspension, which is filtered. The filter residue is dried in high vacuum and from the filtrate the solvent is distilled off. This operation is repeated DV the times. Receive 486 mg (92% of theory) of a solid substance in yellow (Z-4-a)2.

Example 2B. Gaining relevant to the invention connection with surgras-extensive core and C-(V-L-K)n-structure

Mn=11800 and Mw=28400, while n, m and p vary from 1 to 100. The total formula of the parent compounds (Si-Hyper-All) match

Sin(CH3)nHn-1[-(CH2)3-]n-1[-(CH2)3-]n+1.

As described in example 2A, in 15 ml of toluene spend interaction 631 mg of the compound from example 1B (HSi-Und-4T-Hex, 0.9 mmole), 76 mg of hyperbranched polymer Si-Hyper-Allyl (76 mg, 0.6 mmole of allyl groups) and 10 μl of platinum divinyltetramethyldisiloxane complex in xylene content of platinum 2-2,4% (produced by ABCR, Karlsruhe) and produce the target product. The output of 465 mg (94% of theory) of the compound (Z-X-a).

1. Macromolecular compounds with nuclear shell structure, the core has a macromolecular dendritic or hyperbranched structure of carbon-based or silicon-based and carbon and related to at least three, in particular at least six, external atoms through the connecting circuit (V) on the basis of carbon, which is selected from the group consisting of linear or branched alkilinity chains with the number of carbon atoms is kind of from two to twenty, linear or branched polyoxyalkylene chains, linear or branched siloxane chain or a linear or branched carbosilane circuits, linear, carbon-based oligomeric chains (L) passing through the entire length of the conjugated double bonds and conjugated chain (L) in each case connected on opposing connecting chain (V) end with another, in particular, aliphatic, arylaliphatic or oxyaliphatic chain (R) without conjugated double bonds, with the circuit (V), (L) and (R) form a shell.

2. Compounds according to claim 1, characterized in that they have the nuclear shell structure of the General formula (Z)

which means n-functional core,
V means connecting chain
L means linear conjugated oligomeric chain,
R denotes a linear or branched alkyl residues with the number of carbon atoms ranging from two to twenty, one - or multi-unsaturated alkeneamine remains with the number of carbon atoms ranging from two to twenty, CNS remains with the number of carbon atoms ranging from two to twenty, arylalkyl remains with the number of carbon atoms ranging from two to twenty or oligoamine remains with the number of carbon atoms ranging from two to twenty or polyester residues with the number of carbon atoms ranging from two to twenty,
n oznachaet is an integer, equal to three or more than three.

3. Compounds according to claim 1, characterized in that the core contains as the basis for dendritic structure of 1,3,5-phenylenebis structural unit.

4. Compounds according to claim 1, characterized in that the hyperbranched structure is formed hyperbranched polymer.

5. Compounds according to claim 1 or 2, characterized in that the shell comprises a linear conjugated oligomeric chains chains with structural units of the unsubstituted or substituted 2,5-thiophenol or unsubstituted or substituted 1,4-fenelonov.

6. Compounds according to claim 1 or 2, characterized in that the shell comprises a linear conjugated oligomeric chains chains with structural units of the unsubstituted 2,5-thiophenol or 2,5-(3,4-ethylenedioxythiophene).

7. Compounds according to claim 1 or 2, wherein the linear conjugated oligomeric chains are chains, including the length of the chains from two to seven Monomeric structural units.

8. Compounds according to claim 1 or 2, wherein the linear conjugated oligomeric chains are in each case connected on the terminal points of binding to the same or different branched or unbranched alkyl groups or alkoxygroup.

9. Connection of claim 8, wherein alkyl groups or alkoxygroup represent unbranched who skylinee group with the number of carbon atoms ranging from two to twenty or alkoxygroup with the number of carbon atoms ranging from two to twenty.

10. Connection of claim 8, wherein alkyl groups or alkoxygroup represent n-hexoloy, n-decile or n-dodecyloxy group.

11. Compounds according to claim 1 or 2, characterized in that the connecting chain (V) are ethylene, n-butylene, n-hexylene, n-ActiveMovie or n-dodecylamine chain, oligoamine chain containing segments-och2-, -Och(CH3)- or-O-(CH2)4-or is it chain with dimethylsiloxane structural units.

12. Compounds according to claim 1 or 2, characterized in that they are semiconductors.

13. The connection section 12, characterized in that the charge carriers in semiconductors have a mobility of not less than 10-4cm2/(·).

14. Method of preparing compounds according to one of claims 1 to 13, characterized in that the connection with the nuclear shell structure prepared as in reactions with ORGANOMETALLIC compounds.

15. The method according to 14, characterized in that the connection with the nuclear shell structure is obtained using the combination reaction of Comedy.

16. The method according to 14, characterized in that the connection with the nuclear shell structure is obtained using the combination for the Suzuki reaction.



 

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1 tbl, 9 ex

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< / BR>
(patent N 4220600, CL

FIELD: chemical technology.

SUBSTANCE: invention describes a method for preparing metallopolycarbosilanes. Method involves interaction of polycarbosilanes with molecular mass above 200 Da and with the main chain consisting of links of the formula: [-(R)2Si-CH2-] wherein R means hydrogen atom (H), (C1-C4)-alkyl or phenyl groups with metalloorganic compounds of the formula MXz wherein M means transient metal of III-VIII group of Periodic system; z = 2-4; X means NR12 wherein R1 means (C1-C4)-alkyl group in organic solvent medium at temperatures from 20°C to 400°C under pressure from 5.05 MPa to 0.2 kPA. Method provides preparing fusible soluble polymers with homogeneous distribution of chemically bound metal atoms that elicit high capacity for fiber- and film-formation from solutions or melts that are hardened in thermochemical treatment and provides high yield of ceramic residue in pyrolysis (up to 85 wt.-%).

EFFECT: improved preparing method.

1 tbl, 9 ex

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