Compound for organic electronic devices

FIELD: chemistry.

SUBSTANCE: present invention relates to organic electroluminescent devices based on compounds of formula

where Y, Z is selected from N, P, P=O, C=O, O, S, S=O and SO2; Ar1, Ar2, Ar3 are selected from benzene, naphthaline, anthracene, phenanthrene, pyridine, pyrene or thiophene, optionally substituted with R1; Ar4, Ar5, Ar6, Ar7 are selected from benzene, naphthaline, anthracene, phenanthrene, pyridine, pyrene, thiophene, triphenylamine, diphenyl-1-naphthylamine, diphenyl-2-naphthylamine, phenyldi(1-naphthyl)amine, phenyldi(2-naphthyl)amine or spirobifluorene, optionally substituted with R1; E is a single bond, N(R1), O, S or C(R1)2; R1 denotes H, F, CN, alkyl, where the CH2 can be substituted with -R2C=CR2 -, -C=C-, -O- or -S-, and H can be substituted with F, optionally substituted aryl or heteroaryl, where R1 can form a ring with each other; R2 denotes H, aliphatic or aromatic hydrocarbon; X1, X4, X2, X3 are selected from C(R1)2, C=O, C=NR1, O, S, S=O, SO2, N(R1), P(R1), P(=O)R1, C(R1)2-C(R1)2, C(R1)2-C(R1)2-C(R1)2, C(R1)2-O and C(R1)2-O-C(R1)2; n, o, p, q, r and t are equal to 0 or 1; s = 1.

EFFECT: obtaining novel compounds - emission layer dopants, and novel electroluminescent devices based on said compounds which emit a blue colour.

18 cl, 91 ex, 6 tbl

 

The invention describes new compounds and their use in organic electronic devices.

The General structure of organic electroluminescent devices are described, for example, in US 4539507, US 5151629, EP 0676461 and WO 98/27136. However, these devices still exhibit large problems that require immediate solutions through improvements:

1. Efficiency, especially in the case of fluorescent acid (organic light-emitting diodes), remains very low and should be raised.

2. Operating life expectancy remains low, particularly in the case of blue emission, this means that it is still possible to achieve only a simple commercial applications.

3. The operating voltage is high enough in the case of fluorescent acid and, therefore, must be reduced in order to improve efficiency. It is of utmost importance for mobile applications.

4. Many of emitting blue light emitters, which include both aromatic amines and vinyl groups, are thermally unstable and decompose when sublimation or deposition by evaporation. Consequently, the use of these systems is possible only with great loss and with high technical difficulty, if at all possible.

p> 5. The materials for the layer, which provides transport of holes, in accordance with the prior art voltage depends on the thickness of the transport layer. In practice would be desirable large layer thickness, which provides transport of holes. However, this cannot be achieved with the use of the materials in accordance with the prior art by reason associated with this voltage.

As the closest analogue may be mentioned the application of certain kilwinning Idemitsu (for example, WO 04/013073, WO 04/016575, WO 04/018587). In these sources provided a very good service life for devices with a dark blue light. However, these results are extremely dependent on the used material basis, which means that the time service can't be compared as absolute values, but instead always using the optimized system. In addition, these compounds are thermal unstable and cannot evaporate in the absence of decomposition, which, thus, makes it technically very difficult getting acid and, thus, represents an important technical obstacle. An additional obstacle is the color of the emission of these compounds. Although Idemitsu showed a dark-blue emission (CIE interval coordinates 0,15-0,18), it had not been for the m to reproduce these color coordinates in a simple device in accordance with the prior art. In contrast, there was obtained a green-blue emission. It is unclear how the image could be actually received the blue emission when using these compounds.

Thus, a need exists for compounds that emit blue light, which leads to good performance in electroluminescence devices and at the same time ensures a long service life, these compounds can be subjected to processing without any technical problems. It has been unexpectedly discovered that the devices for organic electroluminescence, which include certain compounds mentioned below as emitting blue radiation dopants (deruosi substances) in the material master, have important advantages over the prior art. When using these materials, it is possible to obtain a longer service life with higher efficiency. In addition, these compounds can, in contrast to compounds of the prior art, to be freeze-dried without any noticeable decomposition, even in relatively large quantities, and are thus much easier to handle than the materials in accordance with the prior art. The present invention thus relates to compounds and to their use in acid.

The invention relates to the compounds is contained in the formulas (1)

where we use the following symbols and indices:

Y, Z are identical or different and represent N, R, P=O, PF2P=S, As, As=O, As=S, Sb, Sb=O, Sb=S, Bi, Bi=O, Bi=S, C=O, O, S, Se, Te, S=O, SO2, Se=O, SeO2, Te=O or teo2;

Ar1, Ar2, Ar3are in each case identical or different and represent aryl or heteroaryl group containing from 5 to 24 aromatic ring atoms, which may be substituted by one or more radicals R1;

Ar4, Ar5, Ar6, Ar7are in each case identical or different and represent an aromatic or heteroaromatic ring system containing from 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R1;

E. in each case, identical or different, represents a single bond, N(R1), O, S, C(R1)2Si(R1)2or B(R1);

R1in each case, identical or different, represents H, F, Cl, Br, I, CN, NO2B(OR2)2Si(R2)3, alkyl with non-branched chain alkoxy or dialkoxy group containing from 1 to 40 C atoms, branched or cyclic alkyl group, alkoxy or dialkoxy group containing from 3 to 40 C atoms, each of which which may be substituted by one or more radicals R 2where one or more non-adjacent CH2groups may be replaced by-R2C=CR2-, -C≡C-, Si(R2)2Ge(R2)2, Sn(R2)2, C=O, C=S, C=Se, C=NR2, -O-, -S-, -COO - or-CONR2- and where one or more atoms of N may be replaced by F, Cl, Br, I, CN or NO2or an aromatic or heteroaromatic ring system containing from 5 to 40 aromatic ring atoms, which may be substituted by one or more nonaromatic radicals R1or aryloxy or heteroaromatic group containing from 5 to 40 aromatic ring atoms, which may be substituted by one or more nonaromatic radicals R1or a combination of these systems; two or more substituents R1may form a mono - or polycyclic ring system with one another;

R2in each case, identical or different, represents H, an aliphatic or aromatic hydrocarbon radical containing from 1 to 20 atoms;

X1X4are in each case identical or different and represent a bridge connection that with AG1and AG2defines the cyclic system selected from B(R1), C(R1)2Si(R1)2, C=O, C=NR1, C=C(R1)2, O, S, S=O, SO2N(R1), P(R1), P(=O)R1, P(=S)R1or who is Inacio two, three or four of these groups;

X2X3are in each case identical or different and represent a bridge connection that with AG2and AG3defines a cyclic ring system selected from B(R1), C(R1)2Si(R1)2, C=O, C=NR1C-C(R1)2, O, S, S=O, SO2N(R1), P(R1), P(=O)R1, P(=S)R1or a combination of two, three or four of these groups;

n, o, p are in each case identical or different and represent 0 or 1, provided that n, p and can only be equal to 0 if X1represents a group other than C(R1)2bridge communications, where R1= alkyl radical with an open circuit; n=0 and o=0 and p=0 in this case means that the two radical N or R1present instead of bridging ties;

q, r in each case is equal to 1 if the corresponding Central atom of the group Y or Z is an element of the 5th main group, and in each case are equal to 0, if the corresponding Central atom of the group Y or Z is an element of the 4th or 6th main group;

s is 1, 2 or 3;

t in each case, identical or different, represent 0 or 1, where t=0 means that R1radicals are linked instead of group E; moreover, t=0 if q=0.

For the purpose of this is part II of the invention, aryl group or heteroaryl group denotes an aromatic group or heteroaromatic group, respectively, containing the common aromatic electron system, where the aryl group contains from 6 to 24 C atoms, and the heteroaryl group contains from 2 to 24 C atoms and a total of at least 5 aromatic ring atoms. The heteroatoms are preferably selected from N, O and/or S. For the purposes of the present invention it may be Homo - or heterocyclic ring, for example, benzene, pyridine, thiophene, etc. or it may be a condensed aromatic ring system in which at least two aromatic or heteroaromatic rings, for example, benzene rings are condensed to each other, i.e. have at least one common edge and, thus, is also a common aromatic system. This aryl or heteroaryl group can be substituted or unsubstituted; any present Deputy may also form an additional ring system. Accordingly, such systems, as for example, naphthalene, anthracene, phenanthrene, pyrene, etc. are those which refer to aryl groups for the purposes of the present invention, and quinoline, acridine, benzothiophene, carbazole, etc. are those which refer to heteroaryl groups DL the purposes of the present invention, despite the fact that, for example, biphenyl, fluorene, spirobifluorene etc. are not aryl groups, as there are separate aromatic electron system.

For the purposes of the present invention aromatic ring system contains from 6 to 40 C atoms in the ring system. For the purposes of the present invention heteroaromatic ring system contains from 2 to 40 C atoms and at least one heteroatom in the ring system, provided that the total number of atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and/or S. For the purposes of the present invention, an aromatic or heteroaromatic ring system means a system which does not necessarily aryl or heteroaryl groups, but in which, in addition, a variety of aryl or heteroaryl groups may be interrupted by a short non-aromatic unit (less than 10% of the atoms other than H, preferably less than 5% of the atoms other than H), such as, for example, an atom of C, N or O. Thus, such systems such as 9,9'-spirobifluorene, 9,9-veriflora, triarylamine, dailoy eter, etc. also belong to the aromatic ring systems for the purposes of the present invention.

For the purposes of the present invention With1-C40is an alkyl group, to the th individual atoms N or CH 2groups may also be substituted by the above groups, in particular, preferably mean the radicals methyl, ethyl, n-propyl,-propyl, n-butyl, and-butyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-triptorelin, ethynyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctanol, ethinyl, PROPYNYL, butynyl, pentenyl, hexenyl or octenyl. With1-C40-alkoxy group, in particular, means preferably methoxy, ethoxy, n-propoxy, and-propoxy, n-butoxy, and butoxy, sec-butoxy, tert-butoxy or 2-methylbutoxy. With2-C24-aryl or heteroaryl group, which may be monovalent or divalent depending on the application and may also be substituted by the radicals R1and can be linked to the aromatic or heteroaromatic ring system via any desired positions, means, in particular groups which are derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyran, chrysene, perylene, fluoranthene, tetracene, pentacene, benzo (a) pyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzofuran,studied, of pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, fenotiazina, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naftalizola, phenanthroimidazole, peridiniaceae, pyrazinamidase, khinoksalinona, oxazole, benzoxazole, naftagate, anthracite, phenanthraquinone, isoxazol, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridine, benzodiazapine, pyrimidine, benzoperylene, cinoxacin, pyrazine, phenazine, naphthiridine, Zakarpatya, benzoquinoline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole. For the purposes of the present invention aromatic and heteroaromatic ring system means, in particular, biphenylene, tert-phenylene, fluorene, spirobifluorene, dehydrogenation, tetrahydropyran and CIS - or TRANS-indenopyrene, in addition to the above-mentioned aryl and heteroaryl groups.

Preference is given to compounds of the formula (1)in which the symbols Y and Z, identical or different, represent nitrogen, C=O, FOSFA is R or R=O, in particular, preferably nitrogen, C=O or P=O. Y and Z particularly preferably represent nitrogen.

Preference is also given to compounds of the formula (1)in which the symbols AG1, AG2and AG3, identically or differently, in each case denote an aryl or heteroaryl group containing from 5 to 16 aromatic ring atoms, which may be substituted by one or two radicals R1particularly preferably aryl or heteroaryl group selected from benzene, naphthalene, anthracene, phenanthrene, pyridine, pyrene and thiophene, in particular, benzene, each of which may be substituted by one or two radicals R1. Direct linking between Y, AG1, AG2, AG3and Z, in particular, preferably occurs through the para-position of the benzene (or the corresponding provisions of other aromatic compounds).

In particular, preference is thus given to compounds of the formula (1A)

where the symbols and indices have the same meaning as described above.

Preference is also given to compounds of the Formulas (1) and (1A), in which the symbols AG4, AG5, AG6and AG7, identically or differently, in each case denote an aromatic or heteroaromatic ring system containing from 5 to 16 aromatic ring atoms, trial the amine or spirobifluorene, each of which may be substituted by one or more radicals R1in particular, preferably an aromatic or heteroaromatic ring system selected from benzene, naphthalene, anthracene, phenanthrene, pyridine, pyrene, thiophene, triphenylamine, diphenyl-1-naphthalenamine, diphenyl-2-naphthalenamine, phenyldi(1-naphthyl)amine, phenyldi-(2-naphthyl)amine, each of which can be substituted for R1. Symbols AG4, AG5, AG6and AG7in particular, very preferably denote, identically or differently for each instance, phenyl, 1-naphthyl or 2-naphthyl, each of which may be substituted by one or more radicals R1.

Preference is also given to compounds of the Formulas (1) and (1A)where the index t=0 or in which the index t=1, and the corresponding symbol E denotes a single bond, O, S or N(R1). Very preferably, when preference is given to compounds of the Formulas (1) and (1A)where the index t=0 or in which the index t=1, and the corresponding symbol E denotes a single bond.

Preference is also given to compounds of the formula (1)in which the symbol R1, identically or differently for each case, denotes H, F, CN, alkyl group with a non-branched chain, containing from 1 to 5 C atoms or a branched alkyl group containing from 3 to 5 C atoms, where in each case one is or more non-adjacent CH 2groups may be replaced by-R2C=CR2-, -C=C-, -O - or-S - and where one or more atoms of N may be replaced by F, or a monovalent aryl or heteroaryl group containing from 5 to 16 aromatic ring atoms, which may be substituted by one or more nonaromatic radicals R1where two or more radicals R1can form a ring system with one another; R1in particular, preferably denotes H, F, CN, methyl, tert-butyl or a monovalent aryl or heteroaryl group containing from 4 to 6 C atoms which may be substituted by one or more nonaromatic radicals R1where the two aromatic radical R1can form a ring system with one another, R1in particular, very preferably denotes H, if he is associated directly with one of the groups AG1-AG7.

R1it is preferable if it is associated with a group of X1X2X3and/or X4and preferably represents an alkyl group with a non-branched chain, containing from 1 to 10 C atoms or a branched or cyclic alkyl group containing from 3 to 10 C atoms, where in each case one or more non-adjacent CH2groups may be replaced by-R2C=CR2-,-O - or-S-, and g is E. one or more atoms of N may be replaced by F, or a monovalent aryl or heteroaryl group containing from 5 to 16 aromatic ring atoms, which may be substituted by one or more nonaromatic radicals R1; two radicals R1in this case, can also form a ring system with one another.

Preference is also given to compounds in which p=0 and one of the two indices n and is equal to 1, while the other two indices are equal to 0; in particular, preferably, R and n=0 and o=1.

Particular preference is thus given to the structures of formulas (1b) and (1C), in particular, formula (1C)shown below

where the symbols and indices have the same meaning as described above.

Preference is also given to compounds of the formulas (1) and (1A) to (1C), in which the symbols X1X2X3and X4in each case, identical or different, represent a bridge connection, which together with AG1and AG2or AG2and AG3defines the cyclic system selected from C(R1)2, C=O, C=NR1, O, S, S=O, SO2N(R1), P(R1), P(=O)R1C(R1)2-C(R1)2C(R1)2-C(R1)2-C(R1)2C(R1)2-O, C(R1)2-O-C(R1)2. In particular, preference is given to connect enum formula (1), in which the symbols X1X2X3and X4in each case, identical or different, are selected from C(R1)2N(R1), P(R1) and P(=O)(R1), in particular, particularly preferably C(R1)2and N(R1), in particular, C(R1)2.

In particular, special preference is given to compounds of the formula (1d)

where the symbols and indices have the same meaning as described above.

In the structures of the formula (1d) symbols R1are preferably selected from alkyl groups with non-branched chain, containing from 1 to 10 C atoms or a branched or cyclic alkyl groups containing from 3 to 10 C atoms, where in each case one or two non-adjacent CH2group may be replaced by-R2C=CR2-,-O - or-S-, and where one or more H atoms may be replaced by F, or a monovalent aryl or heteroaryl group containing from 5 to 16 aromatic ring atoms, which may be substituted by one or more nonaromatic radicals R1; two radicals R1in this case, can also form a ring system with one another. The radicals R1are, in particular, preferably selected from unbranched alkyl groups containing from 1 to 4 C atoms, and razvetvlennye the alkyl groups, containing 3 or 4 C atoms, in particular methyl groups and phenyl groups; two or more radicals R1in this case, can form a ring system with one another.

If many of the radicals R1form a ring system with one another, is formed spirotricha. This may be preferable if the radicals R1represent phenyl groups. This gives rise to the formation of structures of General formula (1E)

where the symbols and indices have the same meaning as described above and where each spireites may be substituted by one or more nonaromatic radicals R1.

Preference is also given to compounds of the Formulas (1) and (1A) to (1d), in which the symbol s=1 or s=2. Particular preference is given to compounds in which s=1.

Preference is also given to compounds of the formulas (1) and (1A) to (1E), in which Y=z Special preference is given to compounds in which, in addition, AG4=AG6and, in case of presence of AG5=AG7and, in case of presence, both groups of E are chosen identical.

Examples of preferred compounds of formula (1) represent patterns from (1) to (104)below.

Compounds in accordance with the invention described above, for example, the compounds according to structures(63), (85), (86), (89) and (91)can be used, for example, as comonomers to obtain the corresponding conjugated, partially conjugated or non-conjugated polymers, oligomers, as well as the core of dendrimers. The polymerization in this case preferably carried out using a halogen groups.

Thus, the invention also relates to conjugated, partially conjugated or non-conjugated polymers, oligomers and dendrimers comprising one or more compounds of formula (1), where one or more radicals R1represent the connection formulas (1) to the polymer or dendrimer. The unit structure of formula (1) preferably bound in the polymer using group AG4, AG5, AG6and/or AG7.

These polymers may include the repeating unit. Such a repeating structural unit is preferably chosen from the group which consists of fluorine (for example in accordance with EP 842208 or WO 00/22026), spirobifluorene (for example in accordance with EP 70702, EP 894107 or EP 04028865.6), triarylamines, para-fenelonov (for example in accordance with WO 92/18552), carbazoles (for example in accordance with WO 04/070772 and WO 04/113468), thiophenol (for example in accordance with EP 1028136), dehydrogenation (for example in accordance with WO 05/014689), indenopyrene (for example in accordance with WO 04/041901 and WO 04/113412), aromatic ketones (for example in accordance with WO 05/040302), phenanthrenes (for example in accordance with WO 05/104264) and/or complex compounds of metals in particular, autometallographic complexes of iridium. It should be emphasized in this case that the polymers can also contain many different recurring structural units selected from one or more of the above-mentioned groups.

Compounds in accordance with the invention can be obtained by synthetic methods known to the person skilled in the art, such as, for example, bromination, Suzuki condensation, condensation Hartwig-Buchwald, etc.

Thus, indenopyrene predecessors can be obtained, for example, as shown in the synthesis scheme 1: condensation of the Suzuki benthivorous acid and 1,4-dibromo-2,5-bis(methylcarbamoyl)benzene with subsequent opening of the ring when exposed to strong acids and restore provides obtaining TRANS-indenopyrene, which can be alkylated using ALCI arousih agents. Such can be either galogenidov, for example, Bremerhaven or converted into the corresponding aminosidine with nitriding and recovery. Batteryuniversity can be synthesized via condensation Hartwig-Buchwald connection dibromo, as shown in the synthesis scheme 2.

Containing indenopyrene phosphines and phosphine oxide can be synthesized from debromination by litvinovna and reaction with diarylphosphino, as shown in the synthesis scheme 3. Subsequent oxidation provides a phosphine oxide. In this case, can also be used with other electrophiles, such as, for example, AsCl3, l2, SOCl2, Ar2S2etc. Other compounds in accordance with the invention can be easily synthesized in accordance with these and similar schemes synthesis using processes known to the expert in the field of organic synthesis. In addition, the compounds can be bromirovanii using standard processes, and can also be used as monomers for polymers, oligomers and dendrimers.

The scheme of synthesis 1: Precursors derived indenopyrene

Scheme of synthesis of 2: Connection indenopyrene is and

The scheme of synthesis 3: Connection indenopyrene

The electrophiles, which can undergo similar reactions: AsCl3, Sbl3, BiCl3, l2, aryl2l, SCl2, SOCl2, SO2Cl, Ar2S2, Ar2Se2, Ar2Te2etc.

The compounds of formula (1) can be used in organic electroluminescent devices. A specific application of the compounds in this case depends on the substituents and, in particular, from the selection of the groups Y and Z, as well as from select groups of X1to X4.

In the preferred embodiment of the invention the compound of formula (1) used in the emission layer, preferably in a mixture, at least one additional connection. It is preferable for the compounds of formula (1) in the mixture to be emitting compound (dopants). They are used, in particular, if the symbols Y and Z mean nitrogen.

Preferred bases for fluorescent substances are organic compounds, the issuance of which has a shorter wavelength than that of the compounds of formula (1), or those that do not radiate at all.

Thus, the invention also relates to mixtures of one or more compounds of formula (1) with one or more bases of the fluorescent substances is TBA.

The ratio of the compounds of formula (1) in the mixture of the emitting layer is from 0.1 up to 99.0% by weight, preferably from 0.5 to 50.0% by weight, particularly preferably from 1.0 to 20.0% by weight, in particular from 1.0 to 10.0% by weight. Accordingly, the ratio of the base material of the fluorescent substance layer is from 1.0 to 99.9% by weight, preferably from 5.0 to 99.5% by weight, particularly preferably from 80,0 up to 99.0% by weight, in particular from 90,0 and a 99.0% by weight.

Suitable materials fundamentals of fluorescent substances are those of different classes of substances. Preferred core materials are selected from the classes of oligoaniline (for example, 2,2',7,7'-tetraphenylporphyrin in accordance with EP 676461 or disattenuated), in particular, oligoanilines containing condensed aromatic groups, oligoelements (for example DPVBI or Spiro-DPVBI in accordance with EP 676461), polypodine metal complexes (for example in accordance with WO 04/081017), compounds forming holes (for example in accordance with WO 04/058911), compounds forming the electrons, in particular ketones, phosphine oxides, sulfoxidov etc. (for example in accordance with WO 05/084081 or WO 05/084082), atropisomers (for example, in accordance with the unpublished application EP 04026402.0) or derivatives Bronevoy acid (for example, in accordance with the unpublished the second application EP 05009643.7). Particularly preferred core materials are selected from the classes of oligoanilines containing naphthalene, anthracene and/or pyrene, or atropisomers these compounds, oligoelements, ketones, phosphine oxides and sulfoxidov. Especially preferred are the core materials selected from the classes of oligoanilines containing anthracene and/or pyrene, and atropoisomeric these compounds, phosphine oxides and sulfoxidov.

In addition, it is preferred for compounds of formula (1) be used as the material of the transport of holes and/or as a material injection holes. This is particularly applicable if the symbols Y and Z and/or characters from the X1to X4denote nitrogen. The compounds are also preferably used in the layers of the transport of holes and/or layers of the injection holes. For the purposes of the present invention, the layer of the injection holes is a layer that is directly adjacent to the anode. For the purposes of the present invention, the transport layer of holes is a layer which is located between the layer of injection holes and a layer of electron emission. If the compound of formula (1) is used as the material transport holes or material injection holes, it may be preferable for them to be doped with electron-acceptor compounds, for example, F4-TCNQ or with compounds of campisano in EP 1476881 or EP 1596445.

If the compound of formula (1) is used as the material of the transport of holes in the layer to transport holes, may also be preferred to use a ratio of 100%, i.e. to use this connection in the form of pure material.

It is also preferred to use the compounds of formula (1) as a material of electron transport and/or as a material that blocks the hole for fluorescent and photofluorescent of acid and/or as triplet matrix material for fluorescence of acid. This applies in particular to compounds in which the groups Y and Z represent C=O, P=O or S=O.

The compounds of formula (1) can also be used in the polymers, or as a radiating unit, and/or as a unit of transport holes, and/or units of electron transport.

Preference is also given to organic electroluminescent devices, which are characterized by the fact that many emitting compounds are used in the same layer or different layers, where at least one of these compounds has the structure of formula (1). These compounds, particularly preferable are, in General, many of emission maxima between 380 nm and 750 nm, which ultimately leads to the emission of white light, that is, in addition to the compound of formula (1)at least one additional connection, to the which may be fluorescent or phosphorescent and radiate yellow, orange or red light, can also be used. Particular preference is given to three-layer systems, where at least one of these layers comprises the compound of formula (1) and where the layers exhibit blue, green and orange emission (for the basic structure, see, for example, WO 05/011013). The emitters of the wide range can also be used for acid, emitting white light.

In addition to the cathode, the anode and the radiating layer, the organic electroluminescent device may also include additional layers. Such may represent, for example: layer injection holes, the transport layer holes, the blocking layer holes, a layer of electron transport layer injection of electrons and/or a layer of a charge (T. Matsumoto and others, Multiphoton Organic EL Device Having Charge Generation Layer, IDMC 2003, Taiwan; Session 21 OLED (5)). However, it should be noted in this connection that each of these layers does not necessarily have to be present. Thus, in particular, when using the compounds of formula (1) forming the electron materials fundamentals of very good results can be obtained if the organic electroluminescent device does not include a separate layer of electron transport and emitting layer is directly adjacent to the layer injection of electrons or cathode. Alternatively, the base material may also simultaneously serve is the quality of the material transport of electrons in a layer of electron transport. It is also preferable for the organic electroluminescent device, when it does not include a separate layer to transport holes, but also to the emitting layer directly adjoined with a layer of introduction holes or anode. It is also preferred for the compounds of formula (1) be used simultaneously as dopant in sluchayem layer and in the quality of the connection, which creates holes (either as pure substance or as a mixture) in the transport layer of holes and/or layer injection holes.

Preference is also given to an organic electroluminescent device, which is characterized by the fact that one or more layers coated using the process of sublimation. The materials are deposited by evaporation in vacuum sublimation device at a pressure below 10-5mbar, preferably below 10-6mbar, particularly preferably below 10-7mbar.

Preference is also given to an organic electroluminescent device, which is characterized by the fact that one or more layers coated when using OVPD process (application of organic matter in the vapor phase) using sublimation using a carrier gas. In this case, the materials are applied at a pressure of from 10-5mbar to 1 bar.

Preference is also given to the organic the WMD electroluminescent device, which is characterized by the fact that one or more layers obtained from a solution, such as, for example, coating by means of centrifuging or by using the desired printing process, such as, for example, raster print, flexographic printing or offset printing, but particularly preferred is LITI (light-induced thermal forming images, printing using thermal transfer or inkjet printing. Soluble compounds of the formula (1) are necessary for these purposes. High solubility can be achieved with an acceptable substitution compounds. These processes for obtaining layers are particularly well-suited for polymers.

Compounds in accordance with the invention have the following surprising advantages over the prior art when used in organic electroluminescent devices:

1. The performance of these devices is higher compared with systems in accordance with the prior art.

2. The stability of the respective devices is higher compared with systems in accordance with the prior art, which is particularly evident in the significantly longer service life.

3. When using compounds in accordance with the invention, as the material is the means of transport of holes in the layer to transport holes and/or layer injection holes were found, what voltage is independent of the thickness of the corresponding layer to transport holes and/or injection of holes. In contrast, the materials in accordance with the prior art, relatively large thickness of the layer to transport holes or injection of holes give a significant increase in voltage, which in turn leads to a lower efficiency of acid.

4. Connections can be well sublimated without significant decomposition, they are therefore more tractable and thus more acceptable for use in acid than the materials in accordance with the prior art. Having no desire to be limited to a particular theory, we hypothesize that the higher thermal stability can be attributed to the absence of olefinic double bonds.

In the text of this application and in the examples below, the goal was to use the connection in accordance with the invention in respect of acid and the corresponding displays. Despite this restriction of the description, for a specialist in the field of technology is possible, without resorting to inventive creativity, to use the compounds in accordance with the invention for other purposes in excellent electronic devices such as organic transistors with controllable field (O-FET), organic thin-film t is ancestoral (O-TFT), organic light-emitting transistor (O-LET), organic integrated circuits (O-ICS), organic solar cells (O-SC), organic devices with quenching field (O-FQD), light emitting electrochemical cells (LEC), organic photoreceptors or organic laser diodes (O-lasers), which are mentioned only as an example.

The present invention also relates to the use of compounds in accordance with the invention in the respective devices, and these devices by itself.

In more detail, the invention is explained using the following examples, without intending to be limited as such.

Examples:

The following syntheses were carried out in a protective gas atmosphere, unless otherwise noted. The raw materials can be purchased from ALDRICH or ABCR (palladium(II) acetate, di-tert-butylphosphine, amines, inorganic substances, solvents). 6,12-dihydro[1,2b]indenopyrene receive in accordance with the method Hadizad and others, Org. Lett. 2005, 7(5), 795-797, [1,2b]indenopyrene-6,12-dione was produced using the method Deuschel and others, Helv. With/g/. Acta 1951, 34, 2403, 2-bromo-4,4'-di-tert-butylbiphenyl obtained using the method Tashiro, etc., J. Org. Chem. 1979, 44(17), 3037, 1,4-dibromo-2,5-biodanza obtained using the method Chanteau and others, J. Org. Chem. 2003, 68(23), 8750, 3,9-dibromo-5,11-dimethylindole[3,2-b]carbazole get similarly obtaining 3,9-dibro the -5,11-bondagecontrol[3,2-b]carbazole using the method of Li et al. Adv. Mat. 2005, 17(7), 849.

Example 1: 2,8-bis(diphenylamino)-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluoren

a) 6,6,12,12-tetramethyl-6,12-dihydroindeno|1,2b]fluoren

Getting exercise is similar to getting 9,9-dimethylfuran of 6,12-dihydroindeno[1,2b]fluorene, dimethylsulfate and sodium hydroxide in accordance with JP 08113542. Output 86,0% of theoretical; purity 98% in accordance with1H-NMR.

b) 2,8-dibromo-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluoren

The solution 155,9 g (1260 mmol) of sodium carbonate in 1000 ml of water was added to the solution 122,0 g (393 mmol) 6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluorene in 1800 ml of dichloromethane. Was added dropwise of 56.4 ml (1100 mmol) of bromine diluted with 200 ml dichloromethane, at +5°C in the absence of light and under vigorous stirring, the mixture was stirred for further 6 hours, the precipitate was filtered with suction and washed three times with 300 ml of a mixture of water:ethanol (1:1, by vol.:vol.), and then three times with 300 ml of ethanol. Output: 178,1 g (380 mmol), to 96.8% of theoretical; purity: 99% in accordance with1H-NMR.

C) 2,8-bis(diphenylamino)-6,6,12,12-tetramethyl-6,12-dihydroindeno-[1,2b]fluoren

23.1 g (240 mmol) of tert-butoxide sodium 235 mg (1.3 mmol) of di-tert-butylphosphine and 225 mg (1 mmol) Palladia) acetate was added to a suspension of 46.8 g (100 mmol) of 2,8-dibromo-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluorene 37.2 g (220 mmol) of diphenylamine in 1000 ml of toluene, and the mixture is successively boiled for 6 hours. After cooling, was added 300 ml of water, was filtered and the solids washed three times each time with 300 ml water and three times with 300 ml of ethanol each time, successively recrystallized from NMP (N-methylpyrrolidone) and then sublimated under reduced pressure (p=1×10-5mbar, T=360°C). Output: 52,0 g (81 mmol), 80,6% of theoretical; purity: 99,9% according to HPLC.

Example 2: 2,8-bis(bis(4-were)amino)-6,6,12,12-tetramethyl-6,12-dihydroindeno(1,2b]fluoren

The procedure is similar to that of Example 1. Instead of diphenylamine used to 43.4 g (220 mmol) of bis(4-were)amine. Recrystallization six times from o-dichlorobenzene, sublimation p=1 × 10-5mbar, T - 365°C. Yield: 45.1 g (64 mmole), and 64.3% of theoretical; purity: 99.8% according to HPLC.

Example 3: 2,8-bis(bis(2-were)amino)-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluoren

The procedure is similar to that of Example 1. Instead of diphenylamine used to 43.4 g (220 mmol) of bis(4-were)amine. Recrystallization five times from o-dichlorobenzene, sublimation p=1×10-5mbar, T - 360°C. Output: 57.4 g (82 mmol), 81.9% of theoretical; purity: 99,9% according to HPLC.

Example 4: 2,8-bis(bis(4-tert-butylphenyl)amino)-6,6,12,12-tetramethyl-6,12-dihydro who indeno[1,2b]fluoren

The procedure is similar to that of Example 1. Instead of diphenylamine used for 61.9 g (220 mmol) of bis(4-tert-butylphenyl)amine. Recrystallization five times from NMP, sublimation p=1×10-5mbar, T=350°C. Output: 73,0 g (84 mmol), 84,0% of theoretical; purity: 99,9% according to HPLC.

Example 5: Synthesis of additional indenopyrene

The following products were obtained analogously to Example 1 with a purity of 99.9% according to HPLC:

Etc.AminProduct
6
7
8

Etc.AminProduct
9
10
11
12
13
14

Etc.AminProduct
15
16

The corresponding derivatives of CIS-indenopyrene can also be synthesized similarly these syntheses, where CIS-indeno warandeberg as a starting compound can be synthesised in accordance with WO 04/113412.

Example 17: 2,8-bis(bis(4-tert-butylphenyl)amino)despero[2,7-di-tert-butylfluorene-9,6'-indenopyrene[1,2b]fluoren-12',9"-fluorene]

and Despero[2,7-di-tert-butylfluorene-9,6'-indenopyrene[1,2b]fluoren-12',9"-fluorene]

The corresponding Grignard reagent was obtained from 6.2 g (255 mmol) of magnesium and 86.3 g (250 mmol) of 2-bromo-4,4'-di-tert-butylbiphenyl in 500 ml of THF. An additional 500 ml of THF and 28.8 g (100 mmol) of [1,2b]indenopyrene-6,12-dione was added to this Grignard reagent. The reaction mixture is boiled for 10 hours, cooled, added to 50 ml of ethanol, and the mixture is evaporated to drying under conditions of reduced pressure. The residue was subjected to boiling for 3 hours in a mixture of 1000 ml of acetic acid and 25 ml of concentrated hydrochloric acid. After cooling, was filtered colorless crystals with suction, washed with 100 ml of acetic acid and then three times each time with 100 ml of ethanol, and dried under reduced pressure. Product consistently twice recrystallized from NMP. Output: 56,9 g (73 mmol), 73.0% of theoretical; purity: 99% in accordance with1H-NMR.

b) 2,8-Dibromobis[2,7-di-tert-butylfluorene-9,6'-Interflora-[1,2b]fluoren-12',9"-fluorene]

A solution of 16.8 g (200 mmol) of sodium bicarbonate in 500 ml of water was added to a solution of 39.0 g(50 mmol) of despero[2,7-di-tert-butyl-fluorene-9,6'-indenopyrene[1,2b]fluoren-12',9"-fluorene] in 2000 ml of dichloromethane. of 5.4 ml (105 mmol) of bromine was added dropwise to a two-phase mixture under vigorous stirring, and the mixture was stirred for further 16 hours. After addition of 1000 ml of ethanol was filtered solid with suction, washed five times with 300 ml of water each time and three times with 200 ml of ethanol each time, dried under reduced pressure and recrystallized from o-dichlorobenzene. Output: 38.7 g (41 mmol), 82,6% of theoretical; purity 99% in accordance with1H-NMR.

C) 2,8-bis(bis(4-tert-butylphenyl)amino)despero[2,7-di-tert-butyl-fluorene-9,6'-indenopyrene[1,2b]fluoren-12',9"-fluorene]

The procedure is similar to that of Example 1. Instead of 2,8-dibromo-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluorene used to 28.1 g (30 mmol) of 2,8-dibromobis[2,7-di-tert-butylfluorene-9,6'-indenopyrene[1,2b]fluoren-12',9"-fluorene], and instead of diphenylamine used to 18.6 g (66 mmol) of di(4-tert-butylphenyl)amine. Recrystallization five times from o-dichlorobenzene, sublimation p=1×10-5mbar, T - 390°C. Output: 23,2 g (17 mmol), 57,8% of theoretical; purity: 99,9% according to HPLC.

Example 18: 2,8-bis(bis(4-were)amino)despero[fluorene-9,6'-indenopyrene[1,2b]fluoren-12',9"-fluorene]

a) 2,8-dibromo[1,2b]indenopyrene-6,12-dione

a 30.7 ml (600 mmol) of bromine primav the Yali dropwise at 80°C to a suspension of 56.5 g (200 mmol) of [1,2b]indenopyrene-6,12-dione and 3.0 g of ferric chloride (anhydrous) in 2000 ml of 1,2-dichloroethane, and the mixture was stirred at 80°C for 30 hours. After cooling, the precipitated precipitated solid was filtered with suction, washed with stirring twice by boiling with 1000 ml of ethanol each time and dried under reduced pressure. Output: 81,6 g (85 mmol), of 92.7% of theoretical; purity 95% in accordance with1H-NMR.

b) 2,8-Dibromobis[fluorene-9,6'-indenopyrene(1,2b]fluoren-12',9"-fluorene]

Receiving is similar to that of Example 17A. Instead of 2-bromo-4,4'-di-tert-butylbiphenyl and [1,2b]indenopyrene-6,12-dione was used 58,3 g (250 mmol) of 2-bromobiphenyl and 44.0 g (100 mmol) of 2,8-dibromo[1,2b]indenopyrene-6,12-dione. Recrystallization from o-dichlorobenzene. Output: 24.5 g (34 mmole), 34.4% of theoretical; purity: 98% in accordance with1H-NMR.

C) 2,8-Bis(diphenylamino)despero(fluorene-9,6'-indenopyrene[1,2b]-fluoren-12',9"-fluorene]

Obtaining analogous to that of Example 1C. Instead of 2,8-dibromo-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluorene used 71,3 g (100 mmol) of 2,8-dibromobis[fluorene-9,6'-indenopyrene[1,2b]fluoren-12',9"-fluorene]. Recrystallization from o-dichlorobenzene, sublimation at p=1×10-5mbar, T=390°C. Output: 71,9 g (81 mmol), 80.9% of theoretical; purity: 99,7% according to HPLC.

Example 19: 2,8-bis(phenylcarbamoyl)(6,6,12,12-tet is amatil-6,12-dihydroindeno[1,2b]fluoren)

84,0 ml (210 mmol) of n-utility (2.5 M in hexane) was added dropwise to a suspension of 46.8 g (100 mmol) of 2,8-dibromo-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluorene in 700 ml of THF, cooled to -78°C. the Mixture was left to warm to 0°C for 2 hours and was stirred at 0°C for a further 1 hour, then was added a mixture of 27.5 ml (230 mmol) of 4-methylbenzonitrile in 100 ml of THF, and the resulting mixture was stirred at room the temperature during the subsequent 16 hours. 20 ml of ethanol, then 100 ml of IN hydrochloric acid was added dropwise to the mixture, which was then heated for 5 hours. After cooling, the solvent was removed at reduced pressure, and the residue was transferred into a 500 ml NMP, 20 ml of water and 5 ml of acetic acid and subjected to boiling for 5 hours. After cooling, the crystals were filtered off under suction and recrystallized three times from NMP. Sublimation at p=1×10-5mbar, T=320°C. Output: a 44.2 g (81 mmol), 80,8% of theoretical; purity: 99,9% according to HPLC.

Example 20: Synthesis of additional intenational

The following products were obtained analogously to Example 19 with a purity of 99.9% according to HPLC:

Etc.NitrileProduct
21
22

Etc.NitrileProduct
23
24
25
26
27
28
29
30

Example 31: 2,8-bis(diphenylphosphinyl)(6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluoren)

84,0 ml (210 mmol) of n-utility (2.5 M in n-hexane) was added to a suspension of 46.8 g (100 mmol) of 2,8-dibromo-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluorene in 700 ml of THF, cooled to -78°C. the Mixture was allowed to slowly warm to 0°C over a period of time of 2 hours and stirred at 0°C for subsequent hours, then added the mixture to 41.3 ml (230 mmol) of chlorodiphenylmethane in 100 ml of THF, and the mixture was stirred at room temperature over the next 16 hours. After addition of 10 ml of ethanol, the solvent was removed in a vacuum, the residue was dissolved in 500 ml of ethyl acetate, the organic phase is washed three times with 300 ml of water then was added dropwise a mixture of 22.2 ml (250 mmol) of hydrogen peroxide and 100 ml of water with vigorous stirring, and the mixture was stirred at room temperature for 16 hours. Precipitated precipitated solid was filtered with suction, washed with ethanol, dried and paracrystalline ivali from chlorobenzene. Sublimation at p=1×10-5mbar, T=340°C. Output: 46,0 g (65 mmol), 64.7% of theoretical; purity: 99,9% according to HPLC.

Example 32: Synthesis of additional oxides indenopyrene

The following products were obtained similarly to those of Example 31 with a purity of 99.9% according to HPLC:

Etc.KlohopinProduct
33

Etc.KlohopinProduct
34
35
36

Example 37: 3,9-bis(diphenylamino)-5,11-dimethylindole[3,2-b]carbazole

Getting one is camping similar to that of Example 1C. Instead of 2,8-dibromo-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluorene used a 44.2 g (100 mmol) of 3,9-dibromo-5,11-dimethylindole[2,3-b]carbazole. Recrystallization from NMP. Sublimation p=1×10-5mbar, T=350°C. Output: 43,9 g (71 mmol), 70.9% of theoretical; purity: 99.8% according to HPLC.

Example 38: Synthesis of additional derivative indolocarbazole

The following products were obtained similarly to those of Example 37 with a purity of 99.9% according to HPLC:

PRAminProduct
39
40
41
42
43
44

Example 45: 3,9-bis(diphenylamino)-5,11-diphenylphosphinoethyl-(3,2-b]dibenzofuran

a) 2',5'-dibromo-4,4,4',4'-Tetra-p-tolyl-[1,1,4,4]-terphenyl-4,4'-diamine

Suspension 24.4 g (50 mmol) of 1,4-dibromo-2,5-diadesol, 51.9 g (130 mmol) of 4-[4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl]-di-p-tolylamino, 26,5 g (250 mmol) of sodium carbonate and 116 mg (0.1 mmol) of tetrakis(triphenylphosphine)palladium(0) in a mixture of 300 ml of toluene, 100 ml of dioxane and 300 ml of water was subjected to boiling for 18 hours. After cooling, was added 500 ml of ethanol to the reaction mixture and was filtered solid with suction, washed three times with 200 ml of water each time and three times with 200 ml of ethanol each time, dried under reduced pressure and recrystallized from dioxane. Yield: 18.6 g (24 mmol), 47,7% of theoretical; purity: 97% according to NMR.

b) 3,9-bis(diphenylamino)-5,11-diphenylphosphinoethyl[3,2-b]dibenzofuran 5,11-oxide

16,8 ml (42 mmol) of n-utility (2.5 M in n-hexane) was added dropwise to a solution of 15.6 g (20 mmol) of 2',5'-dibromo-4,4,4',4'-Tetra-p-tolyl-[1,1',4,4]-trefoil-4,4'-diamine in 500 ml of THF, cooled to -78°C. the mixture was stirred at -78°C in t is a significant added 3 hours and there was added a mixture of 6.2 ml (44 mmol) phenylphosphine dichloride and 50 ml of THF over a period of time of 1 minute. After slow heating fully solvent was removed at reduced pressure, the residue was transferred into 200 ml of 1,2-dichloroethane, was added 26.7 g (200 mmol) of anhydrous aluminium chloride and the mixture was subjected to boiling for 15 hours. After cooling, was added 200 ml of 5N hydrochloric acid, separating the organic phase, once washed with 100 ml of 5N hydrochloric acid and five times with 300 ml of water each time and dried over magnesium sulfate, the solvent was removed at reduced pressure, after which the product was recrystallized from NMP. Sublimation p=1×10-5mbar, T=360°C. Yield: 6.2 g (7.7 mmol), 38,3% of theoretical; purity: 99.8% according to HPLC, including all stereoisomers.

Example 46: Obtaining acid, including interfluidity as material injection holes or material transport holes in fluorescent acid

Acid get through the overall process, as described in WO 04/058911, which is adapted in the individual case to the relevant circumstances (for example, variations in the thickness of the layer in order to achieve optimum efficiency or colour).

The results for different acid represented in the Examples 47-62 below. The basic structure and mA used the materials (separately from the layer to transport holes) are identical in the examples for better comparison. Acid having the following structure, get similarly to the above-mentioned General process:

Layer injection holes (HIL) 20 nm PEDOT (cover by centrifugation of water purchased from the NS Starck, Goslar, Germany; poly(3,4-Ethylenedioxy-2,5-thiophene))

Layer transport holes (NTM)B2 (a compound in accordance with Example 2)

or B1 (compound according to Example 1)

or B9 (a compound in accordance with Example 9)

or B15 (compound according to Example 15)

or V (compound according to Example 37)

as a comparative example, 4,4',4"-Tris(N-1-naphthyl-N-phenylamino)triphenylamine (abbreviated name NaphDATA purchased from SynTec)

Layer transport holes (NTM) 20 nm NPB (N-naphthyl-N-phenyl-4,4'-diaminobiphenyl)

Emission layer (EML) 30 nm doped layer 9,10-bis(1-naphthyl-anthracene) as the substrate (abbreviated name H1), doped with 5% of Tris[4-(2,2-diphenylvinyl)phenyl]amine as dopant (abbreviated name D1, application of the method of evaporation, synthesised in accordance with WO 06/000388)

The conductor of the first kind (ETC) 20 nm A1Q3(purchased from SynTec, Tris(hineline)aluminum(III))

The cathode 1 nm LiF, 150 nm A1 above.

Acid can also be obtained without PEDOT as a layer injection holes. In these cases, the derivative of interfluidity in accordance with the invention represents Obedinenie injection holes. These acid demonstrate relatively good properties.

These acid characterized using standard methods; for this purpose, the electroluminescence spectra of the efficiency (measured in CD/a) and the efficiency (measured in Im/W) is determined as a function of luminosity, derived from the characteristic line current/voltage/luminance (IUL characteristic lines).

Table 1 shows the results for some of asid (Examples 47 to 62), which varies the thickness of the layer to transport holes (NTM). Material for comparison, which is used in the comparative examples, represents NaphDATA.

The base material H1 represents a 9,10-bis(1-naphthyl)anthracene, and used dopant D1. The structure of both is shown below:

As you can see from the Examples 51-62 in accordance with the invention in Table 1, osid, including material transport holes in accordance with the invention (NTM)demonstrate significant lower voltage operating DC voltage compared using NaphDATA as material transport holes of the prior art. Voltage operating DC voltage is independent of the thickness of the layer to transport holes. This property is the main advantage to construct a full-color display is, since the density of pixels of the primary colors blue, green and red can be made the same by variation of the layer thickness of the transport of holes. Material transport holes in accordance with the invention can thus, in this case to serve as a compensation layer thickness in the absence of harmful effects on electro-optical properties of this device. As can be seen from the comparative examples, this does not apply to material transport holes (NaphDATA) in accordance with the prior art: in this case, a much higher voltage operating DC voltage required at the greater layer thickness of the transport of holes.

Table 1
ExampleHTL1 or HILHTL2Max. effective. (CD/A)Voltage (V) 1000
CD/m2
CIE
Example 47 (comparison)NaphDATA (20 nm)NPB (20 nm)7,56,1x=0.16 and y=0,25
Example 48 (comparison)NaphDATA (50 nm)NP (20 nm) 7,26,0x=0.16 and y=0,25
Example 49 (comparison)NaphDATA (100 nm)NPB (20 nm)6,47,9x=0.16 and y=0,24
Example 50 (comparison)NaphDATA (150 nm)NPB (20 nm)the 5.78,4x=0.16 and y~0,26
Example 51B2 (20 nm)NPB (20 nm)8,55,2x=0.16 and y=0,25
Example 52B2 (50 nm)NPB (20 nm)8,65,3x=0.16 and y=0,25
Example 53B2 (100 nm)NPB (20 nm)8,65,5x=0.16 and y=0,24
Example 54B2 (150 nm)NPB (20 nm)8,7 5,6x=0.16 and y=0,26
Example 55Vs (20 nm)NPB (20 nm)8,2of 5.4x=0.16 and y=0,25
Example 56Vs (100 nm)NPB (20 nm)8,35,5x=0.16 and y=0,24
Example 57B9 (20 nm)NPB (20 nm)8,26,1x=0.16 and y=0,25
Example 58B9 (100 nm)NPB (20 nm)8,16,3x=0.16 and y=0,24
Example 59B15 (20 nm)NPB (20 nm)8,85,6x=0.16 and y=0,25
Example 60B15 (100 nm)NPB (20 nm)8,95,8x=0.16 and y=0,24
Example 61V (20 nm)NPB (20 nm)7,96,3x=0.16 and y=0,25
Example 62V (100 nm)NPB (20 nm)8,06,5x=0.16 and y=0,24

Example 63: Getting acid, including interfluidity as material injection holes or material transport holes in fluorescent acid

Acid get through the overall process, as described in WO 04/093207, which is adapted in the individual case to the relevant circumstances (for example, variations in the thickness of the layer in order to achieve optimum efficiency or colour).

The results for different acid represented in the Examples 64-68 below. The basic structure and the materials used (separately from the layer to transport holes) are identical in the examples for better comparison. Acid having the following structure, get similarly to the above-mentioned General process:

Layer injection holes (HIL) 20 nm PEDOT (coating by centrifuging of water purchased from the NS Starck, Goslar, Germany; poly(3,4-Ethylenedioxy-2,5-thiophene))

Layer transport holes (NTM) B2 (compound matched the accordance with Example 2)

or as a comparative example, 4,4',4"-Tris(N-1-naphthyl-N-phenylamino)triphenylamine (abbreviated name NaphDATA purchased from Sn) (standard of comparison)

Layer transport holes (NTM) 20 nm (applied by the method of evaporation; S-TAD, obtained in accordance with WO 99/12888; 2,2',7,7' tetrakis(diphenylamino)spirobifluorene)

or 20 nm NPB (N-naphthyl-N-phenyl-4,4'-diaminobiphenyl)

Emission layer (EML) 40 nm ketone 1 (bis(9,9'-spirobifluorene-2-yl) ketone (caused by the evaporation method, synthesised in accordance with WO 04/093207)doped with 15% triple emitter E1 (synthesised in accordance with WO 04/085449)

A1Q320 nm (applied by the method of evaporation; A1Q purchased from SynTec, Tris(hineline)aluminum(III))

The cathode 1 nm LiF, 150 nm A1 above.

Acid can also be obtained without PEDOT as a layer injection holes. In these cases, the derivative of interfluidity in accordance with the invention is a compound of injection holes. These acid demonstrate relatively good properties.

These acid characterized using standard methods; for this purpose, the electroluminescence spectra of the efficiency (measured in CD/a) and the efficiency (measured in Im/W) is determined as a function of luminosity, derived from the characteristic line current/voltage/luminance (IUL characteristic lines).

Table 2 on the it shows the results for some of asid (Examples 64-68), in which varies the thickness of the layer to transport holes (NTM). Material for comparison, which is used in the comparative examples, represents NaphDATA.

As you can see from the Examples 65-68 in accordance with the invention in Table 2, osid, including material transport holes in accordance with the invention (NTM)demonstrate significant lower voltage operating DC voltage compared using NaphDATA as material transport holes of the prior art. Voltage operating DC voltage is independent of the thickness of the layer to transport holes. Material transport holes in accordance with the invention can, thus, serve as a compensation layer thickness in this case, in the absence of harmful effects on electro-optical properties of this device.

Table 2
ExampleHTL1 or HILHTL2Max. effective. (CD/A)Voltage (V) at 1000 CD/m2CIE
Example 64 (comparison)NaphDATA (20 nm) S-TAD (20 nm)334,5x=0,38 y=0,58
Example 65B2 (20 nm)S-TAD (20 nm)42the 3.8x=0,38 y=0,58
Example 66B2 (150 nm)S-TAD (20 nm)40a 3.9x=0,36
y=0,60
Example 67B2 (20 nm)NPB (20 nm)374,2x=0,38 y=0,58
Example 68B2 (150 nm)NPB (20 nm)354,3x=0.36 and y=0,60

Example 69: Getting acid, including Interflora ketones or oxide indenopyrene as material transport of electrons in a fluorescent acid

Acid get through the overall process, as described in WO 04/093207, which is adapted in the individual case to the relevant circumstances (for example, variations in the thickness of the layer to the achievement of the occasions optimum efficiency or colour).

The results for different acid represented in the Examples 70-73 below. The basic structure and the materials used (separately from the layer of electron transport) are identical in the examples for better comparison. Acid having the following structure, get similarly to the above-mentioned General process:

Layer injection holes (HIL) 20 nm PEDOT (drawing by centrifuging of water purchased from the NS Starck, Goslar, Germany; poly(3,4-Ethylenedioxy-2,5-thiophene))

Layer transport holes (NTM)20 nm 4,4',4"-Tris(N-1-naphthyl-N-phenylamino)triphenylamine (abbreviated name NaphDATA purchased from SynTec)

Layer transport holes (NTM) 20 nm S-TAD (caused by the evaporation method; S-TAD, obtained in accordance with WO 99/12888; 2,2'7,7'-tetrakis(diphenylamino)spirobifluorene)

Emission layer (EML) 40 nm ketone 1 (bis(9,9'-spirobifluorene-2-yl) ketone (caused by the evaporation method, synthesised in accordance with WO 04/093207)doped with 15% triple emitter E1 (synthesised in accordance with WO 04/085449)

The layer of electron transport 20 nm B19 (compound according to Example 19)

or 20 nm V (compound according to Example 26)

or 20 nm V (connection in accordance with Example 31)

or 20 nm 1Q3(1Q3for udaetsya from SynTec; Tris(hineline)aluminum(III), comparison)

The cathode 1 nm LiF, 150 nm A1 above.

These acid characterized using standard methods; for this purpose, the electroluminescence spectra of the efficiency (measured in CD/a) and the efficiency (measured in Im/W) is determined as a function of luminosity, derived from the characteristic line current/voltage/luminance (IUL characteristic lines).

Table 3 shows the results for some of asid (Examples 70-73), which varies the thickness of the layer of electron transport (ETL). Material for comparison, which is used in the comparative examples, is a Alq. The emitter E1 and the base material ketone 1 shown in Example 63.

As you can see from the Examples 71-73 in accordance with the invention in Table 3, asid, including the material of electron transport in accordance with the invention, showing a significant lower voltage operating DC voltage and higher efficiency compared with the use of Alq in accordance with the prior art.

Table 3
ExampleETLMax. effective. (CD/A)Voltage (V) at 1000 CD/m2 CIE
Example 70 (comparison)Alq (20 nm)334,5x=0,38; y=0,58
Example 71B19 (20 nm)354,2x=0,38; y=0,58
Example 72V (20 nm)38a 3.9x=0,38; y=0,58
Example 73V (20 nm)374,1x=0,38; y=0,58

Example 74: Getting red fluorescence of acid, including Interflora ketones or oxide indenopyrene as a triplet of base material

Acid get through the overall process, as described in WO 04/093207, which is adapted in the individual case to the relevant circumstances (for example, variations in the thickness of the layer in order to achieve optimum efficiency or colour).

The results for different acid represented in the Examples 75-78 below. The basic structure and the materials used (separately from the layer of electron transport) are identifying the parameters in the examples for better comparison. Acid having the following structure, get similarly to the above-mentioned General process:

Layer injection holes (HIL) 20 nm PEDOT (drawing by centrifuging of water purchased from the NS Starck, Goslar, Germany; poly(3,4-Ethylenedioxy-2,5-thiophene))

Layer transport holes (NTM) 20 nm 4,4',4"-Tris(N-1-naphthyl-N-phenylamino)triphenylamine (abbreviated name NaphDATA purchased from SynTec)

Layer transport holes (NTM) 20 nm S-TAD (caused by the evaporation method; S-TAD obtained in accordance with WO 99/12888; 2,2'7,7'-tetrakis(diphenylamino)spirobifluorene)

Emission layer (EML) 20 nm 19 (a compound in accordance with Example 26)

or 20 nm V (connection in accordance with Example 31)

or 20 nm V (connection in accordance with Example 31)

or ketone 1 (bis(9,9'-spirobifluorene-2-yl) ketone (caused by the evaporation method, synthesised in accordance with WO 04/093207) (standard of comparison), in each case doped with 10% of the triplet emitter E2 (synthesised in accordance with WO 05/033244)

The layer of electron transport 20 nm 1Q3(caused by the evaporation method: 1Q3purchased from SynTec; Tris(hineline)aluminum(III))

The cathode 1 nm LiF, 150 nm A1 above.

These acid characterized using standard methods; for this purpose, the electroluminescence spectra of the efficiency (measured in CD/a) and the efficiency (measured in MVt) is determined as a function of luminosity, derived from the characteristic lines of the current/voltage/luminance (IUL characteristic lines).

Table 4 shows the results for some of asid (Examples 75-78), which varies the thickness of the triplet base material of the emission layer (EML). Material for comparison, which is used in the comparative examples, is a ketone 1.

The emitter E1 and triplet substrate ketone 1 below for clarity:

As you can see from the Examples 76-78 in accordance with the invention in Table 4, asid, including the material of electron transport in accordance with the invention, showing a significant lower voltage operating DC voltage and higher efficiency compared to the use of ketone 1 in accordance with the prior art.

Table 4
ExampleEML base: emitterMax. efficiency (CD/A)Voltage (V) at 1000 CD/m2CIE
Example 75 (comparison)E2: the ketone 1 (40 nm)13,35,5/td> x=0,65; y=0,35
Example 76E2: B19 (40 nm)15,45,2x=0,65; y=0,35
Example 77E2: V (40 nm)14,8of 5.4x=0,65; y=0,35
Example 78E2: V (40 nm)14,55,1x=0,65; y=0,35

Example 79: Getting acid, including interfluidity as emitter

Acid get through the overall process, as described in WO 04/093207, which is adapted in the individual case to the relevant circumstances (for example, variations in the thickness of the layer in order to achieve optimum efficiency or colour).

The results for different acid represented in the Examples 80-86 below. The basic structure and the materials used (separately from the emission layer) are identical in the examples for better comparison. Acid having the following structure, get similarly to the above-mentioned General process:

Layer injection holes (HIL) 20 nm PEDOT (drawing by centrifuging of water purchased from the NS Sarck, Goslar, Germany; poly(3,4-Ethylenedioxy-2,5-thiophene))

Layer transport holes (NTM) 20 nm B2 (compound obtained in accordance with Example 2)

Layer transport holes (NTM) 20 nm NPB (N-naphthyl-N-phenyl-4,4'-diaminobiphenyl)

Emission layer (EML) 30 nm layer H1, H2 or H3 as base material doped with x% (see table) B2 (a compound in accordance with Example 2) or 17 (a compound in accordance with Example 17) as dopant

The conductor of the first kind (ETC) 20 nm (applied by the method of evaporation; lQ3purchased from SynTec, Tris(hineline)aluminum (III)

The cathode 1 nm LiF, 150 nm Al on top.

These acid characterized using standard methods; for this purpose, the electroluminescence spectra of the efficiency (measured in CD/A) and the efficiency (measured in lm/W) is determined as a function of luminosity, derived from the characteristic line current/voltage/luminance (IUL characteristic lines).

Table 5 shows the results for some of asid (Examples 80-86), where B2 (compound according to Example 2) or 17 (a compound in accordance with Example 17) is used as emitter dark blue light, and the degree of doping varies.

Materials fundamentals of H1, H2 and H3 are shown below:

As in idete example 80-86 in Table 5, Acid, including dopanti B2 (compound according to Example 2) and 17 (a compound in accordance with Example 17) in accordance with the invention, demonstrate effective dark blue radiation. In contrast, the color ratio only (0,15; 0,15) can be achieved using commercial acid. The internal quantum yield is close to 100%.

Table 5
ExampleEMLMax. efficiency (CD/A)Voltage (V) at 1000 CD/m2CIE
Example 80H2 2% B22,56,6x=0.16 and y=0,09
Example 81H2 5% B22,86,4x=0.16 and y=0,10
Example 82H2 10% B22,76,3x=0.16 and y=0,13
Example 83H3 5% B22,36,8 x=0.16 and y=0,04
Example 84H3 10% B22,26,5x=0.16 and y=0,05
Example 85H3 15% B22,06,3x=0.16 and y=0,05
Example 86H1 10% B172,46,2x=0.16 and y=0,08

Example 87: Bis(N-(4-tert-butylphenyl)-N-(4-bromophenyl)amino)-6,6,12,12-tetraoctyl-6,12-dihydroindeno[1,2b]fluoren

(a) Bis(N-(4-tert-butylphenyl)-N-phenylamino)-6,6,12,12-tetraoctyl-6,12-dihydroindeno[1,2b]fluoren

A solution of 17.2 g (20.0 mmol) 6,6,12,12-tetraoctyl-6,12-dihydro-[1,2b]indenopyrene dibromide and 10.0 g (44,4 mmole) of 4-tert-butylbenzylamine in 130 ml dry toluene was saturated with argon. Then he added 81,0 mg of tri-tert-butylphosphine, 45 mg paradiastole and 5,97 g of tert-butoxide sodium. The reaction mixture is boiled for 12.5 hours. After cooling to room temperature, the mixture was extracted with 2M Hcl (2×100 ml). Separated organic phase was filtered through celite and evaporated on a rotary evaporator. The raw product was recrystallized from tO/toluene, getting 186 g (81%) of yellow crystals.

b) Bis(N-(4-tert-butylphenyl)-N-(4-bromophenyl)amino)-6,6,12,12-tetraoctyl-6,12-dihydroindeno[1,2b]fluoren

5.0 g (3.8 mmol) of bis(N-(4-tert-butylphenyl)-N-phenylamino)-6,6,12,12-tetraoctyl-6,12-dihydroindeno[1,2b]fluorene was dissolved in 22.4 ml of dry THF, was added dropwise a solution of 1.5 g of NBS in 22.4 ml of THF at 0°C. the Reaction mixture was left to reach room temperature, and the solvent was removed. The solid was washed by boiling with ethanol and filtered with suction. After drying under reduced pressure, the raw product was recrystallized from acetonitrile/toluene, while receiving 2.16 g (43%) of crystals of pale yellow color.

Bis(N-(4-tert-butylphenyl)-N-(4-bromophenyl)amino)-6,6,12,12-tetraoctyl-6,12-dihydroindeno[1,2b]fluoren can be used as a monomer for polymerization, for example, for polymerization by Suzuki or Yamamoto. This connection is particularly well-suited for embedding in a conjugated or partially conjugated polymers and is particularly acceptable in the quality of the connection forming hole in these polymers.

Example 88: 2,10-bis(diphenylamino)-12,15-dihydro-6,6,12,12,15,15-HEXAMETHYL-6N-dhingana(1,2-b:2,1'-h]fluoren

a) 12,15-Dihydro-6,6,12,12,15,15-HEXAMETHYL-6N-dhingana-[1,2-b:2',1'-h]fluoren

Getting exercise is similar to 9,-dimethylfuran from 12,15-dihydro-6N-dhingana[1,2-b:2',1'-h]fluorene (Stauner, and others, Helv. Chim. Acta 1970, 53(6), 1311), dimethylsulfate and sodium hydroxide in accordance with JP 08113542. Output 61,0% of theoretical; purity 97% in accordance with1H-NMR.

b) 2,10-Dibromo-12,15-dihydro-6,6,12,12,15,15-HEXAMETHYL-6N-dhingana[1,2-b:2',1"-h]fluoren

Receiving is similar to that of Example 1b. Instead 122,0 g (393 mmole) 6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluorene used 167,7 g (393 mmole) 12,15-dihydro-6,6,12,12,15,15-HEXAMETHYL-6N-dhingana-[1,2-b:2"1'-h]fluorene. Output: 198,5 g (339 mmol), 86.4 per cent of theoretical; purity: 98% in accordance with1H-NMR.

C) 2,10-bis(diphenylamino)-12,15-dihydro-6,6,12,12,15,15-HEXAMETHYL-6N-dhingana[1,2-b:2',1'-h]fluoren

Receiving is similar to that of Example 1C. Instead of 46.8 g (100 mmol) of 2,8-dibromo-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluorene used 58,4 g (100 mmol) 2,10-dibromo-12,15-dihydro-6,6,12,12,15,15-HEXAMETHYL-6N-dhingana[1,2-b:2',1'-h]fluorene. Sublimation p=1×10-5mbar, T=390°C. Output: 55,0 g (72 mmol), 72.3% of theoretical; purity: 99,9% according to HPLC.

Example 89: 2,8-bis(bis(4-diphenylamine)amino)-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluoren

a) 2,8-bis(bis(4-bromophenyl)amino)-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluoren

74,8 g (420 mmol) of N-bromosuccinimide was added in parts when intensive the om stirring to a solution of 64.5 g (100 mmol) of 2,8-bis(diphenylamino)-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluorene in 1500 ml of dichloromethane, and the mixture was stirred at room temperature for 16 hours. The reaction mixture was concentrated to a volume of 200 ml under conditions of reduced pressure, was added 1000 ml of ethanol, the precipitate was filtered with suction, stirred with 1000 ml of hot ethanol, filtered with suction, washed three times with 300 ml of ethanol each time and dried under reduced pressure. Output: 82,1 g (85 mmol), 85.5% of theoretical; purity: 97%, in accordance with1H-NMR.

b) 2,8-bis(bis(4-diphenylamine)amino)-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluoren

The procedure is similar to that of Example 1C. Instead of 46.8 g (100 mmol) of 2,8-dibromo-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluorene used to 48.0 g (50 mmol) of 2,8-bis(bis(4-bromophenyl)amino)-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluorene. Recrystallization from dioxane; sublimation (p=1×10-5mbar, T=380°C. Output: 48,8 g (37 mmol), 74,3% of theoretical; purity: 99.8% according to HPLC.

Example 90: 2,8-bis((4-were)(4-diphenylamine)amino)-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluoren

a) 2,8-bis((4-bromophenyl)(4-were)amino)-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluoren

74,8 g (420 mmol) of N-bromosuccinimide was added in portions with vigorous stirring to a solution of 134,6 g (200 mmol) of a 28-bis((phenyl)(4-were)amino)-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluorene (preparation similar to that of Example 1C) in 1500 ml of dichloromethane, and the mixture was stirred at room temperature for 16 hours. The reaction mixture was concentrated to a volume of 200 ml under conditions of reduced pressure, was added 1000 ml of ethanol, the precipitate was filtered with suction, stirred with 1000 ml of hot ethanol, filtered with suction, washed three times with 300 ml of ethanol each time and dried under reduced pressure. Output: 139,0 g (167 mmol), 83.6% of theoretical; purity: 98% in accordance with1H-NMR.

b) 2,8-bis((4~were)(4-diphenylamine)amino)-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluoren

The procedure is similar to that of Example 1C. Instead of 46.8 g (100 mmol) of 2,8-dibromo-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluorene used 83,1 g (100 mmol) of 2,8-bis((4-bromophenyl)(4-were)amino)-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2b]fluorene. Recrystallization from NMP; sublimation (p=1×10-5mbar, T - 370°C. Output: 83,6 g (83 mmol), 82,9% of theoretical; purity: 99,7% according to HPLC.

Example 91: Getting acid, including indenopyrene or hexamine as material injection holes or material transport holes in fluorescent acid

Acid received in accordance with the General process as described in WO 04/058911, which is adapted in the individual case to the relevant circumstances (e.g. the measures variations of the layer thickness in order to achieve optimum efficiency or colour).

The results for different acid represented in the Examples 92-94 below. The basic structure and the materials used (separate from layer to transport holes) are identical in the examples for better comparability. Acid having the following structure was obtained similarly to the above-mentioned General process.

Layer injection holes (HIL) 20 nm PEDOT (drawing by centrifuging of water purchased from the NS Starck, Goslar, Germany; poly(3,4-Ethylenedioxy-2,5-thiophene))

Layer transport holes (NTM) V (compound according to Example 89)

or V (compound according to Example 90)

or as a comparative example, 4,4',4"-Tris(N-1-naphthyl-N-phenylamino)triphenylamine (abbreviated name NaphDATA purchased from SynTec)

Layer transport holes (NTM) 20 nm NPB (N-naphthyl-N-phenyl-4,4'-diaminobiphenyl)

Emission layer (EML) 30 nm doped layer 9,10-bis(1-naphthyl-anthracene) as the substrate (abbreviated name - H1), doped with 5% of Tris[4-(2,2-diphenylvinyl)phenyl]amine as dopant (short - D1), caused by the evaporation method, synthesized as described in WO 06/000388)

The conductor of the first kind 20 nm 1Q3(purchased from SynTec, Tris(hineline)aluminum (III))

The cathode 1 nm LiF, 150 nm A1 above.

Acid can also be p is obtained without PEDOT as a layer injection holes. In these cases, the derivative indenopyrene or hexamine in accordance with the invention then is a combination of injection holes. These acid demonstrate relatively good properties.

These acid characterized using standard methods; for this purpose, the electroluminescence spectra of the efficiency (measured in CD/a) and the efficiency (measured in Im/W) is determined as a function of luminosity, derived from the characteristic line current/voltage/luminance (IUL characteristic lines).

Table 6 shows the results for some of asid (Examples from 92-94), which varies the thickness of the layer to transport holes (NTM). Material for comparison, which is used in the comparative examples, represents NaphDATA.

The material bases of H1, which is used, is a 9,10-bis(1-naphthyl)anthracene, used dopant is a D1. Both are presented below:

As you can see from the Examples 92 and 93 in accordance with the invention in Table 6, asid, including material transport holes in accordance with the invention (NTM)demonstrate significant lower voltage operating DC voltage compared using NaphDATA as material transport holes of the prior art. Voltage of the operational the aqueous DC is independent of the thickness of the layer to transport holes. This property is the main advantage for the design of full-color displays, since the density of pixels of the primary colors blue, green and red can be made the same by variation of the layer thickness of the transport of holes. Material transport holes in accordance with the invention can, thus, serve as a compensation layer thickness in this case, in the absence of harmful effects on electro-optical properties of this device. As can be seen from the comparative examples, this does not apply to material transport holes (NaphDATA) in accordance with the prior art: in this case, a much higher voltage operating DC voltage required at the greater layer thickness of the transport of holes.

Table 6
ExampleHTL1 or HILHTL2Max. effective. (CD/A)Voltage (V) at 1000 CD/m2CIE
Example 92V (20 nm)NPB (20 nm)8,9of 5.4x=0,16
Prima is 93 V (20 nm)NPB (20 nm)9,05,5x=0,16
Example 94 (comparison)NaphDATA (20 nm)NPB (20 nm)7,56,1x=0,16

1. The compounds of formula (1)

where we use the following symbols and indices:
Y, Z are identical or different and represent N, R, P=O, C=O, Oh, S, S=O or SO2;
Ar1, Ar2, Ar3are in each case identical or different and represent a benzene, naphthalene, anthracene, phenanthrene, pyridine, pyrene or thiophene, which may be substituted by one or more radicals R1;
Ar4, Ar5, Ar6, Ar7are in each case identical or different and represent a benzene, naphthalene, anthracene, phenanthrene, pyridine, pyrene, thiophene, triphenylamine, diphenyl-1-naphtylamine, diphenyl-2-naphtylamine, phenyldi(1-naphthyl)amine, phenyldi(2-naphthyl)amine or spirobifluorene, which can be substituted by one or more radicals R1;
E. in each case identical or different represents a single bond, N(R1), O, S, or C(R1)2;
R1/sup> in each case is identical or different and represents H, F, CN, alkyl with non-branched chain containing 1-5 carbon atoms, or a branched alkyl chain containing 3-5 carbon atoms, where in each case one or more non-adjacent CH2groups may be replaced by-R2C=CR2-, -C≡C-, -O - or-S-, and where one or more atoms N can be replaced by F, or a monovalent aryl or heteroaryl group containing 2-16 carbon atoms which may be substituted by one or more radicals R2two or more substituents R1can also form a ring system with one another;
R2in each case is identical or different, represents H or an aliphatic or aromatic hydrocarbon radical containing 1-20 carbon atoms;
X1X4are in each case identical or different and represent a bridge connection, which together with Ar1and Ar2is a cyclic system selected from C(R1)2, C=O, C=NR1, O, S, S=O, SO2N(R1), P(R1), P(=O)R1C(R1)2-C(R1)2C(R1)2-C(R1)2-C(R1)2C(R1)2-O and C(R1)2-O-C(R1)2;
X2X3are in each case identical or different which represent a bridge connection, together with Ar2and Ar3is a cyclic ring system selected from C(R1)2, C=O, C=NR1, O, S, S=O, SO2N(R1), P(R1), P(=O)R1C(R1)2-C(R1)2C(R1)2-C(R1)2-C(R1)2C(R1)2-O and C(R1)2-O-C(R1)2;
n, o, p are in each case identical or different and are 0 or 1, provided that n, p and can only be equal to 0 if X1represents a group other than bridge C(R1)2where R1is an alkyl radical with an open circuit; n=0 and o=0 and p=0 in this case means that the two radicals R1present instead of the bridge;
q, r in each case is equal to 1 if the corresponding Central atom of the group Y or Z is an element of the 5th main group, and in each case equal to 0 if the corresponding Central atom of the group Y or Z is an element of the 4th or 6th main group;
s is equal to 1;
t in each case is identical or different, are 0 or 1, where t=0 means that the radicals R1related instead of group E; moreover, t=0 if q=0 and t=0 if r=0.

2. Compounds according to claim 1, characterized by the fact that the symbols Y, Z are identical or different, represent nitrogen, C=O, phosphorus or P=O.

3. The compounds of formula (1A) according to claim 1
img src="https://img.russianpatents.com/1080/10801263-s.jpg" height="56" width="128" />
where the symbols and indices have the same value as specified in claim 1.

4. Compounds according to claim 1, characterized in that the index p=0 and one of the two indices n and is equal to 1, while the other two indices are equal to 0, having the structure of formulas (1b) and (1C)


where the symbols and indices have the same value as specified in claim 1.

5. Compounds according to claim 1, characterized by the fact that the symbols X1X2X3and X4in each case are identical or different, represent a bridge connection, which together with AG1and AG2or AG2and AG3denotes a cyclic system selected from C(R1)2N(R1), P(R1) and P(=O)R1.

6. The compounds of formula (1d) according to claim 1

where the symbols and indices have the same value as specified in claim 1.

7. Compounds according to claim 6, characterized in that the radicals R form a ring system with one another.

8. Compounds according to claim 1, characterized in that Y=Z.

9. Compounds according to claim 1, selected from the following structures:

10. The use of compounds according to claim 1 in organic electronic devices selected from the group consisting of organic electroluminescent devices (acid), organic transistors with a controlled field (O-FET), organic that is coplenary transistor (O-TFT), organic light-emitting transistor (O-LET), organic integrated circuits (O-ICS), organic solar cells (O-SC), organic devices with quenching field (O-FQD), light emitting electrochemical cells (LEC), organic photoreceptors or organic laser diodes (O-lasers).

11. Organic electronic device is selected from the group consisting of organic electroluminescent devices (acid), organic transistors with a controlled field (O-FET), organic thin-film transistor (O-TFT), organic light-emitting transistor (O-LET), organic integrated circuits (O-ICS), organic solar cells (O-SC), organic devices with quenching field (O-FQD), light emitting electrochemical cells (LEC), organic photoreceptors or organic laser diodes (O-lasers), including at least one connection according to claim 1.

12. Organic electroluminescent device comprising an anode, a cathode and at least one emitting layer, characterized in that the emitting layer includes at least one compound according to claim 1.

13. Organic electroluminescent device according to item 12, characterized in that the compound according to claim 1 is used as the emitter, and the base material in sluchayem layer selected from the classes of oligoanilines, oligoanilines, sod is rasih condensed aromatic group, oligoelements, polypodine complex compounds of metals, compounds forming holes, connections that make up electrons, ketones, phosphine oxides, sulfoxidov or atropisomers.

14. Organic electroluminescent device according to item 12, characterized in that there are additional layers selected from the layer injection hole, transport layer holes, blocking layer holes, a layer of electron transport and/or injection layer of electrons.

15. Organic electronic device according to item 12, characterized in that the compound according to claim 1 is used as the material of the transport of holes in the layer to transport holes and/or layer injection holes, and the fact that the connection of these layers may be optionally doped with electron-acceptor compounds.

16. Organic electronic device according to item 12, characterized in that the compound according to claim 1 is used as a material of electron transport layer transport of electrons and/or material blocking the holes in the blocking layer holes, and/or as triplet matrix material in the emission layer.



 

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5 cl, 1 tbl, 2 dwg

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

FIELD: chemistry.

SUBSTANCE: invention can be used in manufacturing organic light-emitting diodes, liquid-crystal displays, plasma display panel, thin-film solar cell and other electronic and semi-conductor devices. Claimed is element, including target of ionic dispersion, where said target includes processed MoO2 plate of high purity. Method of such plate manufacturing includes isostatic pressing of component consisting of more than 99% of stoichiometric MoO2 powder into workpiece, sintering of said workpiece under conditions of supporting more than 99% of MoO2 stoichiometry and formation of plate which includes more than 99% of stoichiometric MoO2. In other version of said plate manufacturing component, consisting of powder, which contains more than 99% of stoichiometric MoO2, is processed under conditions of hot pressing with formation of plate. Method of thin film manufacturing includes stages of sputtering of plate, which contains more than 99% of stoichiometric MoO2, removal of MoO2 molecules from plate and application of MoO2 molecules on substrate. Also claimed is MoO2 powder and method of said plate sputtering with application of magnetron sputtering, pulse laser sputtering, ionic-beam sputtering, triode sputtering and their combination.

EFFECT: invention allows to increase work of output of electron of ionic sputtering target material in organic light-emitting diodes.

16 cl, 5 ex

FIELD: physics; optics.

SUBSTANCE: invention relates to organic displays. The organic electroluminescent display has an organic electroluminescent device which has first and second display electrodes and at least one organic functional layer between the display electrodes and consisting of an organic compound; a base for holding the organic electroluminescent device; a film of a high-molecular compound which covers the organic electroluminescent device and the surface of the base along the perimetre of the organic electroluminescent device; and in inorganic barrier film which covers the high-molecular compound film, edges of the high-molecular compound film and the surface of the base along the perimetre of the high-molecular compound film; the high-molecular compound film used is a film made from aliphatic polyurea.

EFFECT: design of an organic electroluminescent display which is not dyed and is shock resistant.

6 cl, 2 dwg, 2 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to new chemical compounds, particularly to complexes of scandium with heterocyclic ligands tris[2-(1,3-benzox(ti/imid)azol-2-yl)phenolate-O,N]scandium of general formula , where X - is oxygen, or sulphur, or NH, which can be used as an electroluminescent (emission) layer in organic light-emitting diodes (OLED). Invented also is an organic light-emitting diode, in which the emission layer is made from tris[2-(1,3-benzoxazol-2-yl)phenolate-O,N]scandium.

EFFECT: obtaining new chemical compounds which can be used as electroluminescent (emission) layer in organic light-emitting diodes (OLED).

6 cl, 3 ex

FIELD: physics.

SUBSTANCE: in receiver of optical radiation comprising at least one heterostructure located on transparent substrate and enclosed between two light-transmitting anode and cathode electrodes and consisting of two layers of organic semi-conducting materials with different width of prohibited zone, layers of heterostructure are made of materials with maximums of absorption spectrums located in area λ≤450 nm and high light transmission in visible area of spectrum, at that light transmission of incident flux of radiation from receiver of optical radiation in visible area of spectrum makes at least 30%.

EFFECT: creation of optical radiation receiver transparent in visible area of spectrum.

3 cl, 5 dwg

FIELD: physics.

SUBSTANCE: organic light-emitting diode contains the bearing bottom executed in the form of glass or plastic layer with the anode transparent layer disposed on it. The layer of organic substance with hole conductivity (the hole-transport layer) is located on the anode, then the organic radiating (emission) layer, organic layer with n-type conduction (an electro-transport layer) follow. The emission layer can simultaneously carry out function of an electro-transport stratum. Over organic layers the cathode stratum is located. The cathode is executed from the composite material containing ytterbium, doped by thulium or europium in amount of not less than 10%. The device is characterised by high technical characteristics: the insert voltage makes 4 V, a running voltage at luminosity 150 cd/m2, that there corresponds to quantity of the working monitor, 4 V, efficiency of a luminescence - 2 lm/W. At the mentioned running voltage luminosity slope on 10% makes not less than 4000 hours.

EFFECT: expansion of a circle of substances for emission layer, capable to generate all basic and intermediate colours.

4 cl, 1 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: there is disclosed method of injector polyaniline coating on the surface of transparent conductive oxide or metal layer on transparent substrate for the polymer electroluminescent diode, characterised that polyaniline coating is ensured with electrochemical synthesis of polyaniline from aniline solution being in contact with transparent conductive oxide or metal layer. Invention prevents softening ensured by prevented current spreading along the polyaniline layer, as well as by simplified procedure of polyaniline coating; homogeneous coating of easily controlled thickness; polyaniline coating of high continuity without through holes; with required pixel array addressing without additional polymer layers of reduced conductivity.

EFFECT: simplified and cheap making polymeric electroluminescent diodes.

10 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention discloses a radiation-chemical method of producing luminescent fluoroplast-4. A block or film type article made from polytetrafluoroethylene undergo treatment with gamma-rays with average energy of 1.25 MeV at temperature higher than the melting point of the crystalline phase. Treatment is carried out in the presence of water vapour at pressure 10-2-1 mm Hg and dose rate of 1-5 Gy/s to an absorbed dose of 200 kGy.

EFFECT: disclosed method ensures obtaining a novel modification of fluoroplast-4 - polytetrafluoroethylene having intense fluorescence in the visible spectrum.

1 dwg, 1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: electroluminescent device has a hole injection layer, a hole transport layer, an active luminescent layer based on electroluminescent substance of formula I , a hole blocking layer, an electron transport layer and an electron injection layer.

EFFECT: high luminance of devices emitting in the green spectral region.

1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel 1-substituted 3-(2-chloro-1H-indol-3-yl)-4-phenyl-1H-pyrrole-2,5-diones of formula 1: , where R1 denotes H, C1-C6alkyl; R2 denotes compounds which, under the effect of visible light, form fluorescent 2,8-substituted benzo[a]pyrrolo[3,4-c]carbazole-1,3-(2H,8H)diones of formula II: , where R1 and R2 are as described above.

EFFECT: more effective use of the compounds.

10 cl, 2 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention describes an aqueous dispersion of an optical bleaching agent which is stable during storage, does not contain dispersants and stabilisers and contains 20-40% active substance in form of one or more optical bleaching agents obtained through successive reaction of cyanuric chloride with 4,4'-diamino-2,2'- stilbene sulphonic acid, amine and a product of reacting monoethanol amine with acrylamide.

EFFECT: disclosed dispersion of optical bleaching agent does not require dispersants or other stabilising additives to prevent settling during storage and has excellent properties for bleaching paper and other cellulose materials.

8 cl, 2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel 1-substituted-3-[(1E)-1-alkenyl]-4-(5-alkoxy-1,2-dimethyl-1H-indol-3-yl)-1H-pyrrole-2,5-diones of general formula

, where R1=C1-C6alkyl, R2=C1-C6 alkyl, R3=CH2C6H5, C6H5.

EFFECT: obtaining novel compounds which can be used as fluorescent photochromes.

4 cl, 1 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel branched oligoarylsilanes and their synthesis method. The engineering problem is obtaining branched oligoarylsilanes which contain not less than 5 functional arylsilane links and have a set of properties which enable their use as luminescent materials. The disclosed branched oligoarylsilanes have general formula where R denotes a substitute from: straight or branched C1-C20 alkyl groups; straight or branched C1-C20 alkyl groups separated by at least one oxygen atom; straight or branched C1-C20 alkyl groups separated by at least one sulphur atom; branched C3-C20 alkyl groups separated by at least one silicon atom; C2-C20 alkenyl groups; Ar denotes identical or different arylene or heteroarylene radicals selected from: substituted or unsubstituted thienyl-2,5-diyl, substituted or unsubstituted phenyl-1,4-diyl, substituted or unsubstituted 1,3-oxazole-2,5-diyl, substituted fluorene-4,4'-diyl, substituted cyclopentadithiophene-2,7-diyl; Q is a radical selected from the same group as Ar; X is at least one radical selected from the same group as Ar and/or a radical selected from: 2,1,3-benzothiodiazole-4,7-diyl, anthracene-9,10-diyl, 1,3,4-oxadiazole-2,5-diyl, 1-phenyl-2-pyrazoline-3,5-diyl, perylene-3,10-diyl; L equals 1 or 3 or 7 and preferably 1 or 3; n is an integer from 2 to 4; m is an integer from 1 to 3; k is an integer from 1 to 3. The method of obtaining branched oligoarylsilanes involves reaction of a compound of formula where Y is a boric acid residue or its ester or Br or I, under Suzuki reaction conditions with a reagent of formula (IV) A - Xm - A (IV), where A denotes: Br or I, provided that Y denotes a boric acid residue or its ester; or a boric acid residue or its ester, provided that Y denotes Br or I.

EFFECT: obtaining novel compounds distinguished by high luminescence efficiency, efficient intramolecular transfer of energy between molecule fragments and high thermal stability.

24 cl, 12 dwg, 1 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel compounds, specifically to 4-substituted-3-(1-alkyl-2-chloro-1H-indol-3-yl)furan-2,5-diones of general formula I , where R1=H, C1-C6 alkyl; R2=H, C1-C6 alkyl, C1-C6 alkoxy; R3=phenyl, naphthyl, 2-phenyl-1-ethenyl, thienyl, furyl, pyrrolyl, benzothiophenyl, benzofuranyl, indolyl, synthesis method thereof and use as compounds capable of photochemical generation of stable fluorophores of formula II, which can be used, for instance in information storage systems, particularly as photosensitive components of material for three-dimensional recording and storage of information. The invention also relates to novel 4,5-substituted-6-alkyl-1H-furo[3,4-c]carbazole-1,3(6H)diones of general formula II , where R1=H, C1-C6 alkyl; R2=H, C1-C6 alkyl, C1-C6 alkoxy; R4=H, R5=phenyl, R4, R5=benzo, naphtho, thieno, furo, pyrrolo, benzothieno, benzofuro, indolo, method for synthesis of said compounds and use as fluorophores.

EFFECT: obtaining novel compounds and possibility of using said compounds as fluorophores.

14 cl, 2 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to zinc bis[2-(tosylamino)benzylidene-N-alkyliminates] of general formula , where Ts = tosyl, R=C7-C18 alkyl.

EFFECT: compounds exhibit luminescent properties and can be used as luminophors for making white and visible light organic light-emitting diodes.

3 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to compositions which contain electrically conducting organic materials, particularly to compositions for obtaining hole injecting or hole conveying layers in electroluminescent devices, organic solar cells, organic laser diodes, organic thin-film transistors or organic field-effect transistors, and for making electrodes or electroconductive coatings. The proposed composition contains polythiophene which contains a link of formula (I): , as well as at least one vinyl polymer which contains SO3-M+ - or COO-M+- groups and at least one partially or perfluorinated polymer which contains SO3-M+ - or COO-M+- groups, where M+ denotes H+, Li+, Na+, K+, Rb+, Cs+ , NH4+. Described also is an electroluminescent device in which hole injecting layers contain this composition.

EFFECT: composition provides devices with longer service life.

25 cl, 2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: described is a polyfunctional chemiluminescent composition which contains luminal, alkali, Trilon B, methanol, glycine and water. The composition contains alkali preferably in form of potassium alkali with negative hydration properties, which has a positive effect on the analytic effect during analysis of solutions and liquids of organic nature. Methanol serves as a solvent and glycine serves as a stabiliser for the composition.

EFFECT: proposed composition is polyfunctional and contrary to the known level, it is designed for efficient qualitative and quantitative determination, in water and solutions, of microbial cells in vegetative and spore forms; cations of heavy metals and phenol; plant and animal enzymes; formed elements of haemoglobin; organic and inorganic oxidising agents.

4 cl, 3 tbl, 11 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for preparing complexes of 2-isopropoxy-2-methylvinyl trichlorophosphonium hexachlorometals of the general formula: [(I-PrO-C(CH3)=CHP+Cl3)nMCln-6] wherein M means Sn; n = 2; M means Sb or Bi; n = 3. Method involves interaction of diisopropyl ester with phosphorus pentachloride in the inert solvent medium followed by treatment of formed compound with tin, antimony of bismuth dichloride. Before treatment of formed compound with the corresponding anhydrous metal dichloride nitromethane as a polar solvent is added to its in the amount 1.1-1.25 mole per 1 mole of phosphorus pentachloride, and mixture is heated to temperature above 55°C up to formation of the end product. Method provides increasing yield of the end product.

EFFECT: improved preparing method.

3 ex

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