COMPOUNDS THAT CAN BE USED IN AN ORGANIC ELECTRONIC DEVICE

Abstract

The invention relates to compounds that can be used in an organic electronic device as an active compound, in particular for use in electronic devices. The invention further relates to a process for preparing the compounds according to the invention, and to electronic devices comprising the same.

Claims

1.-20. (canceled)

21. A compound usable as active compound in an organic electronic device, characterized in that the compound comprises at least one structure of the formula (I) ##STR00142## where: l is an integer in the range from 1 to 8; R is the same or different at each instance and is H, D, OH, F, Cl, Br, I, CN, NO.sub.2, N(Ar).sub.2, N(R.sup.1).sub.2, C(═O)N(Ar).sub.2, C(═O)N(R.sup.1).sub.2, Si(Ar).sub.3, Si(R.sup.1).sub.3, B(Ar).sub.2, B(R.sup.1).sub.2, C(═O)Ar, C(═O)R.sup.1, P(═O)(Ar).sub.2, P(═O)(R.sup.1).sub.2, P(Ar).sub.2, P(R.sup.1).sub.2, S(═O)Ar, S(═O)R.sup.1, S(═O).sub.2Ar, S(═O).sub.2R.sup.1, OSO.sub.2Ar, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, Ge(R.sup.1).sub.2, Sn(R.sup.1).sub.2, C═O, C═S, C═Se, C═NR.sup.1, —C(═O)O—, —C(═O)NR.sup.1—, NR.sup.1, P(═O)(R.sup.1), —O—, —S—, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; at the same time, two R radicals together may also form a ring system; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted by one or more R radicals; at the same time, it is possible for two Ar radicals bonded to the same silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined together via a bridge by a single bond or a bridge selected from B(R.sup.1), C(R.sup.1).sub.2, Si(R.sup.1).sub.2, C═O, C═NR.sup.1, C═C(R.sup.1).sub.2, O, S, S═O, SO.sub.2, N(R.sup.1), P(R.sup.1) and P(═O)R.sup.1; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, CN, NO.sub.2, N(Ar.sup.1).sub.2, N(R.sup.2).sub.2, C(═O)Ar.sup.1, C(═O)R.sup.2, P(═O)(Ar.sup.1).sub.2, P(Ar.sup.1).sub.2, B(Ar.sup.1).sub.2, B(R.sup.2).sub.2, Si(Ar.sup.1).sub.3, Si(R.sup.2).sub.3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms or an alkenyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, Ge(R.sup.2).sub.2, Sn(R.sup.2).sub.2, C═O, C═S, C═Se, C═NR.sup.2, —C(═O)O—, —C(═O)NR.sup.2—, NR.sup.2, P(═O)(R.sup.2), —O—, —S—, SO or SO.sub.2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or an aralkyl or heteroaralkyl group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or a combination of these systems; at the same time, two or more R.sup.1 radicals together may form a ring system; at the same time, one or more R.sup.1 radicals with a further part of the compound may form a ring system; Ar.sup.1 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals; at the same time, two Ar.sup.1 radicals bonded to the same silicon atom, nitrogen atom, phosphorus atom or boron atom may also be joined together via a bridge by a single bond or a bridge selected from B(R.sup.2), C(R.sup.2).sub.2, Si(R.sup.2).sub.2, C═O, C═NR.sup.2, C═C(R.sup.2).sub.2, O, S, S═O, SO.sub.2, N(R.sup.2), P(R.sup.2) and P(═O)R.sup.2; R.sup.2 is the same or different at each instance and is H, D, F, Cl, Br, I, CN, B(OR.sup.3).sub.2, NO.sub.2, C(═O)R.sup.3, CR.sup.3═C(R.sup.3).sub.2, C(═O)OR.sup.3, C(═O)N(R.sup.3).sub.2, Si(R.sup.3).sub.3, P(R.sup.3).sub.2, B(R.sup.3).sub.2, N(R.sup.3).sub.2, NO.sub.2, P(═O)(R.sup.3).sub.2, OSO.sub.2R.sup.3, OR.sup.3, S(═O)R.sup.3, S(═O).sub.2R.sup.3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.3 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, C═O, C═S, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO or SO.sub.2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or a combination of these systems; at the same time, two or more substituents R.sup.2 together may also form a ring system; R.sup.3 is the same or different at each instance and is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; at the same time, two or more substituents R.sup.3 together may form a ring system.

22. The compound as claimed in claim 21, characterized in that the compound usable as active compound in an organic electronic device is selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters that exhibit TADF (thermally activated delayed fluorescence), host materials, electron transport materials, exciton blocker materials, electron injection materials, hole conductor materials, hole injection materials, n-dopants, p-dopants, wide bandgap materials, electron blocker materials and/or hole blocker materials.

23. The compound as claimed in claim 21, characterized in that the compound comprises at least one structure of the formula (II) ##STR00143## where the R radical has the definition given in claim 21 and in addition: l is an integer in the range from 1 to 8; m is an integer in the range from 0 to 7; m+l is not more than 8; R.sup.a is the same or different at each instance and is OH, F, Cl, Br, I, CN, NO.sub.2, N(Ar).sub.2, N(R.sup.1).sub.2, C(═O)N(Ar).sub.2, C(═O)N(R.sup.1).sub.2, Si(Ar).sub.3, Si(R.sup.1).sub.3, B(Ar).sub.2, B(R.sup.1).sub.2, C(═O)Ar, C(═O)R.sup.1, P(═O)(Ar).sub.2, P(═O)(R.sup.1).sub.2, P(Ar).sub.2, P(R.sup.1).sub.2, S(═O)Ar, S(═O)R.sup.1, S(═O).sub.2Ar, S(═O).sub.2R.sup.1, OSO.sub.2Ar, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, Ge(R.sup.1).sub.2, Sn(R.sup.1).sub.2, C═O, C═S, C═Se, C═NR.sup.1, —C(═O)O—, —C(═O)NR.sup.1—, NR.sup.1, P(═O)(R.sup.1), —O—, —S—, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; at the same time, R.sup.a radicals together with an R radical may also form a ring system, where the Ar and R.sup.1 radicals have the definition given in claim 21.

24. The compound as claimed in claim 21, characterized in that the compound has point symmetry and/or axial symmetry.

25. The compound as claimed in claim 23, characterized in that the compound has at least one structure of the formulae (IIIa), (IIIb) and (IIIc) ##STR00144## where the R radical has the definition given in claim 21, the R.sup.a radicals have the definition given in claim 23, and n is an integer in the range from 0 to 6.

26. The compound as claimed in claim 23, characterized in that the compound has at least one structure of the formulae (IVa), (IVb) and (IVc) ##STR00145## where the R.sup.a radicals have the definition given in claim 23, and o is an integer in the range from 0, 1, 2 or 3.

27. The compound as claimed in claim 23, characterized in that the compound has at least one structure of the formula (V) ##STR00146## the R.sup.a radicals have the definition given in claim 23.

28. The compound as claimed in claim 21, characterized in that the compound comprises a hole transport group, where one of the R and/or R.sup.a groups comprises and is a hole transport group.

29. The compound as claimed in claim 21, characterized in that the compound comprises an electron transport group, where one of the R and/or R.sup.a groups comprises and is an electron transport group.

30. The compound as claimed claim 21, characterized in that at least one of the R and/or R.sup.a radicals comprises at least one group that leads to with wide bandgap materials.

31. The compound as claimed in claim 21, characterized in that at least one of the R and/or R.sup.a radicals comprises at least one aromatic or heteroaromatic ring system having two or three, fused aromatic or heteroaromatic rings.

32. The compound as claimed in claim 21, characterized in that at least one of the R and/or R.sup.a radicals is selected from the group of the fluorenes, indenofluorenes, spirobifluorenes, carbazoles, indenocarbazoles, indolocarbazoles, spirocarbazoles, pyrimidines, triazines, lactams, triarylamines, dibenzofurans, dibenzothienes, imidazoles, benzimidazoles, benzoxazoles, benzothiazoles, 5-arylphenanthridin-6-ones, 9,10-dehydrophenanthrenes, fluoranthenes, anthracenes, benzanthracenes and fluoradenes.

33. The compound as claimed in claim 21, characterized in that at least one of the R and/or R.sup.a radicals is selected from the group consisting of phenyl, ortho-, meta- or para-biphenyl, terphenyl, quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 9,9′-diarylfluorenyl 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl, pyrenyl, triazinyl, imidazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1-, 2-, 3- or 4-carbazolyl, 1- or 2-naphthyl, anthracenyl, trans- and cis-indenofluorenyl, indenocarbazolyl, indolocarbazolyl, spirocarbazolyl, 5-aryl-phenanthridin-6-on-yl, 9,10-dehydrophenanthrenyl, fluoranthenyl, tolyl, mesityl, phenoxytolyl, anisolyl, triarylaminyl, bis(triarylaminyl), tris(triarylaminyl), hexamethylindanyl, tetralinyl, monocycloalkyl, biscycloalkyl, tricycloalkyl, alkyl, for example tert-butyl, methyl, propyl, alkoxyl, alkylsulfanyl, alkylaryl, triarylsilyl, trialkylsilyl, xanthenyl, 10-arylphenoxazinyl, phenanthrenyl and/or triphenylenyl, each of which may be substituted by one or more radicals.

34. The compound as claimed claim 21, wherein the compound is defined by the formulae (I), (II), (IIIa), (IIIb), (IIIc), (IVa), (IVb), (IVc) and (V) ##STR00147## where the R radical has the definition given in claim 21 and in addition: l is an integer in the range from 1 to 8; m is an integer in the range from 0 to 7; m+l is not more than 8; n is an integer in the range from 0 to 6; o is an integer in the range from 0, 1, 2 or 3; R.sup.a is the same or different at each instance and is OH, F, Cl, Br, I, CN, NO.sub.2, N(Ar).sub.2, N(R.sup.1).sub.2, C(═O)N(Ar).sub.2, C(═O)N(R.sup.1).sub.2, Si(Ar).sub.3, Si(R.sup.1).sub.3, B(Ar).sub.2, B(R.sup.1).sub.2, C(═O)Ar, C(═O)R.sup.1, P(═O)(Ar).sub.2, P(═O)(R.sup.1).sub.2, P(Ar).sub.2, P(R.sup.1).sub.2, S(═O)Ar, S(═O)R.sup.1, S(═O).sub.2Ar, S(═O).sub.2R.sup.1, OSO.sub.2Ar, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, Ge(R.sup.1).sub.2, Sn(R.sup.1).sub.2, C═O, C═S, C═Se, C═NR.sup.1, —C(═O)O—, —C(═O)NR.sup.1—, NR.sup.1, P(═O)(R.sup.1), —O—, —S—, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; at the same time, R.sup.a radicals together with an R radical may also form a ring system.

35. An oligomer, polymer or dendrimer containing one or more compounds as claimed in claim 21, wherein, rather than a hydrogen atom or a substituent, there are one or more bonds of the compounds to the polymer, oligomer or dendrimer.

36. A composition comprising at least one compound as claimed in claim 21 or an oligomer, polymer or dendrimer as claimed in claim 35 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters that exhibit TADF (thermally activated delayed fluorescence), host materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials and hole blocker materials.

37. A formulation comprising at least one compound as claimed in claim 21 and at least one solvent.

38. A process for preparing the compound as claimed in claim 21 which comprises in a coupling reaction, a compound comprising at least one nonaromatic or nonheteroaromatic polycyclic ring system having a cubane structure is joined to a compound comprising at least one aromatic or heteroaromatic group.

39. An electronic device comprising at least one compound as claimed in claim 21,

40. The electronic device as claimed in claim 39, wherein the electronic device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells and organic laser diodes.

Description

EXAMPLES

[0253] The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The metal complexes are additionally handled with exclusion of light or under yellow light. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The respective figures in square brackets or the numbers quoted for individual compounds relate to the CAS numbers of the compounds known from the literature. In the case of compounds that can display multiple tautomeric forms, one tautomeric form is shown representatively.

Example M1

[0254] ##STR00103##

[0255] A well-stirred mixture of 3.8 g (10.0 mmol) of 1-[phenyl]-4-(phen-4-ylboronic acid pinacol ester)pentacyclo[4.2.0.0.sup.2,5.0.sup.3,8.0.sup.4,7]octane [2179263-81-9], 6.1 g (11.0 mmol) of 3-bromo-9-(5′-phenyl[1,1′:3,1″-terphenyl]-3-yl)-9H-carbazole [1846559-13-4], 4.2 g (30.0 mmol) of potassium carbonate, 231 mg (0.2 mmol) of tetrakis(triphenylphosphino)palladium(0), 60 ml of toluene, 30 ml of dioxane and 30 ml of water is heated under reflux for 16 h. After cooling, the organic phase is separated off and concentrated under reduced pressure. The remaining solids are dissolved in 100 ml of dichloromethane (DCM), and the solution is filtered through a silica gel bed in the form of a DCM slurry. 50 ml of ethanol is added to the filtrate and the filtrate is concentrated to about 30 ml, with crystallization of the product. The crystals are filtered off with suction, washed once with 30 ml of ethanol and then dried under reduced pressure. Purification is effected by five continuous hot extractions with toluene (cellulose extraction thimbles from Whatman), followed by heat treatment under high vacuum (p about 10.sup.−6 mbar, T<20000). Yield: 1.7 g (2.3 mmol), 23%; purity: >99.7%. .sup.1H NMR.

[0256] The following compounds can be prepared analogously:

TABLE-US-00021 Boronic ester Ex. Aryl/heteroaryl halide Product Yield M2 [00104] [00105] 26% M3 [00106] [00107] 19% M4 [00108] [00109] 21%

Example D1

[0257] ##STR00110##

[0258] Procedure analogous to example M1, except that, 2.5 g (5.0 mmol) of 1,4-bis(phen-4-ylboronic acid pinacol ester)pentacyclo[4.2.0.0.sup.2,5.0.sup.3,8.0.sup.4,7]octane [2179263-82-0] is used rather than 1-[phenyl]-4-(phen-4-ylboronic acid pinacol ester)pentacyclo[4.2.0.0.sup.2,5.0.sup.3,8.0.sup.4,7]octane, and 4.4 g (11.0 mmol) of 9-[1,1′-biphenyl]-3-yl-3-bromo-9H-carbazole rather than 3-bromo-9-(5′-phenyl[1,1′:3′,1″-terphenyl]-3-yl)-9H-carbazole. Yield: 1.2 g (1.3 mmol), 26%; purity: >99.7%. .sup.1H NMR.

[0259] The following compounds can be prepared analogously:

TABLE-US-00022 Ex. Reactants Product Yield D2 [00111] [00112] 24%

Example: octa(4-chlorophenyl)cubane=O-4-CIPh-C

[0260] ##STR00113##

[0261] Procedure analogous to P. M. Maitlis et al., Proceedings of the Chemical Society, 1962, 330.

[0262] To a well-degassed, stirred suspension, heated to 80° C., of 6.7 g (10.0 mmol) of dichloro[1,1′,1″,1′″-(η.sup.4-1,3-cyclobutadiene-1,2,3,4-tetrayl)tetrakis[4-chlorobenzene]]palladium(II) [12132-23-9] (calculated as monomer) in 200 ml of toluene is added dropwise a solution of 5.4 g (20.5 mmol) of triphenylphosphine over the course of 20 min. The mixture is stirred at 80° C. for a further 8 h, then allowed to cool, and the precipitated solids are filtered off. The solids are suspended in 100 ml of DCM and stirred at 30° C. for 1 h. The solids are filtered off again, and washed twice with 20 ml each time of DCM. The crude product thus obtained is recrystallized twice from 3-phenoxytoluene. Yield: 6.3 g (6.4 mmol), 64%; purity: about 97% by HPLC.

[0263] The filtrate is admixed with 50 ml of ethanol and concentrated gradually under reduced pressure until the bis(triphenylphosphino)palladium(II) chloride present therein crystallizes. It can be obtained by filtration and used subsequently as palladium source.

[0264] The following compound can be prepared analogously:

TABLE-US-00023 Ex. Reactant Product Yield O-3-ClPh—C dichloro [1,1′,1″, 1′′′-(η.sup.4- 1,3- cyclobu- tadiene- 1,2,3,4- tetrayl) tetrakis [00114] 56% [3- chloro- benzene]] palla- dium(II), prepared analo- gously to O-4- ClPh—C as per R. C. Cookson et al., J. Chem. Soc., 1881, 1965. [00115]

Example: octa(phen-4-ylboronic acid pinacol ester)cubane=O-4-BRSE-Ph-C

[0265] ##STR00116##

[0266] To a well-stirred suspension, heated to 60° C., of 4.9 g (5.0 mmol) of O-4-CIPh-C, 15.2 g (60 mmol) of bis(pinacolato)diborane [73183-34-3], 11.8 g (120 mmol) of anhydrous potassium acetate and 50 g of glass beads (diameter 3 mm) in 200 ml of THE is added a solution of 1232 mg (3 mmol) of S-Phos and 449 mg (2 mmol) palladium(II) acetate in 30 ml THE that has been heated to 60° C. while stirring for 10 min. The reaction mixture is stirred at 60° C. for 24 h. Then a further 5.1 g (20 mmol) of bis(pinacolato)diborane and ⅓ of the catalyst solution used above are added, and the mixture is heated for a further 16 h. After cooling, the THF is largely removed under reduced pressure, and the residue is taken up in 300 ml of hot methanol while stirring. After cooling, the crude product is filtered off with suction and washed three times with 50 ml each time of methanol. Further purification is effected by continuous hot extraction (cellulose extraction thimbles from Whatman), twice with DCM/methanol 2:1 and twice with DCM/acetonitrile 2:1. Yield: 5.0 g (2.9 mmol), 58%; purity: about 98% by HPLC.

[0267] The following compound can be prepared analogously:

TABLE-US-00024 Ex. Reactant Product Yield O-3-BRSE-Ph—C O-3-ClPh—C [00117] 47% [00118]

Example O1

[0268] ##STR00119## [0269] X is the functional [0270] radical shown in each case

[0271] A well-stirred mixture of 8.6 g (5 mmol) of O-4-BRSE-Ph-C, 14.0 g (60 mmol) of 3-bromo-1,1′-biphenyl [2113-57-7], 27.6 g (120 mmol) of tripotassium phosphate monohydrate, 1.15 g (1 mmol) of tetrakis(triphenylphosphino)palladium(0), 50 g of glass beads (diameter 3 mm) and 150 ml DMSO is heated to 120° C. for 24 h. After cooling to 60° C., the reaction mixture is poured into 300 ml of a water-methanol mixture (1:1, vv) and stirred for a further 30 min, and the crude product is filtered off with suction and washed three times with 30 ml each time of methanol. The crude product is dissolved in 200 ml of DCM, and the solution is filtered through a silica gel bed in the form of a DCM slurry. 50 ml of ethanol is added to the filtrate and the filtrate is concentrated to about 30 ml, with crystallization of the product. The crystals are filtered off with suction, washed once with 30 ml of ethanol and then dried under reduced pressure. Purification is effected by five continuous hot extractions with o-xylene (cellulose extraction thimbles from Whatman), followed by heat treatment under high vacuum (p about 10.sup.−6 mbar, T<300° C.). Yield: 3.5 g (1.8 mmol), 36%; purity: >99.7%. .sup.1H NMR.

[0272] The following compounds can be prepared analogously:

TABLE-US-00025 Ex. Reactants Product Yield O2 [00120] [00121] 44% O3 [00122] [00123] 35% O4 [00124] [00125] 37% O5 [00126] [00127] 35% O6 [00128] [00129] 41% O7 [00130] [00131] 26% O8 [00132] [00133] 29%

[0273] It is analogously possible to react O-3-BRSE-Ph-C and O-4-BRSE-Ph-C with mono-bromo-functionalized oligo-phenylenes, fluorene, carbazole, dibenzofuran or mixtures thereof. Purification is effected by reprecipitation of the crude product from DCM in methanol or by chromatography, flash chromatography or gel permeation chromatography. Some examples of suitable bromides are listed in the table which follows in the form of the CAS numbers:

TABLE-US-00026 Ex. CAS  O9 180802-93-1 O10 180802-96-4 O11 797789-75-4 O12 1382210-35-6 O13 1310675-72-9 O14 5121-77-7 O15 1184456-33-4 O16 863111-73-3 O17 1134375-86-2 O18 446879-01-2 O19 1609238-90-5 O20 1356465-30-9

Solution-Processed Devices:

A: From Soluble Functional Materials of Low Molecular Weight

[0274] The materials of the invention can be processed from solution. The production of such components is based on the production of polymeric light-emitting diodes (PLEDs), which has already been described many times in the literature (for example in WO 2004/037887). The structure is composed of substrate/ITO/hole injection layer (60 nm)/interlayer (20 nm)/emission layer (60 nm)/hole blocker layer (10 nm)/electron transport layer (40 nm)/cathode. For this purpose, substrates from Technoprint (soda-lime glass) are used, to which the ITO structure (indium tin oxide, a transparent conductive anode) is applied. The substrates are cleaned in a cleanroom with DI water and a detergent (Deconex 15 PF) and then activated by a UV/ozone plasma treatment. Thereafter, likewise in a cleanroom, a 20 nm hole injection layer is applied by spin-coating (PEDOT:PSS from Clevios™). The required spin rate depends on the degree of dilution and the specific spin-coater geometry. In order to remove residual water from the layer, the substrates are baked on a hotplate at 200° C. for 30 minutes. The interlayer used serves for hole transport, in this case, HL-X from Merck is used. The interlayer may alternatively also be replaced by one or more layers which merely have to fulfill the condition of not being leached off again by the subsequent processing step of EML deposition from solution. For production of the emission layer, the triplet emitters of the invention are dissolved together with the matrix materials in toluene or chlorobenzene. The typical solids content of such solutions is between 16 and 25 g/I when, as here, the layer thickness of 60 nm which is typical of a device is to be achieved by means of spin-coating. The solution-processed devices contain an emission layer composed of Material1:Material2:Material3:Emitter (for percentages by weight see table 1). The emission layer is spun on in an inert gas atmosphere, argon in the present case, and baked at 160° C. for 30 min. Vapor-deposited atop the latter are the hole blocker layer (10 nm ETMx) and the electron transport layer (40 nm ETM1 (50%)/ETM2 (50%)) (vapor deposition systems from Lesker or the like, typical vapor deposition pressure 5×10.sup.−6 mbar). Finally, a cathode of aluminum (100 nm) (high-purity metal from Aldrich) is applied by vapor deposition. In order to protect the device from air and air humidity, the device is finally encapsulated and then characterized. The OLED examples cited are yet to be optimized; table 1 summarizes the data obtained. The lifetime LT50 is defined as the time after which the luminance in operation drops to 50% of the starting luminance with a starting brightness of 1000 cd/m.sup.2.

TABLE-US-00027 TABLE 1 Results for the devices Material1 EQE Voltage Material2 (%) (V) Material3 1000 1000 LT50 (h) Ex. Emitter cd/m.sup.2 cd/m.sup.2 CIE x/y 1000 cd/m.sup.2 Sol-D1  M4 (20%) 20.1 4.6 0.33/0.62 300000 TMM2 (58%) — IrL (22%) Sol-D2  O4 (10%) 21.8 4.4 0.33/0.62 330000 TMM2 (66%) — IrL (24%) Sol-D3  M1 (10%) 20.6 4.2 0.33/0.63 320000 TMM2 (58%) M2 (10%) IrL (22%) Sol-D4  M3 (10%) 20.2 4.3 0.32/0.63 300000 TMM2 (58%) M2 (10%) IrL (22%) Sol-D5  D1 (12%) 22.0 4.5 0.33/0.63 290000 TMM2 (58%) D2 (8%) IrL (22%) Sol-D6  TMM1 (40%) 20.3 4.2 0.32/0.62 320000 O1 (40%) — IrL (20%) Sol-D7  TMM1 (40%) 20.5 4.4 0.32/0.62 360000 O2 (40%) — IrL (20%) Sol-D7  O4 (40%) 22.0 4.3 0.32/0.63 340000 O8 (40%) — IrL (20%) Sol-D8  O3 (10%) 21.7 4.3 0.33/0.63 320000 TMM2 (60%) O5 (10%) IrL (20%) Sol-D9  3.0 5.4 0.14/0.12 — Sol-D10 O9 (10%) 19.7 4.4 0.33/0.62 260000 TMM2 (60%) — IrL (30%) Sol-D11 O12 (10%) 14.9 4.2 0.33/0.64 330000 TMM2 (60%) — IrL (30%)

B: Use of the Compounds of the Invention in Crosslinkable Hole Conductor Layers

[0275] The production of solution-processed OLEDs with a crosslinkable hole conductor unit has already been described in WO 2004/037887 and WO 2010/097155. The basic production method is adapted to the materials and layer thicknesses described below. The compounds of the invention are used in the following structure: [0276] substrate, [0277] indium tin oxide ITO (50 nm), [0278] PEDOT (80 nm), [0279] hole transport layer (HTL) (20 nm), [0280] emission layer (EML) (60 nm), [0281] hole blocker layer (HBL) (10 nm), [0282] electron transport layer (ETL) (40 nm), [0283] cathode.

[0284] For this purpose, substrates from Technoprint (soda-lime glass) are used, to which the ITO structure (indium tin oxide, a transparent conductive anode) is applied. The substrates are cleaned in a cleanroom with DI water and a detergent (Deconex 15 PF) and then activated by a UV/ozone plasma treatment. Thereafter, likewise in a cleanroom, an 80 nm hole injection layer of PEDOT-PSS (commercially available from Heraeus GmbH & Co. KG, Germany) is applied by spin-coating. The required spin rate depends on the degree of dilution and the specific spin-coater geometry. In order to remove residual water from the layer, the substrates are baked on a hotplate at 180° C. for 20 minutes. The compounds of the invention serve as hole transport layer, optionally in combination with other hole conductor materials. They are applied from toluenic solution, solids content typically about 7 g/l, at a layer thickness of about 20 nm, by spin-coating under inert atmosphere (argon), and baked at 220° C. for 60 min.

[0285] For production of the emission layer, the triplet emitters are dissolved together with the matrix materials in toluene or chlorobenzene. The typical solids content of such solutions is between 16 and 25 g/I when, as here, the layer thickness of 60 nm which is typical of a device is to be achieved by means of spin-coating. The solution-processed triplet devices contain an emission layer composed of Material1:Material2:Material3:Emitter (for percentages by weight see table 1). The emission layer is spun on in an inert gas atmosphere, argon in the present case, and baked at 160° C. for 20 min. Vapor-deposited atop the latter are the hole blocker layer (10 nm ETM1) and the electron transport layer (40 nm ETM1 (50%)/ETM2 (50%)) (vapor deposition systems from Lesker or the like, typical vapor deposition pressure 5×10.sup.−6 mbar). Finally, a cathode of aluminum (100 nm) (high-purity metal from Aldrich) is applied by vapor deposition. In order to protect the device from air and air humidity, the device is finally encapsulated and then characterized. The OLED examples cited are yet to be optimized; table 2 summarizes the data obtained. The lifetime LT50 is defined as the time after which the luminance in operation drops to 50% of the starting luminance with a starting brightness of 1000 cd/m.sup.2.

TABLE-US-00028 TABLE 2 Results for the triplet devices EML Material1 EQE Voltage HLT Material2 (%) (V) LT50 (h) Material1 Material3 1000 1000 1000 Ex. Material2 Emitter cd/m.sup.2 cd/m.sup.2 CIE x/y cd/m.sup.2 Sol-C1 O7 TMM1 19.8 4.6 0.33/0.62 280000 (100 %) (20%) — TMM2 (58%) — IrL (22%) Sol-C2 O7 TMM1 20.2 4.4 0.32/0.62 310000 (70 %) (20%) HTM1 TMM2 (30 %) (60%) — IrL (20%)

TABLE-US-00029 TABLE 4 Structural formulae of the materials used [00134] [00135] [00136] [00137] [00138] [00139] [00140] [00141]