MATERIALS FOR ORGANIC ELECTROLUMINESCENT DEVICES

Abstract

The present invention relates to compounds of the formula (1) and mixture comprising these compounds, which are suitable for use in electronic devices, in particular organic electroluminescent devices, and to electronic devices which comprise these compounds and mixtures.

Claims

1.-17. (canceled)

18. A compound of the formula (1), ##STR00470## where the following applies to the symbols and indices used: Ar.sup.1 stands on each occurrence, identically or differently, for an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1; Ar.sup.2 stands on each occurrence, identically or differently, for an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.2; Ar.sup.3 stands on each occurrence, identically or differently, for an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.3; -E- is a single bond, —B(R.sup.0)—, —C(R.sup.0).sub.2—, —Si(R.sup.0).sub.2—, —C(═O)—, —C(═NR.sup.0)—, —C(═C(R.sup.0).sub.2)—, —O—, —S—, —S(═O)—, —S(O.sub.2)—, —N(R.sup.0)—, —P(R.sup.0)— or —P((═O)R.sup.0)—; R.sup.0, R.sup.1, R.sup.2, R.sup.3 stand on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, N(Ar).sub.2, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, NO.sub.2, Si(R).sub.3, B(OR).sub.2, OSO.sub.2R, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by RC═CR, C≡C, Si(R).sub.2, Ge(R).sub.2, Sn(R).sub.2, C═O, C═S, C═Se, P(═O)(R), SO, SO.sub.2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R, where two radicals R.sup.0, two radicals R.sup.1, two radicals R.sup.2 and/or two radicals R.sup.3 may form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another, which may be substituted by one or more radicals R; R stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, N(Ar).sub.2, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, NO.sub.2, Si(R′).sub.3, B(OR′).sub.2, OSO.sub.2R′, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R′, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by R′C═CR′, C≡C, Si(R′).sub.2, Ge(R′).sub.2, Sn(R′).sub.2, C═O, C═S, C═Se, P(═O)(R′), SO, SO.sub.2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R′, where two radicals R may form a ring system with one another, which may be substituted by one or more radicals R′; Ar is an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may in each case also be substituted by one or more radicals R; R′ stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by SO, SO.sub.2, O, S and where one or more H atoms may be replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 24 C atoms; n is 0 or 1; wherein when n is 0, the group -E- is absent; wherein the compound of formula (1) comprise at least one group Ar.sup.3, R.sup.1, R.sup.2 or R.sup.3, which stand for a triphenylene derivative of the formula (T), ##STR00471## where the dashed bond indicates the bonding to the structure of formula (1), and where: R.sup.4 is C at the position of the bonding to Ar.sup.S or, R.sup.4 is C at the position of the bonding to the structure of formula (1) if m is 0; and at other positions, R.sup.4 stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, N(Ar).sub.2, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, NO.sub.2, Si(R).sub.3, B(OR).sub.2, OSO.sub.2R, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by RC═CR, C≡C, Si(R).sub.2, Ge(R).sub.2, Sn(R).sub.2, C═0, C═S, C═Se, P(═O)(R), SO, SO.sub.2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R, where two radicals R.sup.4 may form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R; Ar.sup.S is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case also be substituted by one or more radicals R; and m is an integer selected from 0, 1, 2, 3 or 4; and where the following compounds are excluded: ##STR00472## ##STR00473## ##STR00474## ##STR00475## ##STR00476##

19. The compound according to claim 18, wherein the compound is selected from compounds of formulae (1A) or (1B), ##STR00477## where the symbol -E- has the same meaning as in claim 18; X is CR.sup.1 or N; Y is CR.sup.2 or N; where the symbols R.sup.1, R.sup.2 have the same meaning as in claim 18; and Ar.sup.3 has the same meaning as in claim 18, with the proviso that Ar.sup.3, in formula (1B), is connected to the group -E- and the atom N via two adjacent C atoms as represented in formula (1B); characterized in that, in formula (1A), at least one group Ar.sup.3, R.sup.1 or R.sup.2 stands for a triphenylene derivative of the formula (T) and, in formula (1B), at least one group R.sup.1 or R.sup.2 stands for a triphenylene derivative of the formula (T), where the triphenylene derivative of the formula (T) is as defined in claim 18.

20. The compound according to claim 18, wherein the compound is selected from the compounds of formulae (2), (3), (4), (5), (6) or (7), ##STR00478## ##STR00479## ##STR00480## where the symbols and indices E, R.sup.4, Ar.sup.S and m have the same meaning as in claim 18; and where X is CR.sup.1 or N, with the proviso that X is C at the position of the bonding to Ar.sup.S or, if m is 0 and Ar.sup.S is absent, to the triphenylene group in formulae (4) and (6); Y is CR.sup.2 or N, with the proviso that Y is C at the position of the bonding to Ar.sup.S or, if m is 0 and Ar.sup.S is absent, to the triphenylene group in formulae (3) and (5); V is CR.sup.3 or N, with the proviso that V is C at the position of the bonding to Ar.sup.S or, if m is 0 and Ar.sup.S is absent, to the triphenylene group in formula (7); or two adjacent groups V stand for a group of formula (V-1) or (V-2), ##STR00481## where the symbols .sup.v indicate the corresponding adjacent groups V in formulae (2) to (7); E.sup.0 stands for —C(R.sup.0).sub.2—, —Si(R.sup.0).sub.2—, —C(═O)—, —C(═NR.sup.0)—, —C(═C(R.sup.0).sub.2)—, —O—, —S—, —S(═O)—, —S(O.sub.2)—, —N(R.sup.0)—, —P(R.sup.0)— or —P((═O)R.sup.0)—; where R.sup.0 has the same meaning as in claim 18; and W stands for CR or N.

21. The compound according to claim 18, wherein the index m is equal to 0 or 1.

22. The compound according to claim 18, wherein the group Ar.sup.S stands on each occurrence, identically or differently, for phenyl, biphenyl, fluorene, spirobifluorene, naphthalene, phenanthrene, anthracene, dibenzofuran, dibenzothiophene, carbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, benzopyridine, benzopyridazine, benzopyrimidine and quinazoline, each of which may be substituted by one or more radicals R.

23. The compound according to claim 18, wherein the group Ar.sup.S stands on each occurrence, identically or differently, for phenyl, biphenyl, fluorene, naphthalene, dibenzofuran, dibenzothiophene and carbazole, each of which may be substituted by one or more radicals R.

24. The compound according to claim 19, wherein there is 0 or 1 group X standing for N in the six-membered ring comprising the groups X, there is 0 or 1 group Y standing for N in the six-membered ring comprising the groups Y and there is 0 or 1 group V in the six-membered ring comprising the groups V.

25. The compound according to claim 20, wherein the compound is selected from compounds of formulae (2A) to (7B), ##STR00482## ##STR00483## ##STR00484## ##STR00485## wherein the symbols X, Y and V are defined in claim 20.

26. The compound according to claim 20, wherein the compound is selected from compounds (2A-1) to (7B-1), ##STR00486## ##STR00487## ##STR00488## ##STR00489## ##STR00490## where the symbols X, Y, V have the same meaning as in claim 20.

27. The compound according to claim 18, wherein the compound comprises at least one of the substituent R.sup.1 or R.sup.2, which is selected from aromatic and heteroaromatic ring systems.

28. A mixture comprising at least one compound according to claim 18 and a second compound comprising at least one group of formula (10), ##STR00491## where R.sup.10 stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, N(Ar).sub.2, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, NO.sub.2, Si(R).sub.3, B(OR).sub.2, OSO.sub.2R, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by RC═CR, C≡C, Si(R).sub.2, Ge(R).sub.2, Sn(R).sub.2, C═O, C═S, C═Se, P(═O)(R), SO, SO.sub.2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R, where two radicals R.sup.10 may form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another, which may be substituted by one or more radicals R; Ar.sup.10 is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case also be substituted by one or more radicals R; p is an integer selected from 0, 1, 2, 3 and 4; T is CR.sup.11 or N; or two adjacent groups T stand for a group of formula (T-1), ##STR00492## where the symbols .sup.v in formula (T-1) indicate the corresponding adjacent groups T in formula (10); E.sup.10 stands for —C(R.sup.0).sub.2—, —Si(R.sup.0).sub.2—, —C(═O)—, —C(═NR.sup.0)—, —C(═C(R.sup.0).sub.2)—, —O—, —S—, —S(═O)—, —S(O.sub.2)—, —N(Ar.sup.10)—, —P(R.sup.0)— or —P((═O)R.sup.0)—; where R.sup.0 has the same meaning as in claim 18; Z stands for CR.sup.10 or N; and the groups R and Ar have the same meaning as in claim 18.

29. The mixture according to claim 28, wherein the second compound comprising at least one group of formula (10) is selected from compounds of formulae (11) and (12), ##STR00493## where the symbols and indices Ar.sup.10, E.sup.10, R.sup.10 and p have the same meaning as in claim 28; E.sup.11 stands for —C(R.sup.0).sub.2—, —Si(R.sup.0).sub.2—, —C(═O)—, —C(═NR.sup.0)—, —C(═C(R.sup.0).sub.2)—, —O—, —S—, —S(═O)—, —S(O.sub.2)—, —N(Ar.sup.10)—, —P(R.sup.0)— or —P((═O)R.sup.0)—; where R.sup.0 has the same meaning as in claim 18; L.sup.1 is a single bond or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case also be substituted by one or more radicals R; R stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, N(Ar).sub.2, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, NO.sub.2, Si(R′).sub.3, B(OR′).sub.2, OSO.sub.2R′, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R′, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by R′C═CR′, C≡C, Si(R′).sub.2, Ge(R′).sub.2, Sn(R′).sub.2, C═O, C═S, C═Se, P(═O)(R), SO, SO.sub.2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R′, or an aryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R′, where two radicals R may form a ring system with one another, which may be substituted by one or more radicals R′; Ar is an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may in each case also be substituted by one or more radicals R; R′ stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by SO, SO.sub.2, O, S and where one or more H atoms may be replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 24 C atoms.

30. The mixture according to claim 28, wherein the second compound comprising at least one group of formula (10) is selected from compounds of formulae (11-1) to (12-4), ##STR00494## E.sup.12 stands for —C(R.sup.0).sub.2—, —O—, —S—, —N(Ar.sup.10)—; where Ar.sup.10 is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case also be substituted by one or more radicals R; R.sup.0 is H, D, F, Cl, Br, I, CHO, CN, N(Ar).sub.2, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, NO.sub.2, Si(R).sub.3, B(OR).sub.2, OSO.sub.2R, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by RC═CR, C≡C, Si(R).sub.2, Ge(R).sub.2, Sn(R).sub.2, C═O, C═S, C═Se, P(═O)(R), SO, SO.sub.2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R, where two radicals R.sup.0, two radicals R.sup.1, two radicals R.sup.2 and/or two radicals R.sup.3 may form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another, which may be substituted by one or more radicals R; R stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, N(Ar).sub.2, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, NO.sub.2, Si(R′).sub.3, B(OR′).sub.2, OSO.sub.2R′, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R′, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by R′C═CR′, C≡C, Si(R′).sub.2, Ge(R′).sub.2, Sn(R′).sub.2, C═O, C═S, C═Se, P(═O)(R′), SO, SO.sub.2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R′, where two radicals R may form a ring system with one another, which may be substituted by one or more radicals R′; Ar is an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may in each case also be substituted by one or more radicals R; R′ stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by SO, SO.sub.2, O, S and where one or more H atoms may be replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 24 C atoms.

31. The mixture according to claim 28, wherein the second component comprising at least one group of formula (10) is selected from compounds of formulae (13-1) to (14-4), ##STR00495## where the symbols and indices R.sup.10, E.sup.10 and p have the same meaning as in claim 28, E.sup.12 stands for —C(R.sup.0).sub.2—, —O—, —S—, —N(Ar.sup.10)—; where Ar.sup.10 is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case also be substituted by one or more radicals R; R.sup.0 is H, D, F, Cl, Br, I, CHO, CN, N(Ar).sub.2, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, NO.sub.2, Si(R).sub.3, B(OR).sub.2, OSO.sub.2R, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by RC═CR, C≡C, Si(R).sub.2, Ge(R).sub.2, Sn(R).sub.2, C═O, C═S, C═Se, P(═O)(R), SO, SO.sub.2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R, where two radicals R.sup.0, two radicals R.sup.1, two radicals R.sup.2 and/or two radicals R.sup.3 may form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another, which may be substituted by one or more radicals R; R stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, N(Ar).sub.2, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, NO.sub.2, Si(R′).sub.3, B(OR′).sub.2, OSO.sub.2R′, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R′, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by R′C═CR′, C≡C, Si(R′).sub.2, Ge(R′).sub.2, Sn(R′).sub.2, C═O, C═S, C═Se, P(═O)(R′), SO, SO.sub.2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R′, where two radicals R may form a ring system with one another, which may be substituted by one or more radicals R′; Ar is an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may in each case also be substituted by one or more radicals R′; R′ stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, where in each case one or more non-adjacent CH.sub.2 groups may be replaced by SO, SO.sub.2, O, S and where one or more H atoms may be replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 24 C atoms, Ar.sup.10 stands for an aromatic or heteroaromatic ring system selected from benzene, naphthalene, pyrene, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, cis- or trans-indenofluorene, dibenzofuran, dibenzothiophene, carbazole, indolocarbazole, indenocarbazole, which may be substituted by one or more radicals R; or combinations of these groups; L.sup.2 stands for a single bond or an aromatic or heteroaromatic rings system having 6 to 18 aromatic rings atoms, which may be substituted by one or more radicals R; Ar.sup.12 stands for an heteroaromatic ring system selected from pyridine, pyrazine, pyrimidine, triazine, which may be substituted by one or more radicals R.

32. A formulation comprising the compound according to claim 18 and a solvent.

33. A formulation comprising the mixture according to claim 28, and a solvent.

34. An electronic device comprising at least one compound according to claim 18, wherein the 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, dye-sensitised organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes and organic plasmon emitting devices.

35. An electronic device comprising the mixture according to claim 28, wherein the device is selected from the group consisting of 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, dye-sensitised organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes and organic plasmon emitting devices.

36. An organic electroluminescent devices which comprises the compound according to claim 18 is employed as a matrix material for phosphorescent emitters in a light-emitting layer.

37. An organic electroluminescent devices which comprises the mixture according to claim 28 is employed as a matrix material for phosphorescent emitters in a light-emitting layer.

Description

A) SYNTHESES EXAMPLES

[0137] The following syntheses are carried out, unless indicated otherwise, under a protective-gas atmosphere in dried solvents. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The corresponding CAS numbers are also indicated in each case from the compounds known from the literature.

Example a

6-(3-Triphenylen-2-yl-phenyl)-6H-benzo[c][2,6]naphthyridin-5-one

[0138] ##STR00318##

[0139] 19.6 g (100 mmol) of benzo[c]-2,6-naphthyridinone, 51.6 g (120 mmol) of 2-(3-iodo-phenyl)-triphenylene and 2.3 g (20 mmol) of L-proline are dissolved in 100 mL of DMF and stirred at 150° C. for 30 h. The solution is diluted with water, extracted with ethyl acetate twice, the combined organic phases dried over Na.sub.2SO.sub.4 and concentrated by rotary evaporation. The residue is purified by chromatography (EtOAc/hexane: 2/3). The residue is recrystallized from toluene and from dichloromethane/toluene and finally sublimed under high vacuum. The yield is 39 g (78 mmol) 66% of theory.

[0140] The following compounds are obtained analogously:

TABLE-US-00005 Ex. Educt 1 Educt 2 Product Yield  1a [00319]   [157848-49-2] [00320]   [19111-87-6] [00321] 53%  2a [00322]   [109553-68-6] [00323]   [24253-52-9] [00324] 60%  3a [00325]   [1186039-92-8] [00326]   [1395888-84-2] [00327] 66%  4a [00328]   40197-38-4 [00329]   [1395888-84-2] [00330] 62%  5a [00331]   [157848-49-2] [00332]   [1888414-28-5] [00333] 77%  6a [00334]   [157848-49-2] [00335]   [1616514-20-5] [00336] 75%  7a [00337]   [157848-49-2] [00338]   [1616514-13-6] [00339] 78%  8a [00340]   [157848-49-2] [00341]   [1570190-91-8] [00342] 64%  9a [00343]   [1015-89-0] [00344]   [1505512-76-4] [00345] 79% 10a [00346]   [1015-89-0] [00347]   [19111-87-6] [00348] 80% 11a [00349]   [1015-89-0] [00350] [00351] 77%

Example b: 5-(4-Brom-phenyl)-5H-phenanthridin-6-one

[0141] ##STR00352##

[0142] 6.0 g (22.2 mmol) of 5-phenyl-5H-phenanthridin-6-one are initially put in 150 mL of DMF. A solution of 4 g (22.5 mmol) of NBS is then added dropwise in 100 mL of DMF at room temperature, with exclusion of light. The mixture is further stirred during 4 h at room temperature. Then, the mixture is mixed with 150 mL of water and extracted with CH.sub.2Cl.sub.2. The organic phase is dried over MgSO4 and the solvents are removed in vacuo. The product is stirred with hot hexane and filtered. Yield: 7.4 g (21 mmol), 80% of theory.

[0143] The following compounds are obtained analogously:

TABLE-US-00006 Ex. Educt 1 Product 1 Yield 1b [00353]   [129647-00-3] [00354] 68% 2b [00355] [00356] 85%

[0144] Analogously, the following compounds are obtained with 2 equivalents of NBS in chloroform as solvent:

TABLE-US-00007 Ex. Educt 1 Product 1 Yield 3b [00357] [00358] 87% 4b [00359] [00360] 82% 5b [00361] [00362] 83%

Example c: 5-(4-Triphenylen-2-yl-phenyl)-5H-phenanthridin-6-one

[0145] ##STR00363##

[0146] 29.9 g (110.0 mmol) of triphenylene-2-boronic acid, 38 g (110.0 mmol) of 5-(4-bromo-phenyl)-5H-phenanthridin-6-one and 44.6 g (210.0 mmol) of tripotassium phosphate are suspended in 500 mL of toluene, 500 mL of dioxane and 500 mL of water. Then, 913 mg (3.0 mmol) of tri-o-tolyl-phosphine and subsequently 112 mg (0.5 mmol) of palladium(II)acetate are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is collected, filtered through silica gel, washed three times with 200 mL of water and then concentrated to dryness. The residue is recrystallized from toluene and from dichloromethane/isopropanol and finally sublimed under high vacuum, purity is 99.9%. The yield is 43 g (86 mmol), corresponding to 80% of theory.

[0147] The following compounds are obtained analogously:

TABLE-US-00008 Ex. Educt 1 Educt 2 1c [00364] [00365]   [890042-13-4] 2c [00366] [00367]   [890042-13-4] 3c [00368] [00369]   [890042-13-4] 4c [00370] [00371]   [1394813-63-8] 5c [00372] [00373]   [890042-13-4] 6c [00374] [00375]   [1714136-45-4] 7c [00376]   [1629245-82-4] [00377]   [2020404-50-4] 8c [00378]   [1629245-81-3] [00379]   [1235876-72-8] 9c [00380]   [1369958-42-8] [00381]   [890042-13-4] 10c [00382] [00383]   [1235876-72-8] 11c [00384]   [1346571-48-9] [00385]   [890042-13-4] 12c [00386]   [1346571-41-2] [00387]   [1235876-72-8] 13c [00388]   [1346571-39-8] [00389]   [890042-13-4] 14c [00390]   [25890-89-5] [00391]   [654664-63-8] 15c [00392]   [904503-80-6] [00393]   [654664-63-8] 16c [00394]   [904503-77-1] [00395]   [654664-63-8] 17c [00396]   [2088465-03-4] [00397]   [1943719-84-3] 18c [00398]   [2088464-91-7] [00399]   [1620765-26-5] 19c [00400]   [1887014-91-6] [00401]   [1638272-53-3] 20c [00402]   [1840905-70-5] [00403]   [1372893-20-3] 21c [00404]   [1615703-25-7] [00405]   [1235876-72-8] 22c [00406]   [1433190-03-4] [00407]   [654664-63-8] 23c [00408]   1433190-00-1] [00409]   [1158227-50-9] 24c [00410]   [1346571-50-3] [00411]   [654664-63-8] 25c [00412]   [1346571-45-6] [00413]   [1235876-72-8] 26c [00414]   [88312-88-3] [00415]   [1372893-20-3] 27c [00416]   [101879-84-9] [00417]   [2020404-50-4] 28C [00418]   [1615703-25-7] [00419]   [654664-63-8] 29c [00420]   [1346571-45-6] [00421]   [654664-63-8] 30c [00422] [00423]   [1235876-72-8] 31c [00424]   1346571-40-1] [00425]   [1235876-72-8] Ex. Product Yield 1c [00426] 84% 2c [00427] 68% 3c [00428] 67% 4c [00429] 71% 5c [00430] 75% 6c [00431] 76% 7c [00432] 70% 8c [00433] 66% 9c [00434] 73% 10c [00435] 71% 11c [00436] 80% 12c [00437] 78% 13c [00438] 81% 14c [00439] 63% 15c [00440] 59% 16c [00441] 79% 17c [00442] 75% 18c [00443] 79% 19c [00444] 64% 20c [00445] 81% 21c [00446] 77% 22c [00447] 79% 23c [00448] 76% 24c [00449] 68% 25c [00450] 84% 26c [00451] 63% 27c [00452] 81% 28C [00453] 67% 29c [00454] 86% 30c [00455] 83% 31c [00456] 84%

[0148] A) Fabrication of OLEDs

[0149] The following examples V1 and E1 (see Table 1) show data of OLEDs.

[0150] Substrate Pre-Treatment of Examples V1-E1:

[0151] Glass plates with structured ITO (50 nm, indium tin oxide) form the substrates on which the OLEDs are processed. Before evaporation of the OLED materials, the substrates are cleaned in a wet process (using filtered deionized water and the detergent “Extran” of Merck KGaA). Glass substrates are then dried for 15 minutes at 170° C.

[0152] Subsequently the clean and dry substrates are exposed to a oxygen and subsequently to an Argon plasma.

[0153] The OLEDs have in principle the following layer structure: substrate/hole-transport layer (HTL)/optional interlayer (IL)/electron-blocking layer (EBL) I emission layer (EML)/optional hole-blocking layer (HBL)/electron-transport layer (ETL)/optional electron-injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm. The exact layer structure is denoted in Table 1 (ITO and Aluminium layers are omitted for clarity). The materials used for the OLED fabrication are presented in Table 2.

[0154] All materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer here always consists of at least one matrix material (host material) and an emitting dopant (emitter), which is admixed with the matrix material or matrix materials in a certain proportion by volume by co-evaporation. An expression such as CbzT1:SdT1:TEG1 (41%:41%:18%) here means that material CbzT1 is present in the layer in a proportion by volume of 41%, SdT1 is present in the layer in a proportion of 41% and TEG1 is present in the layer in a proportion of 18%. Analogously, the electron-transport layer may also consist of a mixture of two materials.

[0155] The OLEDs are characterized by standard methods.

[0156] For this purpose, the electroluminescence spectra and the lifetime are determined. The electroluminescent spectra are determined at a brightness of 1000 cd/m.sup.2 and the corresponding CIE 1931 x and y color coordinates are determined.

[0157] Lifetime LT is defined as the time in hours (h), after which the starting brightness at constant current density jo, is reduced to a certain level L1 in % of the starting brightness.

[0158] Here L1=80% means, that the given lifetime LT corresponds to the time after which the brightness is reduced to 80% of its starting value.

[0159] Use of Inventive Compounds as Host Material in Phosphorescent OLEDs

[0160] The inventive compounds can be used for example in the emission layer (EML) of a phosphorescent green OLED. The inventive combination of the compound CbzT1 with one of the compound EG1 to EG5 is used as matrix material in the emission layer.

[0161] In the following section several examples are described in more detail to show the advantages of the inventive OLEDs.

[0162] Use of Inventive Compounds as Host Material in Phosphorescent OLEDs

[0163] By using the compounds according to the state of the art like in example V1 with high emitter concentrations in the EML of e.g. 18%, good color coordinates with x/y in the range of 0.33/0.63 can be reached.

[0164] Nevertheless, the lifetime of such devices is not very high.

[0165] A substantial improvement of the lifetime by 25-30% versus the state of the art like in example V1 at similar color coordinates, can be reached for example by using the inventive combination of CbzT1 and one of the compound EG1 to EG5 and similar emitter concentrations (e.g. 18%) in the emission layer like in example E1.

TABLE-US-00009 TABLE 1 Structure of the OLEDs HIL HTL EBL EML ETL EIL Ex Thickness Thickness Thickness Thickness HBL Thickness Thickness V1 HATCN SpMA1 SpMA2 CbzT1:SdT1:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (41%:41%:18%) 10 nm (50%:50%) 1 nm 30 nm 30 nm E1 HATCN SpMA1 SpMA2 CbzT1:EG1:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (41%:41%:18%) 10 nm (50%:50%) 1 nm 30 nm 30 nm E2 HATCN SpMA1 SpMA2 CbzT1:EG2:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (41%:41%:18%) 10 nm (50%:50%) 1 nm 30 nm 30 nm E3 HATCN SpMA1 SpMA2 CbzT1:EG3:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (41%:41%:18%) 10 nm (50%:50%) 1 nm 30 nm 30 nm E4 HATCN SpMA1 SpMA2 CbzT1:EG4:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (41%:41%:18%) 10 nm (50%:50%) 1 nm 30 nm 30 nm E5 HATCN SpMA1 SpMA2 CbzT1:EG5:TEG1 ST2 ST2:LiQ LiQ 5 nm 230 nm 20 nm (41%:41%:18%) 10 nm (50%:50%) 1 nm 30 nm 30 nm

TABLE-US-00010 TABLE 2 Chemical structures of the materials used in the OLEDs [00457] HATCN [00458] SpMA1 [00459] SpMA2 [00460] ST2 [00461] TEG1 [00462] LiQ [00463] CbzT1 [00464] SdT1 [00465] EG1 [00466] EG2 [00467] EG3 [00468] EG4 [00469] EG5

TABLE-US-00011 TABLE 3 OLEDs Data U1000 SE1000 EQE 1000 CIE x/y bei L.sub.0; L.sub.1 LD Ex.. (V) (cd/A) (%) 1000 cd/m.sup.2 j.sub.0 % (h) E1 <3.7 >57 >15 0.32/0.62 20 mA/cm.sup.2 80  90 E2 <3.6 >60 >18 0.32/0.62 20 mA/cm.sup.2 80 125 E3 <3.5 >56 >18 0.32/0.62 20 mA/cm.sup.2 80 120 E4 <3.2 >54 >18 0.32/0.62 20 mA/cm.sup.2 80 127 E5 <3.3 >59 >18 0.32/0.62 20 mA/cm.sup.2 80 128