MATERIALS FOR ORGANIC ELECTROLUMINESCENT DEVICES

Abstract

The present invention relates to compounds suitable for use in electronic devices, and to electronic devices, especially organic electroluminescent devices, comprising these compounds.

Claims

1.-24. (canceled)

25. A compound of formula (1) ##STR00505## wherein X is N or CR, with the proviso that not more than two of the X groups in one cycle are N; Y two adjacent Y are a group of the formula (2) below, and the two other Y are X, ##STR00506## where the two dotted bonds represent the linkage of this group; X.sup.1 is N or CR, with the proviso that not more than two of the X.sup.1 groups in the cycle are N; HetAr is an electron-deficient heteroaryl group which has 6 to 18 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals; at the same time, the HetAr radical together with the naphthylene group to which the HetAr radical binds may form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; R is the same or different at each instance and is H, D, F, Cl, Br, I, N(R.sup.4).sub.2, N(Ar′).sub.2, CN, NO.sub.2, OR.sup.4, SR.sup.4, COOR.sup.4, C(═O)N(R.sup.4).sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, C(═O)R.sup.4, P(═O)(R.sup.4).sub.2, S(═O)R.sup.4, S(═O).sub.2R.sup.4, OSO.sub.2R.sup.4, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.4 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.4).sub.2, C═O, NR.sup.4, O, S or CONR.sup.4, 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.4 radicals; R.sup.1 is the same or different at each instance and is a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the straight-chain, branched or cyclic alkyl group may in each case be substituted by one or more R.sup.4 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by O, 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.4 radicals; at the same time, two R.sup.1 radicals together may also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; R.sup.2 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R.sup.4).sub.2, N(Ar′).sub.2, CN, NO.sub.2, OR.sup.4, SR.sup.4, COOR.sup.4, C(═O)N(R.sup.4).sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, C(═O)R.sup.4, P(═O)(R.sup.4).sub.2, S(═O)R.sup.4, S(═O).sub.2R.sup.4, OSO.sub.2R.sup.4, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.4 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.4).sub.2, C═O, NR.sup.4, O, S or CONR.sup.4, 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.4 radicals; at the same time, two R.sup.2 radicals together or one R.sup.2 radical together with one R.sup.3 radical may also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; R.sup.3 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R.sup.4).sub.2, N(Ar′).sub.2, CN, NO.sub.2, OR.sup.4, SR.sup.4, COOR.sup.4, C(═O)N(R.sup.4).sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, C(═O)R.sup.4, P(═O)(R.sup.4).sub.2, S(═O)R.sup.4, S(═O).sub.2R.sup.4, OSO.sub.2R.sup.4, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.4 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.4).sub.2, C═O, NR.sup.4, O, S or CONR.sup.4, 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.4 radicals; at the same time, two R.sup.3 radicals together or one R.sup.3 radical together with one R.sup.2 radical may also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; Ar′ is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.4 radicals; R.sup.4 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R.sup.5).sub.2, CN, NO.sub.2, OR.sup.5, SR.sup.5, Si(R.sup.5).sub.3, B(OR.sup.5).sub.2, C(═O)R.sup.5, P(═O)(R.sup.5).sub.2, S(═O)R.sup.5, S(═O).sub.2R.sup.5, OSO.sub.2R.sup.5, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.5 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.5).sub.2, C═O, NR.sup.5, O, S or CONR.sup.5, 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.5 radicals; at the same time, two or more R.sup.4 radicals together may form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; R.sup.5 is the same or different at each instance and is H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, especially a hydrocarbyl radical, having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; o is the same or different at each instance and is 0, 1, 2, 3, 4, 5 or 6.

26. The compound according to claim 25, selected from the compounds of the formulae (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (1l) and (1m), ##STR00507## ##STR00508## ##STR00509## where o, Y, X, HetAr, R, R.sup.1 and R.sup.2 have the definitions given in claim 25.

27. The compound according to claim 26, wherein, in compounds of the formulae (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (1l) and (1m), not more than four X groups are N; and/or in compounds of the formulae (1), (1a), (1b), (1c), (1d), (1e), (1f), (1g), (1h), (1i), (1j), (1k), (1l) and (1m), not more than one X group is N.

28. The compound according to claim 25, selected from the compounds of formulae (3), (4) and (5) ##STR00510## where o, HetAr, R, R.sup.1 and R.sup.2 have the definitions given in claim 25 and the index r is the same or different at each instance and is 0, 1, 2, 3, 4, 5 or 6, the index n is 0, 1, 2, 3 or 4.

29. The compound according to claim 28, wherein the sum total of the indices m, n, o and r is not more than 6.

30. The compound according to claim 25, selected from the compounds of the formulae (3a-1), (3a-2), (4a-1), (4a-2), (5a-1) and (5a-2) ##STR00511## ##STR00512## where HetAr, R and R.sup.1 have the definitions given in claim 25.

31. The compound according to claim 25, selected from the compounds of the formulae (3b), (4b) and (5b) ##STR00513## where HetAr, R and R.sup.1 have the definitions given in claim 25.

32. The compound according to claim 25, wherein HetAr has 6 to 14 aromatic ring atoms, where HetAr may be substituted in each case by one or more R.sup.3 radicals.

33. The compound according to claim 25, wherein HetAr is selected from the structures of the following formulae (HetAr-1) to (HetAr-8): ##STR00514## where the dotted bond represents the bond to the naphthylene group, and the other symbols are as follows: X.sup.2 is the same or different at each instance and is CR.sup.3 or N, with the proviso that at least one symbol X.sup.2 is N, where R.sup.3 has the definitions given in claim 25; A is C(R.sup.4).sub.2, NR.sup.4, O or S.

34. The compound according to claim 25, wherein HetAr is selected from the structures of the following formula (HetAr-9): ##STR00515## where X.sup.2 is the same or different at each instance and is CR.sup.3 or N, with the proviso that at least one symbol X.sup.2 is N, the dotted bond represents the bond to the naphthylene group, Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.4 radicals, and R.sup.4 has the definitions given in claim 25.

35. The compound according to claim 25, wherein HetAr is selected from the groups of the formulae (HetAr-1a) to (HetAr-1d), (HetAr-2a), (HetAr-2b), (HetAr-3a), (HetAr-4a), (HetAr-5a), (HetAr-6a), (HetAr-6b), (HetAr-6c), (HetAr-7a), (HetAr-7b), (HetAr-7c), (HetAr-8a), (HetAr-8b) and (HetAr-8c) ##STR00516## ##STR00517## ##STR00518## where Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.4 radicals, R.sup.4 has the definitions given in claim 25 and the dotted bond represents the bond to the naphthylene group.

36. The compound according to claim 34, wherein Ar is the same or different at each instance and is selected from phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene and triphenylene, each of which may be substituted by one or more R.sup.4 radicals.

37. The compound according to claim 25, wherein R, R.sup.2 and/or R.sup.3 are the same or different at each instance and are selected from the group consisting of H, D, an aromatic or heteroaromatic ring system which has 6 to 30 aromatic ring atoms and may be substituted by one or more R.sup.4 radicals, and an N(Ar′).sub.2 group.

38. The compound according to claim 25, wherein R, R.sup.2 and/or R.sup.3 are the same or different at each instance and are selected from the group consisting of H, D or an aromatic or heteroaromatic ring system selected from the groups of the following formulae Ar-1 to Ar-75, and/or the Ar group is the same or different at each instance and is selected from the groups of the following formulae Ar-1 to Ar-75: ##STR00519## ##STR00520## ##STR00521## ##STR00522## ##STR00523## ##STR00524## ##STR00525## ##STR00526## ##STR00527## ##STR00528## ##STR00529## ##STR00530## where R.sup.4 has the definitions given above, the dotted bond represents the bond to the corresponding group and in addition: Ar.sup.1 is the same or different at each instance and is a bivalent aromatic or heteroaromatic ring system which has 6 to 18 aromatic ring atoms and may be substituted in each case by one or more R.sup.4 radicals; A is the same or different at each instance and is C(R.sup.4).sub.2, NR.sup.4, O or S; p is 0 or 1, where p=0 means that the Ar.sup.1 group is absent and that the corresponding aromatic or heteroaromatic group is bonded directly to HetAr; q is 0 or 1, where q=0 means that no A group is bonded at this position and R.sup.4 radicals are bonded to the corresponding carbon atoms instead.

39. A process for preparing a compound according to claim 25, comprising synthesizing a base skeleton that does not contain a naphthylene-HetAr group and introducing the naphthylene-HetAr group by a nucleophilic aromatic substitution reaction or a coupling reaction.

40. A composition comprising at least one compound according to claim 25 and at least one further matrix material, wherein the further matrix material is selected from compounds of one of the formulae (6), (7), (8), (9) and (10). ##STR00531## where the symbols and indices used are as follows: R.sup.6 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R.sup.7).sub.2, N(Ar″).sub.2, CN, NO.sub.2, OR.sup.7, SR.sup.7, COOR.sup.7, C(═O)N(R.sup.7).sub.2, Si(R.sup.7).sub.3, B(OR.sup.7).sub.2, C(═O)R.sup.7, P(═O)(R.sup.7).sub.2, S(═O)R.sup.7, S(═O).sub.2R.sup.7, OSO.sub.2R.sup.7, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.7 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.7).sub.2, C═O, NR.sup.7, O, S or CONR.sup.7, 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.7 radicals; at the same time, two R.sup.6 radicals together may also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; Ar″ is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.7 radicals; A.sup.1 is C(R.sup.7).sub.2, NR.sup.7, O or S; Ar.sup.5 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.7 radicals; R.sup.7 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R.sup.8).sub.2, CN, NO.sub.2, OR.sup.8, SR.sup.8, Si(R.sup.8).sub.3, B(OR.sup.8).sub.2, C(═O)R.sup.8, P(═O)(R.sup.8).sub.2, S(═O)R.sup.8, S(═O).sub.2R.sup.8, OSO.sub.2R.sup.8, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.8 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.8).sub.2, C═O, NR.sup.8, O, S or CONR.sup.8, 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.8 radicals; at the same time, two or more R.sup.7 radicals together may form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; R.sup.8 is the same or different at each instance and is H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, especially a hydrocarbyl radical, having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; s is the same or different at each instance and is 0, 1, 2, 3 or 4; t is the same or different at each instance and is 0, 1, 2 or 3; u is the same or different at each instance and is 0, 1 or 2.

41. Composition according to claim 40, wherein the compound of claim 25 has a proportion by mass in the composition in the range from 10% by weight to 95% by weight, based on the total mass of the composition.

42. Composition according to claim 40, wherein the compounds of one of the formulae (6), (7), (8), (9) and (10) have a proportion by mass in the composition in the range from 5% by weight to 90% by weight, based on the overall composition.

43. The composition according claim 40, wherein the composition consists exclusively of the compound of claim 25 and one of the further matrix materials.

44. A formulation comprising at least one compound according to claim 25 and/or at least one composition according to claim 40 and at least one further compound.

45. A method comprising utilizing a compound according to claim 25 in an electronic device.

46. An electronic device comprising at least one compound according to claim 25, wherein the electronic device is an electroluminescent device.

47. The electronic device according to claim 46 which is an organic electroluminescent device, wherein the compound is used as matrix material in an emitting layer and/or in an electron transport layer and/or in a hole blocker layer.

48. The electronic device according to claim 47, wherein the compound is used as matrix material for phosphorescent emitters in combination with a further matrix material selected from compounds of one of the formulae (6), (7), (8), (9) and (10), ##STR00532## where the symbols and indices used are as follows: R.sup.6 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R.sup.7).sub.2, N(Ar″).sub.2, CN, NO.sub.2, OR.sup.7, SR.sup.7, COOR.sup.7, C(═O)N(R.sup.7).sub.2, Si(R.sup.7).sub.3, B(OR.sup.7).sub.2, C(═O)R.sup.7, P(═O)(R.sup.7).sub.2, S(═O)R.sup.7, S(═O).sub.2R.sup.7, OSO.sub.2R.sup.7, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.7 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.7).sub.2, C═O, NR.sup.7, O, S or CONR.sup.7, 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.7 radicals; at the same time, two R.sup.6 radicals together may also form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; Ar″ is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.7 radicals; A.sup.1 is C(R.sup.7).sub.2, NR.sup.7, O or S; Ar.sup.5 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.7 radicals; R.sup.7 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R′).sub.2, CN, NO.sub.2, OR.sup.8, SR.sup.8, Si(R.sup.8).sub.3, B(OR.sup.8).sub.2, C(═O)R.sup.8, P(═O)(R.sup.8).sub.2, S(═O)R.sup.8, S(═O).sub.2R.sup.8, OSO.sub.2R.sup.8, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.8 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.8).sub.2, C═O, NR.sup.8, O, S or CONR.sup.8, 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.8 radicals; at the same time, two or more R.sup.7 radicals together may form an aromatic, heteroaromatic, aliphatic or heteroaliphatic ring system; R.sup.8 is the same or different at each instance and is H, D, F or an aliphatic, aromatic or heteroaromatic organic radical, especially a hydrocarbyl radical, having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; s is the same or different at each instance and is 0, 1, 2, 3 or 4; t is the same or different at each instance and is 0, 1, 2 or 3; u is the same or different at each instance and is 0, 1 or 2.

Description

EXAMPLES

[0172] The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The solvents and reagents can be purchased from ALDRICH or ABCR. The numbers given for the reactants are the corresponding CAS numbers.

a) (2-Chlorophenyl)(11,11-dimethyl-11H-benzo[a]fluoren-9-yl)amine

[0173] ##STR00326##

[0174] 47 g (145 mmol) of 9-bromo-11,11-dimethyl-11H-benzo[a]fluorene, 16.8 g (159 mmol) of 2-chloroaniline, 41.9 g (436.2 mmol) of sodium tert-butoxide, 1.06 g (1.45 mmol) of Pd(dppf)Cl.sub.2 are dissolved in 500 ml of toluene and stirred under reflux for 5 h. The reaction mixture is cooled down to room temperature, extended with toluene and filtered through Celite. The filtrate is concentrated under reduced pressure and the residue is crystallized from toluene/heptane. The product is isolated as a colourless solid. Yield: 33 g (89 mmol), 70% of theory.

[0175] The following compounds can be prepared in an analogous manner:

TABLE-US-00003 Reactant 1 Reactant 2 Product Yield 1a [00327] [00328] [00329] 79% 2a [00330] [00331] [00332] 77% 3a [00333] [00334] [00335] 78% 4a [00336] [00337] [00338] 79% 5a [00339] [00340] [00341] 74% 6a [00342] [00343] [00344] 81% 7a [00345] [00346] [00347] 78% 8a [00348] [00349] [00350] 77%

[0176] b) Cyclization

##STR00351##

[0177] 48 g (129 mmol) of (2-chlorophenyl)(11,11-dimethyl-11H-benzo[a]fluoren-9-yl)amine, 53 g (389 mmol) of potassium carbonate, 4.5 g (12 mmol) of tricyclohexylphosphine tetrafluoroborate, 1.38 g (6 mmol) of palladium(II) acetate and 3.3 g (32 mmol) of pivalic acid are suspended in 500 ml of dimethylacetamide and stirred under reflux for 6 h. After cooling, the reaction mixture is admixed with 300 ml of water and 400 ml of CH.sub.2Cl.sub.2. The mixture is stirred for a further 30 min, the organic phase is separated off and filtered through a short Celite bed, and then the solvent is removed under reduced pressure. The crude product is subjected to hot extraction with toluene and recrystallized from toluene. The product is isolated as a beige solid. Yield: 34 g (102 mmol), 78% of theory.

[0178] The following compounds can be prepared in an analogous manner:

TABLE-US-00004 Reactant Product Yield 1b [00352] [00353] 79% 2b [00354] [00355] 77% 3b [00356] [00357] 78% 4b [00358] [00359] 75% 5b [00360] [00361] 78% 6b [00362] [00363] 73% 7b [00364] [00365] 71% 8b [00366] [00367] 76%

c) 11,11-Dimethyl-3-(2-nitrophenyl)-11H-benzo[b]fluorene

[0179] ##STR00368##

[0180] To a well-stirred, degassed suspension of 59 g (183.8 mmol) of 2-nitrobenzeneboronic acid, 54 g (184 mmol) of 3-bromo-11,11-dimethyl-11H-benzo[b]fluorene and 66.5 g (212.7 mmol) of potassium carbonate in a mixture of 250 ml of water and 250 ml of THE are added 1.7 g (1.49 mmol) of Pd(PPh.sub.3).sub.4, and the mixture is heated under reflux for 17 h. After cooling, the organic phase is separated off, washed three times with 200 ml each time of water and once with 200 ml of saturated aqueous sodium chloride solution, dried over magnesium sulfate and concentrated to dryness by rotary evaporation. The grey residue is recrystallized from hexane. The precipitated crystals are filtered off with suction, washed with a little MeOH and dried under reduced pressure. Yield: 53 g (146 mmol); 80% of theory.

[0181] The following compounds can be prepared in an analogous manner:

TABLE-US-00005 Reactant 1 Reactant 2 Product Yield 1c [00369] [00370] [00371] 74% 2c [00372] [00373] [00374] 77% 3c [00375] [00376] [00377] 63%

[0182] d) Carbazole Synthesis

##STR00378##

[0183] A mixture of 87 g (240 mmol) of 11,11-dimethyl-3-(2-nitrophenyl)-11H-benzo[b]fluorene and 290.3 ml (1669 mmol) of triethyl phosphite is heated under reflux for 12 h. Subsequently, the rest of the triethyl phosphite is distilled off (72-76° C./9 mm Hg). Water/MeOH (1:1) is added to the residue, and the solids are filtered off and recrystallized. Yield: 58 g (176 mmol); 74% of theory.

[0184] The following compounds can be prepared in an analogous manner:

TABLE-US-00006 Reactant Product Yield 1d [00379] [00380] 79% 2d [00381] [00382] 76% 3d [00383] [00384] 62%

[0185] e) Nucleophilic Substitution

##STR00385##

[0186] 4.2 g of NaH, 60% in mineral oil, (106 mmol) is dissolved in 300 ml of dimethylformamide under a protective atmosphere. 34 g (106 mmol) of 7,9-dihydro-7,7-dimethylbenz[6,7]indeno[2,1-b]carbazole is dissolved in 250 ml of DMF and added dropwise to the reaction mixture. After 1 hour at room temperature, a solution of 2-(4-bromo-1-naphthalenyl)-4,6-diphenyl[1,3,5]triazine (48 g, 122 mmol) in 200 ml of THE is added dropwise. The reaction mixture is then stirred at room temperature for 12 h. After this time, the reaction mixture is poured onto ice. After warming to room temperature, the solids that precipitate out are filtered and washed with ethanol and heptane. The residue is subjected to hot extraction with toluene and recrystallized from toluene/n-heptane and finally sublimed under high vacuum; purity is 99.9%. The yield is 50 g (72 mmol); 68% of theory.

[0187] The following compounds can be prepared in an analogous manner:

TABLE-US-00007 Reactant 1 Reactant 2 Product Yield  1e [00386] [00387] [00388] 63%  2e [00389] [00390] [00391] 59%  3e [00392] [00393] [00394] 57%  4e [00395] [00396] [00397] 62%  5e [00398] [00399] [00400] 60%  6e [00401] [00402] [00403] 65%  7e [00404] [00405] [00406] 66%  8e [00407] [00408] [00409] 64%  9e [00410] [00411] [00412] 68% 10e [00413] [00414] [00415] 69% 11e [00416] [00417] [00418] 51% 12e [00419] [00420] [00421] 50% 13e [00422] [00423] [00424] 68% 14e [00425] [00426] [00427] 64% 15e [00428] [00429] [00430] 67% 16e [00431] [00432] [00433] 62% 17e [00434] [00435] [00436] 65% 18e [00437] [00438] [00439] 68% 19e [00440] [00441] [00442] 71% 20e [00443] [00444] [00445] 65% 21e [00446] [00447] [00448] 66% 22e [00449] [00450] [00451] 73% 23e [00452] [00453] [00454] 67% 24e [00455] [00456] [00457] 62% 25e [00458] [00459] [00460] 55% 26e [00461] [00462] [00463] 51% 27e [00464] [00465] [00466] 67% 28e [00467] [00468] [00469] 69% 29e [00470] [00471] [00472] 71%

[0188] f) Bromination

##STR00473##

[0189] 158 g (230 mmol) of compound e is initially charged in 1000 ml of THF. Subsequently, a solution of 41.7 g (234.6 mmol) of NBS in 500 ml of THE is added dropwise in the dark at −15° C., the mixture is allowed to come to RT and stirring is continued at this temperature for 4 h. Subsequently, 150 ml of water are added to the mixture and extraction is effected with CH.sub.2Cl.sub.2. The organic phase is dried over MgSO.sub.4 and the solvents are removed under reduced pressure. The product is subjected to extractive stirring with hot hexane and filtered off with suction. Yield: 104 g (135 mmol), 59% of theory, purity by .sup.1H NMR about 98%.

[0190] The following compounds can be prepared in an analogous manner:

TABLE-US-00008 Reactant 1 Product Yield 1f [00474] [00475] 54%

[0191] g) Suzuki Reaction

##STR00476##

[0192] 33.5 g (44 mmol) of the product from Example f, 13.4 g (47 mmol) of 9-phenylcarbazole-3-boronic acid and 29.2 g of Rb.sub.2CO.sub.3 are suspended in 250 ml of p-xylene. To this suspension are added 0.95 g (4.2 mmol) of Pd(OAc).sub.2 and 12.6 ml of a 1M tri-tert-butylphosphine solution. The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, washed three times with 200 ml of water and then concentrated to dryness. The residue is subjected to hot extraction with toluene, recrystallized from toluene and finally sublimed under high vacuum; the purity is 99.9%. Yield: 28 g (30 mmol), 70% of theory.

[0193] The following compounds can be prepared in an analogous manner:

TABLE-US-00009 Reactant 1 Reactant 2 Product Yield 1g [00477] [00478] [00479] 56% 2g [00480] [00481] [00482] 60%

[0194] Production of the Electroluminescent Devices

[0195] Examples C1 to I9 which follow (see table 1) present the use of the materials of the invention in electroluminescent devices.

[0196] Pretreatment for examples C1-I9: Glass plaques coated with structured ITO (indium tin oxide) of thickness 50 nm are treated prior to coating, first with an oxygen plasma, followed by an argon plasma. These plasma-treated glass plaques form the substrates to which the electroluminescent devices are applied.

[0197] The electroluminescent devices basically have the following layer structure: substrate/hole injection layer (HIL)/hole transport layer (HTL)/electron blocker layer (EBL)/emission layer (EML)/optional hole blocker layer (HBL)/electron transport layer (ETL)/optional electron injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer of thickness 100 nm. The exact structure of the OLEDs can be found in table 1. The materials required for production of the electroluminescent devices are shown in table 2. The data of the electroluminescent devices are listed in table 3.

[0198] All materials are applied by thermal vapour deposition in a vacuum chamber. In this case, the emission layer always consists of at least one matrix material (host material) and an emitting dopant (emitter) which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as 1e:IC2:TER5 (57%:40%:3%) mean here that the material 1e is present in the layer in a proportion by volume of 57%, IC2 in a proportion of 40% and TER5 in a proportion of 3%. Analogously, the electron transport layer may also consist of a mixture of two materials.

[0199] The electroluminescent devices are characterized in a standard manner. For this purpose, the electroluminescence spectra, the current efficiency (CE, measured in cd/A) and the external quantum efficiency (EQE, measured in %) are determined as a function of luminance, calculated from current-voltage-luminance characteristics assuming Lambertian emission characteristics, as is the lifetime. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The parameter U1000 in table 3 refers to the voltage which is required for a luminance of 1000 cd/m.sup.2. CE1000 and EQE1000 respectively denote the current efficiency and external quantum efficiency that are attained at 1000 cd/m.sup.2.

[0200] The lifetime LT is defined as the time after which the luminance drops from the starting luminance to a certain proportion L1 in the course of operation with constant current density j.sub.0. A figure of L1=95% in table 3 means that the lifetime reported in the LT column corresponds to the time after which the luminance falls to 95% of its starting value.

[0201] Use of Mixtures of the Invention in the Emission Layer of Phosphorescent Electroluminescent Devices

[0202] The materials of the invention are used in examples I1 to I9 as matrix material in the emission layer of red-phosphorescing electroluminescent devices. By comparison with the prior art (C1 to C5), it is possible to achieve a distinct improvement in lifetime with otherwise comparable parameters.

TABLE-US-00010 TABLE 1 Structure of the electroluminescent devices HIL HTL EBL EML HBL ETL EIL Ex. thickness thicknes thickness thickne thickness thickne thickness C1 SpMA1:PD1 SpMA1 SpMA2 27e:IC2:TER5 ST2 ST2:LiQ LiQ (95%:5%) 110 nm 10 nm (57%:40%:3%) 10 nm (50%:50%) 1 nm 20 nm 35 nm 30 nm C2 SpMA1:PD1 SpMA1 SpMA2 PA1:IC2:TER5 ST2 ST2:LiQ LiQ (95%:5%) 110 nm 10 nm (57%:40%:3%) 10 nm (50%:50%) 1 nm 20 nm 35 nm 30 nm C3 SpMA1:PD1 SpMA1 SpMA2 28e:IC2:TER5 ST2 ST2:LiQ LiQ (95%:5%) 110 nm 10 nm (57%:40%:3%) 10 nm (50%:50%) 1 nm 20 nm 35 nm 30 nm C4 SpMA1:PD1 SpMA1 SpMA2 PA2:IC2:TER5 ST2 ST2:LiQ LiQ (95%:5%) 110 nm 10 nm (57%:40%:3%) 10 nm (50%:50%) 1 nm 20 nm 35 nm 30 nm C5 SpMA1:PD1 SpMA1 SpMA2 PA3:IC2:TER5 ST2 ST2:LiQ LiQ (95%:5%) 110 nm 10 nm (57%:40%:3%) 10 nm (50%:50%) 1 nm 20 nm 35 nm 30 nm I1 SpMA1:PD1 SpMA1 SpMA2 1e:IC2:TER5 ST2 ST2:LiQ LiQ (95%:5%) 110 nm 10 nm (57%:40%:3%) 10 nm (50%:50%) 1 nm 20 nm 35 nm 30 nm I2 SpMA1:PD1 SpMA1 SpMA2 9e:IC2:TER5 ST2 ST2:LiQ LiQ (95%:5%) 110 nm 10 nm (57%:40%:3%) 10 nm (50%:50%) 1 nm 20 nm 35 nm 30 nm I3 SpMA1:PD1 SpMA1 SpMA2 26e:IC2:TER5 ST2 ST2:LiQ LiQ (95%:5%) 110 nm 10 nm (57%:40%:3%) 10 nm (50%:50%) 1 nm 20 nm SpMA2 35 nm 30 nm I4 SpMA1:PD1 SpMA1 10 nm 12e:IC2:TER5 ST2 ST2:LiQ LiQ (95%:5%) 110 nm (57%:40%:3%) 10 nm (50%:50%) 1 nm 20 nm SpMA2 35 nm 30 nm I5 SpMA1:PD1 SpMA1 10 nm 15e:IC2:TER5 ST2 ST2:LiQ LiQ (95%:5%) 110 nm (57%:40%:3%) 10 nm (50%:50%) 1 nm 20 nm SpMA2 35 nm 30 nm I6 SpMA1:PD1 SpMA1 10 nm 21e:IC2:TER5 ST2 ST2:LiQ LiQ (95%:5%) 110 nm (57%:40%:3%) 10 nm (50%:50%) 1 nm 20 nm SpMA2 35 nm 30 nm I7 SpMA1:PD1 SpMA1 10 nm 17e:IC2:TER5 ST2 ST2:LiQ LiQ (95%:5%) 110 nm (57%:40%:3%) 10 nm (50%:50%) 1 nm 20 nm SpMA2 35 nm 30 nm I8 SpMA1:PD1 SpMA1 10 nm 7e:IC2:TER5 ST2 ST2:LiQ LiQ (95%:5%) 110 nm (57%:40%:3%) 10 nm (50%:50%) 1 nm 20 nm SpMA2 35 nm 30 nm I9 SpMA1:PD1 SpMA1 10 nm 6e:IC2:TER5 ST2 ST2:LiQ LiQ (95%:5%) 110 nm (57%:40%:3%) 10 nm (50%:50%) 1 nm 20 nm 35 nm 30 nm

TABLE-US-00011 TABLE 2 Structural formulae of the materials for the OLEDs [00483] [00484] [00485] [00486] [00487] [00488] [00489] [00490] [00491] [00492] [00493] [00494] [00495] [00496] [00497] [00498] [00499] [00500] [00501] [00502] [00503] [00504]

TABLE-US-00012 TABLE 3 Performance data of the OLEDs U1000 CE1000 EQE1000 CIE x/y at j.sub.0 L1 LT Ex. (V) (cd/A) (%) 1000 cd/m.sup.2 (mA/cm.sup.2) (%) (h) C1 3.6 27 25.3 0.66/0.33 60 95 50 C2 3.6 28 25.7 0.66/0.33 60 95 20 C3 3.6 26 24.9 0.66/0.33 60 95 80 C4 35 28 25.1 0.66/0.34 60 95 40 C5 3.6 27 24.8 0.67/0.33 60 95 30 I1 3.4 29 25.8 0.67/0.33 60 95 210 I2 3.4 27 23.9 0.66/0.33 60 95 120 I3 3.3 26 24.7 0.67/0.34 60 95 160 I4 3.4 28 24.1 0.66/0.34 60 95 125 I5 3.3 26 23.7 0.66/0.33 60 95 118 I6 3.4 26 23.4 0.66/0.33 60 95 100 I7 3.3 27 24.1 0.66/0.33 60 95 122 I8 3.4 28 24.4 0.67/0.33 60 95 121 I9 3.5 26 23.2 0.66/0.33 60 95 113

[0203] The data set out above show that compounds having all the features of Claim 1 lead to unexpected improvements. Compounds having a naphthyl group that functions as connecting group between the nitrogen atom of a benzoindenocarbazole radical and an electron-deficient heteroaryl group have a surprisingly longer lifetime than compounds that have the same electron-deficient heteroaryl groups but do not have a naphthyl group, but rather a phenyl group, as connecting group (cf. comparative experiments C2 and C3 with inventive experiments I1, I2 and I5), or than compounds having the same electron-deficient heteroaryl groups, in which the benzo radical is fused not to the indene group but to the carbazole group, or having no benzo group fused to the indeno group (cf. comparative experiments C1, C4 and C5 with inventive experiments I1, I2, I3 and I5).

[0204] In addition, the data show that compounds in which the group of the formula (2) has been fused on according to compounds of formula (3) have surprising advantages. Accordingly, preference is given to compounds of formula (3).

[0205] In addition, compounds in which the HetAr group forms a ring closure together with the naphthylene group show high performance, as demonstrated by example I3.