MATERIALS FOR ORGANIC ELECTROLUMINESCENT DEVICES

Abstract

The present invention relates to a compound of the formula (1), to the use of the compound in an electronic device, and to an electronic device comprising a compound of the formula (1). The present invention furthermore relates to a formulation comprising one or more compounds of the formula (1).

Claims

1.-20. (canceled)

21. Compound of the formula (1), ##STR00328## where the following applies to the symbols and indices used: X stands on each occurrence, identically or differently, for CR.sup.X or N; Y.sup.1 stands for B(R.sup.0), Si(R.sup.0).sub.2, C═O, C═NR.sup.N, C═C(R.sup.0).sub.2, O, S, S═O, SO.sub.2, N(R.sup.N), P(R.sup.0) or P(═O)R.sup.0; Y.sup.2, Y.sup.3 and Y.sup.4 stand on each occurrence, identically or differently for B(R.sup.0, C(R.sup.0).sub.2, Si(R.sup.0).sub.2, C═O, C═NR.sup.N, C═C(R.sup.0).sub.2, O, S, S═O, SO.sub.2, N(R.sup.N), P(R.sup.0) or P(═O)R.sup.0; R.sup.X, R.sup.0, R.sup.N stand on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, N(R).sub.2, N(Ar).sub.2, 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 a 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 system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, an aralkyl or heteroaralkyl group which has 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; where two adjacent radicals R.sup.X may form an aliphatic, aromatic or heteroaromatic ring system together, which may be substituted by one or more radicals R; and where two adjacent radicals R.sup.0 may form an aliphatic, aromatic or heteroaromatic ring system together, 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, C(═O)Ar, P(═O)(Ar).sub.2, S(═O)Ar, S(═O).sub.2Ar, N(R′).sub.2, N(Ar).sub.2, 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 a 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 R′C═CR′, 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 system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R′; where two adjacent substituents R may form an aliphatic or aromatic ring system together, which may be substituted by one or more radicals R′; Ar is, on each occurrence, identically or differently, 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, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a 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 aromatic ring atoms; n, m, p are on each occurrence, identically or differently, 0 or 1, whereas when n, m or p is 0, then the corresponding group Y.sup.2, Y.sup.3 or Y.sup.4 is absent and the bonds to Y.sup.2, Y.sup.3 and Y.sup.4 are replaced by groups X.

22. Compound according to claim 21, characterized in that at least one of the index n, m or p is equal to 1.

23. Compound according to claim 21, characterized in that m+p is equal to 1 or 2.

24. Compound according to claim 21, characterized in that Y.sup.1 stands for B(R.sup.0), O, S or N(R.sup.N).

25. Compound according to claim 21, characterized in that Y.sup.1 stands for N(R.sup.N).

26. Compound according to claim 21, characterized Y.sup.2, Y.sup.3 and Y.sup.4 stand on each occurrence, identically or differently for B(R.sup.0), C(R.sup.0).sub.2, Si(R.sup.0).sub.2, C═O, O, S or N(R.sup.N).

27. Compound according to claim 21, characterized at least one group Y.sup.2, Y.sup.3 or Y.sup.4 is present, which stands for N(R.sup.N).

28. Compound according to claim 21, characterized in that it is selected from compounds of formulae (2) to (6), ##STR00329## where the symbols have the same meaning as in claim 21.

29. Compound according to claim 21, characterized in that it is selected from compound (2-1) to (6-1), ##STR00330## where the symbols have the same meaning as in claim 21.

30. Compound according to claim 21, characterized in that it is selected from compounds (2-1-1) to (6-1-2), ##STR00331## ##STR00332## where the symbols have the same meaning as in claim 21.

31. Compound according to claim 21, characterized in that it comprises at least one group R.sup.X, R.sup.N or R.sup.0, which is selected: from branched or cyclic alkyl groups represented by the general following formula (RS-a) ##STR00333## wherein R.sup.22, R.sup.23, R.sup.24 are at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.25, and where two of radicals R.sup.22, R.sup.23, R.sup.24 or all radicals R.sup.22, R.sup.23, R.sup.24 may be joined to form a (poly)cyclic alkyl group, which may be substituted by one or more radicals R.sup.25; R.sup.25 is at each occurrence, identically or differently, selected from a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms; with the proviso that at each occurrence at least one of radicals R.sup.22, R.sup.23 and R.sup.24 is other than H, with the proviso that at each occurrence all of radicals R.sup.22, R.sup.23 and R.sup.24 together have at least 4 carbon atoms and with the proviso that at each occurrence, if two of radicals R.sup.22, R.sup.23, R.sup.24 are H, the remaining radical is not a straight-chain; from branched or cyclic alkoxy groups represented by the general following formula (RS-b) ##STR00334## wherein R.sup.26, R.sup.27, R.sup.28 are at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.25 as defined above, and where two of radicals R.sup.26, R.sup.27, R.sup.28 or all radicals R.sup.26, R.sup.27, R.sup.28 may be joined to form a (poly)cyclic alkyl group, which may be substituted by one or more radicals R.sup.25 as defined above; with the proviso that at each occurrence only one of radicals R.sup.26, R.sup.27 and R.sup.28 may be H; from aralkyl groups represented by the general following formula (RS-c) ##STR00335## wherein R.sup.29, R.sup.30, R.sup.31 are at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.32, or an aromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.32, and where two or all of radicals R.sup.29, R.sup.30, R.sup.31 may be joined to form a (poly)cyclic alkyl group or an aromatic ring system, each of which may be substituted by one or more radicals R.sup.32; R.sup.32 is at each occurrence, identically or differently, selected from a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, or an aromatic ring system having 6 to 24 aromatic ring atoms; with the proviso that at each occurrence at least one of radicals R.sup.29, R.sup.30 and R.sup.31 is other than H and that at each occurrence at least one of radicals R.sup.29, R.sup.30 and R.sup.31 is or contains an aromatic ring system having at least 6 aromatic ring atoms; or from aromatic ring systems represented by the general following formula (RS-d) ##STR00336## wherein R.sup.40 to R.sup.44 is at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R.sup.32, or an aromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.32, and where two or more of radicals R.sup.40 to R.sup.44 may be joined to form a (poly)cyclic alkyl group or an aromatic ring system, each of which may be substituted by one or more radicals R.sup.32 as defined above; where the dashed bonds indicate the bonding of the corresponding group R.sup.X, R.sup.N or R.sup.0 to the rest of the structure.

32. Compound according to claim 21, characterized in that it comprises at least one group R.sup.X, R.sup.N or R.sup.0, which is selected from a group of formula (ArL-1), ##STR00337## where the dashed bond in formula (ArL-1) indicates the bonding of the corresponding group R.sup.X, R.sup.N or R.sup.0 to the rest of the structure, where Ar.sup.2, Ar.sup.3 stand 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; and where m is an integer selected from 1 to 10.

33. Polymer, oligomer or dendrimer containing one or more compounds according to claim 21, where the bond(s) to the polymer, oligomer or dendrimer may be localised at any positions in formula (1) which is substituted by R.sup.X, R.sup.0, R.sup.N or R.

34. Formulation comprising at least one compound according to claim 21 or at least one polymer, oligomer or dendrimer according to claim 33 and at least one solvent.

35. Electronic device comprising at least one compound according to claim 21 or at least one polymer, oligomer or dendrimer according to claim 33, 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. Organic electroluminescent device comprising at least one compound according to claim 21 or at least one polymer, oligomer or dendrimer according to claim 33, characterised in that the compound according to claim 21 or the polymer, oligomer or dendrimer according to claim 33 is employed as an emitter in an emitting layer.

37. Organic electroluminescent device according to claim 36, characterized in that the compound according to claim 21 or the polymer, oligomer or dendrimer according to claim 33 is employed as a fluorescent emitter in an emitting layer, wherein the emitting layer comprises at least one further component selected from matrix materials.

38. Organic electroluminescent device according to claim 36, characterized in that the compound according to claim 21 or the polymer, oligomer or dendrimer according to claim 33 is employed as an emitter showing Thermally Activated Delayed Fluorescence in an emitting layer, wherein the emitting layer comprises at least one further component selected from matrix materials.

39. Organic electroluminescent device according to claim 36, characterized in that the compound according to claim 21 or the polymer, oligomer or dendrimer according to claim 33 is employed as a fluorescent emitter in an emitting layer, wherein the emitting layer comprises at least one sensitizer selected from phosphorescent compounds and thermally activated delayed fluorescence compounds.

40. Organic electroluminescent device according to claim 39, characterized in that the emitting layer further comprises at least one organic functional material selected from matrix materials.

Description

A) SYNTHESES EXAMPLES

[0244] Unless otherwise stated, the following syntheses are carried out in a protective gas atmosphere in dried solvents. The solvents and reagents can be obtained from Sigma-ALDRICH or ABCR. The CAS numbers of the compounds known from the literature are also indicated below. The compounds according to the invention can be synthesised by means of synthesis methods known to the skilled person.

a) 1,6-dibromo-5,10-bis(2-chlorophenyl)boranthrene

[0245] ##STR00275##

[0246] A suspension of 21.0 g (57.4 mmol) of 1,6-dibromo-5,10-dihydro-5,10-dihydroxy-boranthrene is added to 2000 ml of benzene in a glass tube with a PTFE tap. Then, 29.0 g (11 ml, 120 mmol) of BBr3 is added to this solution at room temperature. The resulting clear solution is heated to 80° C., the tube is closed, and the temperature is maintained for 6 hours. The mixture is stirred overnight at RT, after which a small amount of the formed solid settles. The supernatant is then transferred via a tube to a Schlenk tube, which is put under vacuum to remove all volatile vapors.

[0247] The solid residue is mixed with 50 ml heptane and kept in an ultrasonic bath and then connected again to vacuum to remove the rest of BBr3.

[0248] The residue is recrystallized into hot hexane. The residue is dissolved in toluene and cooled down to −78° C.

[0249] 236 ml (118 mmol) of bromo(2-chlorophenyl-magnesium (0.5 M solution in THF) is added to the solution. The reaction mixture is heated to room temperature over the night and then quenched with a saturated aqueous NH.sub.4Cl-solution. The two liquid phases are separated, the aqueous phase is extracted with CHCl.sub.3 (3×150 ml), the combined organic phases are dried over MgSO.sub.4, concentrated in vacuum and purified via a column chromatography (silica gel, CHCl.sub.3:n-hexane=1:9) and finally purified by sublimation.

[0250] The yield is 19 g (34 mmol), i.e. 60% of the theory.

[0251] The following compounds can be obtained analogously:

TABLE-US-00005 Educt 1 Educt 2 Product Yield 1a [00276]   [1585174-31-7] [00277]   1428324-28-0 [00278] 62%

b) Cyclisation (Buchwald)

[0252] ##STR00279##

[0253] 11 g (20 mmol) of 1,6-dibromo-5,10-bis(2-chlorophenyl)boranthrene, 0.95 g (1 mmol) of tris(dibenzylidenacetone)dipalladium, 4 mL (1M) of t-Bu.sub.3P solution in toluene and 4.6 g (48 mmol) of sodium tert-butoxide are added to 200 ml toluene. Then, 1.8 g (16 mmol) of aniline are added to the mixture. The mixture is then heated to 110° C. for 20 h, then cooled down to room temperature and 100 ml of water are added. The aqueous phase is then extracted with vinegar ester, then the combined organic phases are dried over sodium sulphate and are concentrated under reduced pressure. The residue is recrystallized from toluene and from heptane/methanol and finally purified by sublimation.

[0254] The yield is 3.3 g (8.64 mmol), corresponding to 43% of the theory. Purity after .sup.1H-NMR is approx. 87%.

[0255] The following compounds can be obtained analogously:

TABLE-US-00006 Educt 1 Educt 2 Product Yield 1b [00280] [00281] [00282] 45%

c) N1,N4-bis(3-bromo-2-chloro-phenyl)-N1,N4-diphenyl-benzene-1,4-diamine

[0256] ##STR00283##

[0257] 10 g (34.7 mmol, 1 eq) of N,N′-diphenyl-1,4-benzenediamine are mixed with 91 g (340 mmol, 10 eq) of 1,3-dibromo-2-chlorobenzene and 10 g (111 mmol, 3 eq) of sodium t-butoxide in 150 ml toluene absolute in a 2 L four-necked flask and degas for 30 minutes. Then, 310 mg (1.3 mmol, 0.04 eq) of palladium(II)acetate and 1.5 g (2.7 mmol, 0.08 eq) of DPPF are added and the mixture is heated overnight with reflux. When the reaction is complete, the batch is cooled down to room temperature and extracted with 500 ml of water. The aqueous phase is then washed three times with toluene, the combined organic phases are dried over sodium sulphate and the solvent is removed using the rotary evaporator. The brown residue is mixed with approx. 200 ml toluene and filtered over silica gel. A further purification is carried out via recrystallization from toluene/heptane.

[0258] The yield is 19.9 g (31 mmol), corresponding to 81% of the theory. Purity after .sup.1H-NMR approx. 89%.

[0259] The following compounds can be obtained analogously:

TABLE-US-00007 Educt 1 Educt 2 Product Yield 1c [00284] [00285]   [101-17-7] [00286] 89% 2c [00287] [00288] [00289] 75% 3c [00290]   [875762-59-3] [00291] [00292] 77% 4c [00293]   [2268821-66-3] [00294] [00295] 80%

d) N3-[4-(N-(3-anilino-2-chloro-phenyl)anilino)phenyl]-2-chloro-N1,N3-diphenyl-benzene-1,3-diamine

[0260] ##STR00296##

[0261] 19.1 g (30 mmol, 1 eq) N1,N4-bis(3-bromo-2-chloro-phenyl)-N1,N4-diphenylbenzene-1,4-diamine together with 8.3 g (90 mmol, 3 eq) aniline and 8 g (90 mmol, 3 eq) sodium t-butoxide in 150 ml toluene absolute in a 2 L four-necked flask and degas for 30 minutes. Then add 286 mg (1.2 mmol, 0.04 eq) of palladium(II)acetate and 1.3 g (2.4 mmol, 0.08 eq) of DPPF and heat the mixture overnight with reflux. When the reaction is complete, cool the batch to room temperature and extract with 500 ml of water. The aqueous phase is then washed three times with toluene, the combined organic phases are dried over sodium sulphate and the solvent is removed at the rotary evaporator. The brown residue is absorbed in approx. 200 ml toluene and filtered over silica gel. For further purification a recrystallization from toluene/heptane is carried out.

[0262] The yield is 17.8 g (26 mmol), corresponding to 90% of the theory. Purity after .sup.1H-NMR approx. 88%.

[0263] The following compounds can be obtained analogously:

TABLE-US-00008 Edukt 1 Edukt 2 Produkt Ausbeute 1d [00297]   [2183476-39-1] [00298] [00299] 87%

e) Ring Formation (Buchwald)

[0264] ##STR00300##

[0265] In a 2 L four-neck flask, 13.26 g (20 mmol, 1 eq) of N3-[4-(N-(3-anilino-2-chloro-phenyl)anilino)phenyl]-2-chloro-N1,N3-diphenyl-benzene-1,3-diamine is mixed with 4.7 g (20 mmol, 3 eq) of 1-4 dibromobenzene and 5.3 g (60 mmol, 3 eq) of sodium t-butoxide in 150 ml of toluene absolute and degassed for 30 minutes. Then, 0.73 g (0.8 mmol, 0.04 eq) of Pd(dba).sub.2 and 2.9 ml (1-M solution in toluene, 0.6 mmol, 0.08 eq) of tri-t-butylphosphine are added to the mixture, which is heated overnight under reflux. When the reaction is complete, the mixture is cooled down to room temperature and extracted with 500 ml of water. The aqueous phase is then washed three times with toluene, the combined organic phases are dried over sodium sulphate and the solvent is removed with the rotary evaporator. The brown residue is mixed with approx. 200 ml of toluene and filtered over silica gel. For further purification a recrystallization from toluene/heptane is carried out.

[0266] The yield is 6 g (8.2 mmol), corresponding to 41% of the theory. Purity after .sup.1H-NMR approx. 88%.

f) Complexation

[0267] ##STR00301##

[0268] A solution of 31.6 ml (1.70 M, 53.7 mmol) of tert-butyl lithium in pentane is slowly added to a solution of 33 g (44.7 mmol) of compound (e) in 150 ml of tert-butyl benzene at −30° C. under a nitrogen atmosphere. After 2 hours stirring at 60° C., the pentane was removed under vacuum. After the addition of 5.1 ml (53.9 mmol) of boron tribromide at −30° C., the reaction mixture is stirred for 0.5 hour at room temperature. Then, 15.6 ml (91.1 mmol) of N-diisopropylethylamine is added at 0° C., the reaction mixture is then heated to room temperature. After 3 h stirring at 120° C., the reaction mixture is cooled down to room temperature. An aqueous solution of 13.0 g of sodium acetate in 100 ml water and 50 ml of ethyl acetate is added to the reaction mixture. The aqueous layer is separated and extracted with 100 ml of ethyl acetate. The combined organic phases are condensed under vacuum. The residue is dissolved in toluene and filtered with a silica gel pad (eluent: toluene). The solvent is removed under vacuum.

[0269] The residue is recrystallized from toluene/heptane and finally purified by sublimation.

[0270] The yield is 9.2 g (13.4 mmol), corresponding to 30% of the theory. Purity after .sup.1H-NMR is approx. 99.9%.

[0271] The following compounds can be obtained analogously:

TABLE-US-00009 Educt 1 Product Yield 1f [00302] [00303] 31% 2f [00304] [00305] 28% 3f [00306] [00307] 27%

g) 2,3-Dibromo-N1,N1,N4,N4-tetraphenyl-benzene-1,4-diamine

[0272] ##STR00308##

[0273] 33 g (200 mmol, 2 eq) of diphenyldiamine are placed in a 2 L four-neck flask and mixed with 48 g (100 mmol, 3 eq) of 2,3-dibromo-1,4-diiodobenzene and 28 g (300 mmol, 1 eq) of sodium t-butoxide in 150 ml of toluene absolute and degassed for 30 minutes. Then, 1.34 g (6 mmol, 0.03 eq) of Pd(OAc).sub.2 and 5.78 g (10 mmol, 0.05 eq) of Xantphos are added and the mixture is heated overnight to 110° C. When the reaction is complete, the mixture is cooled down to room temperature and extracted with 500 ml of water. The aqueous phase is then washed three times with toluene, the combined organic phases are dried over sodium sulphate and the solvent is removed at the rotary evaporator. The brown residue is mixed with approx. 200 ml toluene and filtered over silica gel. For further purification a recrystallization from toluene/heptane is carried out.

[0274] The yield is 39 g (69 mmol), corresponding to 71% of the theory. Purity after 1H NMR is approx. 87%.

h) 2,3-Bis(dimethylsilyl)-N1,N1,N4,N4-tetraphenyl-benzene-1,4-diamine

[0275] ##STR00309##

[0276] A hexane solution of n-BuLi (13.2 ml, 1.6 M, 21 mmol) is added drop by drop at −78° C. to a solution of 5.7 g (10 mmol) of 2,3-dibromo-N1,N1,N4,N4-tetraphenyl-benzene-1,4-diamine in freshly distilled THF (50 ml). The reaction mixture is then stirred for 1.5 hour and 2.6 ml (24 mmol) of chlorodimethylsilane is added.

[0277] The reaction mixture is heated at room temperature overnight and stirred at room temperature. Then, the mixture is quenched with water (15 ml) and extracted with CH.sub.2Cl.sub.2 (3×50 ml). The organic phases are dried with anhydrous Na.sub.2SO.sub.4 and concentrated in a vacuum. The raw product is purified by flash column chromatography on silica gel.

[0278] The yield is 4.8 g (9.1 mmol), corresponding to 91% of the theory. Purity after .sup.1H-NMR is approx. 87%.

i) Cyclisation

[0279] ##STR00310##

[0280] A mixture of 26 g (50 mmol) of 2,3-bis(dimethylsilyl)-N1,N1,N4,N4-tetraphenylbenzene-1,4-diamine, 32 ml (250 mmol) of 3,3-dimethyl-1-butene, 230 mg (0.25 mmol) of RhCl(PPh.sub.3).sub.3 and 500 ml of 1,4-dioxane is stirred at 135° C. for 24 h. The solvent is then removed under vacuum and the product is isolated by column chromatography on silica gel.

[0281] The yield is 23.9 g (45 mmol), corresponding to 93% of the theory. Purity after .sup.1H-NMR is approx. 91%.

j) Cyclisation

[0282] ##STR00311##

[0283] 10 ml (26.4 g, 105 mmol) of BBr.sub.3 are added to a solution of 10.4 g (20 mmol) of compound (i) in 200 ml of anhydrous CH.sub.2Cl.sub.2 at room temperature. After 4.5 h stirring at the same temperature, the mixture is concentrated at 50° C. under vacuum.

[0284] The resulting mixture is dissolved in 70 ml of anhydrous toluene. 20 ml (1M solution, 20 mmol) of a freshly prepared solution of 1,2-phenylene dilithim, synthesized from diiodobenzene and t-BuLi in THF, is added to this solution at 0° C. solution. After 20 hours stirring at 50°, the mixture is mixed with a saturated aqueous NH.sub.4Cl solution. The organic layer is separated and the aqueous layer is extracted three times with CH.sub.2Cl.sub.2. The combined organic phase is dried with Na.sub.2SO.sub.4, filtered and concentrated under reduced pressure.

[0285] The product is recrystallized in toluene and finally purified by sublimation.

[0286] The yield is 8 g (15.9 mmol), corresponding to 80% of the theory. Purity after .sup.1H-NMR is approx. 99.9%.

B) FABRICATION OF OLEDs

[0287] The fabrication of OLEDs is based on a process, which is described for example in WO 04/058911, and which is adapted to the individual conditions (e.g. layer thickness variation to achieve optimum efficiency or color).

[0288] Glass plates coated with structured ITO (indium tin oxide) form the substrates of the OLEDs. In principle, the OLEDs have the following layer structure: substrate/hole injection layer (HIL)/hole transport layer (HTL1) 60 nm/hole transport layer (HTL2) 20 nm/emission layer (EML) 30 nm/electron transport layer (ETL) 20 nm and finally a cathode. 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. The cathode is formed by a 1 nm thin LiF layer and a 100 nm Al layer deposited on it. Table 1 shows the chemical structures of the materials used to build the OLEDs.

[0289] The OLEDs are characterized by standard methods. For this purpose, the electroluminescence spectra, efficiency (measured in cd/A), power efficiency (measured in lm/W) and operating voltage (V) are determined as a function of luminance, calculated from current-voltage-luminance characteristics assuming a Lambertian radiation characteristic. The electroluminescence spectra are determined at a brightness of 1000 cd/m.sup.2 and the CIE 1931 x and y colour coordinates are determined. The lifetime is defined as the time after which the initial brightness of 6000 cd/m.sup.2 (for blue emitting OLEDs) or 25000 cd/m.sup.2 (for green emitting OLEDs) has been divided by two.

[0290] Tables 2 and 3 summarize the results of some OLEDs (examples E1 to E10). The compounds of the examples E1 and E2 are used as inventive host materials or emitter materials for green emission. The compounds of the examples E4, E5, E6, E7, E9 and E10 are used as inventive host materials or emitter materials for blue.

[0291] As can be seen from the results summarized in Table 2 and 3 inventive OLEDs lead to a significantly improved lifetime compared to state-of-the-art OLEDs. Furthermore, with deeper blue color coordinates, a comparable or even higher efficiency is obtained compared to the state-of-the-art OLEDs.

TABLE-US-00010 TABLE 1 [00312] HTM1 [00313] HTM2 [00314] HIM [00315] ETM1 [00316] ETM 2 [00317] ETM3 [00318] H2 [00319] H1 [00320] D1 (f) [00321] D2 (1f) [00322] D3 (b) [00323] D 4 (3f) [00324] D5 (2f) [00325] D6 (j) [00326] D7(JP2013056859) [00327] D8 (CN10741771)

TABLE-US-00011 TABLE 2 Efficiency Voltage (cd/A) (V) at Lifetime at 1000 1000 at 25000 Ex. EML ETL Color cd/m.sup.2 cd/m.sup.2 CIE cd/m.sup.2 (h) E1 H1 + ETM2 green 17.1 4.2 x = 300 9% D1 0.29/ y = 0.61 E2 H1 + ETM2 green 18.3 4.3 x = 320 9% D2 0.29/ y = 0.60 E3 H1 + ETM2 green 15.2 4.9 x = 188 (comp.) 9% D7 0.29/ y = 0.60

TABLE-US-00012 TABLE 3 Efficiency Voltage Lifetime (cd/A) (V) at at 6000 at 1000 1000 cd/m.sup.2 Ex. EML ETM Color cd/m.sup.2 cd/m.sup.2 CIE (h) E4 H1 + ETM1 blau 4.8 5.2 x = 190 5% 0.14/ D3 y = 0.15 E5 H2 + ETM1 blau 4.3 5.0 x = 185 5% 0.15/ D4 y = 0.16 E6 H2 + ETM1 blau 4.7 5.1 x = 200 5% 0.16/ D5 y = 0.10 E7 H2 + ETM1 blau 4.4 5.0 x = 200 5% 0.16/ D6 y = 0.10 E8 H2 + ETM1 blau 4.0 5.6 x = 120 (comp.) 5% 0.16/ D8 y = 0.10 E9 H1 + H2 blau 5.1 4.3 x = 270 5% (50%) + 0.14/ D6 ETM3 y = (50%) 0.16 E10 H2 + H2 blau 5.3 4.4 x = 250 5% (50%) + 0.15/ D3 ETM3 y = (50%) 0.15