MATERIALS FOR ORGANIC ELECTROLUMINESCENT DEVICES

Abstract

The present invention relates to compounds of the formula (1) which are suitable for use in electronic devices, in particular organic electroluminescent devices, to a process for manufacturing the compounds of formula (1), to intermediate compounds for manufacturing the compounds of formula (1) and to electronic devices comprising the compounds of formula (1).

Claims

1.-15. (canceled)

16. A compound of the formula (1), ##STR00355## where the following applies to the symbols and indices used: Ar.sup.1 is on each occurrence, identically or differently, a condensed aryl or heteroaryl group having 10 to 18 aromatic ring atoms, which may be substituted by one or more radicals R; Ar.sup.2 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 be substituted by one or more radicals R; Ar.sup.S is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R; E.sup.1, E.sup.2 are on each occurrence, identically or differently, selected from —BR.sup.0—, —C(R.sup.0).sub.2—, —Si(R.sup.0).sub.2—, —C(═O)—, —O—, —S—, —S(═O)—, —SO.sub.2—, —N(R.sup.0)—, and —P(R.sup.0)—; R.sup.1 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 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, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R, where two substituents R.sup.1 may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R; 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 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 aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R, where one substituent R.sup.2; or for a group of the following formula: ##STR00356## where the dashed bond indicates the bond to the structure of formula (1); and where one adjacent substituent R.sup.1 and/or two substituents R.sup.3 may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R; m stands on each occurrence, identically or differently, for an integer selected from 0, 1, 2, 3 or 4; n stands on each occurrence, identically or differently, for an integer selected from 0, 1, 2, 3 or 4; 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 system 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 60 aromatic ring atoms, which may be substituted by one or more radicals R′, where two adjacent substituents R may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, 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.

17. The compound according to claim 16, wherein the compound is selected from the compounds of formula (2) or (3), ##STR00357## where 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 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, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R, where one substituent R.sup.2 and one adjacent substituent R.sup.1 and/or two substituents R.sup.3 may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R; and where the symbols R.sup.1, E.sup.1, E.sup.2, Ar.sup.1, Ar.sup.2 and Ar.sup.S and the indices m and n have the same meaning as in claim 16.

18. The compound according to claim 16, wherein the group Ar.sup.1 is on each occurrence, identically or differently, selected from the group consisting of anthracene, naphthalene, phenanthrene, tetracene, chrysene, benzanthracene, benzo-phenanthracene, pyrene, perylene, triphenylene, benzopyrene, fluoranthene, each of which may be substituted by one or more radicals R at any free positions.

19. The compound according to claim 16, wherein the group Ar is selected from the groups of formulae (Ar1-1) to (Ar1-11), ##STR00358## where the dashed bonds indicate the bonding to the adjacent group in formula (1); and where the groups of formulae (Ar1-1) to (Ar1-11) may be substituted at each free position by a group R, which has the same meaning as in claim 16.

20. The compound according to claim 16, wherein the compound is selected from the compounds of formula (2-1) or (3-1), ##STR00359## where 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 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, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R, where one substituent R.sup.2 and one adjacent substituent R.sup.1 and/or two substituents R.sup.3 may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R; and where the symbols R, R.sup.1, E.sup.1, E.sup.2, Ar.sup.2 and Ar.sup.S and the indices m and n have the same meaning as above.

21. The compound according to claim 16, 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.

22. The compound according to claim 16, wherein the compound is selected from the compounds of formulae (2-1-1) to (3-1-6), ##STR00360## ##STR00361## ##STR00362## where the symbols R.sup.2, R.sup.3 have the same meaning as in claim 20, the symbols R, R.sup.1, Ar.sup.2 and Ar.sup.S and the index m have the same meaning as in claim 16.

23. The compound according to claim 16, wherein Ar.sup.2 is selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, phenanthrene, anthracene, triphenylene, fluoranthene, tetracene, chrysene, benzanthracene, benzophenanthracene, pyrene, perylene, indole, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, carbazole, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinolone, benzopyridine, benzopyridazine, benzopyrimidine, benzimidazole and quinazoline, each of which may be substituted by one or more radicals R.

24. The compound according to claim 16, wherein the compound is selected from the compounds of formulae (2-1-5) to (3-1-12), ##STR00363## ##STR00364## ##STR00365## where the symbols R.sup.2, R.sup.3 have the same meaning as in claim 20, and the symbols R, R.sup.1, Ar.sup.2 and Ar.sup.S have the same meaning as in claim 16.

25. A process for the preparation of the compound according to formula (1) as defined in claim 16, where the process comprises one of the following synthesis routes a1), a2), a3) or a4): Route a1): ##STR00366## Route a2): ##STR00367## Route a3): ##STR00368## Route a4): ##STR00369## where the symbols R.sup.1, R.sup.2, R.sup.3, Ar.sup.1, Ar.sup.2, Ar.sup.S have the same meaning as above, and where: X.sup.1 is a leaving group selected from halogens and triflate; X.sup.2 is a leaving group selected from boronic acids and boronic esters; X.sup.3 is a leaving group selected from silyl groups.

26. A compound of formulae (Int-1), (Int-2), (Int-3), (Int-4) and (Int-5), ##STR00370## where the symbols R.sup.1, R.sup.2, R.sup.3, E.sup.1 and E.sup.2 have the same meaning as in claim 16 and the symbols X.sup.1 and X.sup.3 have the same meaning as in claim 25.

27. A formulation comprising at least one compound according to claim 16 and at least one solvent.

28. A polymer, oligomer or dendrimer containing one or more compounds according to claim 16, where the bond(s) to the polymer, oligomer or dendrimer may be localised at any positions in formula (1) which is substituted by R, R.sup.1, R.sup.2 or R.sup.3.

29. An electronic device comprising at least one compound according to claim 16 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.

30. An electronic device comprising at least one polymer, oligomer or dendrimer according to claim 28, 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.

31. An organic electroluminescent device comprising the compound according to claim 16 is employed as a fluorescent emitter or as a matrix material for fluorescent emitters.

32. An organic electroluminescent device comprising the polymer, oligomer or dendrimer according to claim 28 is employed as a fluorescent emitter or as a matrix material for fluorescent emitters.

Description

A) SYNTHESES EXAMPLES

A-1) Part 1

[0155] ##STR00262##

Synthesis of BB-2

[0156] ##STR00263##

[0157] Under an argon atmosphere, an oven dried flask is equipped with a magnetic stir bar, 1-((trifluoromethyl)sulfonyl)dibenzo[b,d]furane (20.0 g, 63.2 mmol, 1.0 equiv.), benzofurane-3-ylboronic acid (11.3 g, 69.6 mmol, 1.1 equiv.), potassium phosphate (33.6 g, 158.1 mmol, 2.5 equiv.), palladium acetate (0.3 g, 1.3 mmol, 0.02 equiv.) and XPhos (1.2 g, 2.5 mmol, 0.04 equiv.). THF (400 mL) and water (100 mL) are added and the reaction is refluxed overnight. The raw product is purified by column chromatography. The desired product is isolated as a colorless oil (15.0 g, 52.8 mmol, 83.3%).

Synthesis of BB-3

[0158] ##STR00264##

[0159] An oven dried flask is equipped with BB-2 (15.0 g, 52.7 mmol, 1.0 equiv.) in DCM (150 mL). N-bromosuccinimide (9.4 g, 52.7 mmol, 1.0 equiv.) is added and the resulting mixture is stirred for overnight at rt. The raw product is purified by filtration over AlOx. The desired product is isolated as colorless oil (16.2 g, 44.3 mmol, 84.1%).

Synthesis of BB-4

[0160] ##STR00265##

[0161] Under an argon atmosphere, an oven dried flask is equipped with a magnetic stir bar, BB-3, copper iodide (0.3 g, 1.3 mmol, 0.03 equiv.), bis(triphenylphosphin)palladium(II)chlorid (0.6 g, 0.9 mmol, 0.02 equiv.), and trimethylsilylacetylene (18.9 mL, 133.8 mmol, 3.0 equiv.). Triethylamine (500 mL) is added and the reaction mixture is refluxed overnight. The raw product is purified by column chromatography. The desired product is isolated as a white solid (13.6 g, 35.7 mmol, 80.1%).

Synthesis of BB-5

[0162] ##STR00266##

[0163] An oven dried flask is equipped with a magnetic stir bar, BB-4 (10.0 g, 26.3 mmol, 1.0 equiv.), potassium carbonate (0.7 g, 5.3 mmol, 0.2 equiv.). Methanol (100 mL) is added and the reaction mixture is stirred for 1 h at rt. The solvent is removed under reduced pressure. The residue is taken up with DCM (100 mL) and is washed twice with water (2×50 mL). The organic phase is concentrated under reduce pressure. The desired product is obtained as white solid (8.1 g, 26.3 mmol, 100%).

Synthesis of BB-6

[0164] ##STR00267##

[0165] Under an argon atmosphere, an oven dried flask is charged with BB-5 (8.1 g, 26.0 mmol, 1.0 equiv.), platinum chloride (690 mg, 2.6 mmol, 0.1 equiv.). Toluene (500 mL) is added and the reaction mixture is refluxed overnight. The raw product is purified by column chromatography. The desired product is isolated as white solid (3.1 g, 10.0 mmol, 38.7%).

A-2) Part 2

[0166] ##STR00268##

Synthesis of BB-7

[0167] ##STR00269##

[0168] 5 g (17.4 mmol) 1,8-dibromnapthalene, 7 g (43.7 mmol) [2-(Methylsulfanylphenyl] boronic acid and 28 g (87 mmol) cesium carbonate are mixed in 200 ml water and 200 ml N,N-Dimethylformamide. 0.71 g (1.7 mmol) SPhos and 1,68 g (1.7 mmol) Pd.sub.2(dba).sub.3 are added and the mixture is refluxed for 17 h. After cooling down to room temperature the organic phase is separated and washed with water (3×200 ml) and with 200 ml brine. Afterward it is dried over magnesium sulfate and reduced under reduced pressure to give a gray residue, which is further purified by crystallization out of heptane.

[0169] Yield: 5.9 g, (15.9 mmol; 91%)

Synthesis of BB-8

[0170] ##STR00270##

[0171] To 30 g (80 mmol) BB-7 60 ml acetic acid are added and cooled down to 0° C. 18.2 mL (160 mmol) of a 30% H.sub.2O.sub.2-solution are added dropwise and the mixture is stirred for 16 hours. A solution of Na.sub.2SO.sub.3 is added, the organic phase is separated and solvents are removed under reduced pressure.

[0172] Yield: 26 g (65 mmol; 80%)

Synthesis of BB-9

[0173] ##STR00271##

[0174] A mixture of 133 g (230 mmol) BB-8 and 200 ml triflic acid is stirred at 50° C. for 3 days. Afterwards 600 g (2.9 mol) potassium carbonate in 3 l water are added dropwise and stirred at 75° C. for 5 h. 500 ml toluene are added and the mixture is stirred at room temperature overnight. The organic phase is separated and reduced under reduced pressure. The residue was further purified by column chromatography (heptane/DCM)

[0175] Yield: 39 g (117 mmol, 52%)

A-3) Part 3

[0176] ##STR00272##

Synthesis of BB-10

[0177] ##STR00273##

[0178] Under an argon atmosphere, an oven dried flask is equipped with a magnetic stir bar, BB-6 (10.0 g, 32.4 mmol, 1.0 equiv.). THF (10 mL) is added and the reaction mixture is cooled to −78° C. n-BuLi (2.5 M in hexane, 20 mL, 48.7 mmol, 1.5 equiv.) is added slowly. The reaction mixture is stirred for 1 h at −78° C. Iodine (13.2 g, 52.0 mmol, 1.5 equiv.) dissolved in THF (20 mL) is added. The reaction mixture is warmed to room temperature overnight. The reaction mixture is diluted with ethyl acetate (1000 mL). Excess of iodine is quenched by the addition of saturated sodium thiosulfate solution (200 mL). The organic phase is separated. The solvent is removed under reduced pressure. The raw product is purified by column chromatography. The desired product is isolated as white solid (13.5 g, 31.1 mmol, 95.9%).

[0179] Following compounds can be synthesized in analogous manner:

TABLE-US-00007 Starting material Product BB-10-b BB-9 [00274] BB-10-c* BB-9 [00275] BB-10-d* BB-6 [00276] *Bromine is used instead of iodine

Synthesis of BB-11

[0180] ##STR00277##

[0181] Under an argon atmosphere, an oven dried flask is equipped with a magnetic stir bar, BB-10, (13.0 g, 28.4 mmol, 1.0 equiv.), (10-phenyl-9-anthryl) boronic acid (25.4 g, 85.1 mmol, 3.0 equiv.), tris(dibenzylideneacetone) dipalladium (1.3 g, 1.4 mmol, 0.05 equiv.), SPhos (1.16 g, 2.8 mmol, 0.1 equiv.) and potassium fluoride (4.1 g, 70.9 mmol, 2.5 equiv.). Toluene (150 mL), 1,4-dioxane (150 mL) and water (150 mL) is added and the mixture is refluxed overnight. The raw product is purified by column chromatography and sublimation. The desired product is isolated as white solid (4.0 g, 7.1 mmol, 25.1%).

[0182] Following compounds can be synthesized in analogous manner:

TABLE-US-00008 Starting material Starting material Product BB-11-b BB-10-b [00278] [00279] BB-11-c BB-10-b [00280] [00281] BB-11-d BB-10 [00282] [00283] BB-11-e BB-10 [00284] [00285] BB-11-f BB-10 [00286] [00287] BB-11-g BB-10 [00288] [00289] BB-11-h BB-10-b [00290] [00291] BB-11-i BB-10 [00292] [00293] BB-11-j BB-10 [00294] [00295] BB-11-k BB-10-b [00296] [00297] BB-11-l [00298] [00299]

Synthesis of BB-12

[0183] ##STR00300##

[0184] Under an argon atmosphere, an oven dried flask is equipped with a magnetic stir bar, BB-11 (15.0 g, 26.8 mmol, 1.0 equiv.). THF (200 mL) is added and the reaction mixture is cooled to −78° C. n-BuLi (2.5 M in hexane, 21 mL, 53.5 mmol, 2.0 equiv.) is added slowly. The reaction mixture is stirred for 3 h at −78 OC. Iodine (17.0 g, 66.9 mmol, 2.5 equiv.) dissolved in THF (30 mL) is added. The reaction mixture is warmed to rt overnight. The reaction mixture is diluted with ethyl acetate (1000 mL). Excess of iodine is quenched by the addition of saturated sodium thiosulfate solution (200 mL). The organic phase is separated. The solvent is removed under reduced pressure. The raw product is purified by column chromatography. The desired product is isolated as white solid (15.0 g, 21.9 mmol, 81.7%).

[0185] Following compounds can be synthesized in analogous manner:

TABLE-US-00009 Starting material Product BB-12-b BB-11-b [00301] BB-12-c BB-11-c [00302] BB-12-d BB-11-d [00303] BB-12-e BB-11-e [00304] BB-12-f BB-11-f [00305]

Synthesis of BB-13

[0186] ##STR00306##

[0187] Under an argon atmosphere, an oven dried flask is equipped with a magnetic stir bar, 1-Iodo-BB-12 (14.5 g, 21.1 mmol, 1.0 equiv.), 10-Phenyl-9-anthranyl-boronic acid (28.5 g, 63.4 mmol, 3.0 equiv.), potassium fluoride (73.6 g, 126.7, mmol, 6.0 equiv.) and (2-Dicyclohexylphosphino-2′,6′-dimethoxybiphenyl) [2-(2′-amino-1,1′-biphenyl)]palladium(II) methanesulfonate (1.65 g, 2.11 mmol, 0.1 equiv.). Toluene (300 mL), 1.4-dioxane (300 mL) and water (300 mL) is added and the mixture is refluxed overnight. The raw product is purified by column chromatography. The desired product is isolated as white solid (6.8 g, 7.05 mmol, 33.4%).

[0188] Following compounds can be synthesized in analogous manner:

TABLE-US-00010 Starting material Starting material Product BB-13-b BB-12-b [00307] [00308] BB-13-c BB-12-c [00309] [00310] BB-13-d BB-12-d [00311] [00312] BB-13-e BB-12-e [00313] [00314] BB-13-f BB-12-f [00315] [00316] BB-13-g BB-12 [00317] [00318] BB-13-h BB-12-b [00319] [00320]

Synthesis of BB-14

[0189] ##STR00321##

[0190] Under an argon atmosphere, an oven dried flask is equipped with a magnetic stir bar, BB-6 (14.0 g, 43.1 mmol, 1.0 equiv.). THF (250 mL) is added and the reaction mixture is cooled to −78° C. n-BuLi (2.5 M in hexane, 22.4 mL, 56.1 mmol, 1.3 equiv.) is added. The reaction mixture is stirred for 1 h at −78° C. Trimethylsilyl chloride (24.8 mL, 194.1 mmol, 4.5 equiv.) is added. The reaction mixture is warmed overnight to rt. The raw product is purified by column chromatography. The desired product is obtained as white solid (16.4 g, 43.1 mmol, 99.9%).

[0191] Following compounds can be synthesized in analogous manner:

TABLE-US-00011 Starting material reagent Product BB-14-b BB-9 TMS-Cl [00322] BB-14-c BB-6 Trimethylborate [00323]

Synthesis of BB-15

[0192] ##STR00324##

[0193] Under an argon atmosphere, an oven dried flask is equipped with a magnetic stir bar, BB-14 (16.3 g, 42.8 mmol, 1.0 equiv.). THF (200 mL) is added and the reaction mixture is cooled to −78° C. n-BuLi (2.5 M in hexane, 22.3 mL, 55.7 mmol, 1.3 equiv.) is added. The reaction mixture is stirred for 1 h at −78° C. Trimethylsilyl chloride (27.4 mL, 214.2 mmol, 5.0 equiv.) is added. The reaction mixture is warmed overnight to rt. The raw product is purified by column chromatography. The desired product is obtained as white solid (12.4 g, 27.4 mmol, 63.9%).

[0194] Following compounds can be synthesized in analogous manner:

TABLE-US-00012 Starting material reagent Product BB-15-b BB-14-b TMS-Cl [00325]

Synthesis of BB-16

[0195] ##STR00326##

[0196] Under an argon atmosphere, an oven dried flask is equipped with a magnetic stir bar and BB-15 (11.8 g, 26.1 mmol, 1.0 equiv.). DCM (50 mL) is added and the resulting mixture is cooled down to 0° C. Iodmonochlorid (3.0 mL, 57.4 mmol, 2.2 equiv.) is added via syringe. Excess of Iodmonochlorid is quenched by the addition of saturated sodium thiosulfate solution (200 mL). The resulting mixture is dilute with toluene (300 mL). The organic phase is separated and concentrated under reduced pressure. The desired product is obtained as white solid (14.5 g, 25.9 mmol, 99.3%).

[0197] Following compounds can be synthesized in analogous manner:

TABLE-US-00013 Starting material Product BB-16-b BB-15-b [00327]

Synthesis of BB-17

[0198] ##STR00328##

[0199] Under an argon atmosphere, an oven dried flask is equipped with a magnetic stir bar, 1,4-di-iodo-napthobisbenzofurane, (10.0 g, 17.9 mmol, 1.0 equiv.), (10-phenyl-9-anthryl) boronic acid (29.3 g, 5.5 mmol, 5.5 equiv.), (2-Dicyclohexylphosphino-2′,6′-dimethoxybiphenyl) [2-(2′-amino-1,1′-biphenyl)]palladium(II) methanesulfonate (2.8 g, 3.6 mmol, 0.2 equiv.) and potassium fluoride (6.2 g, 107.1 mmol, 6.0 equiv.). Toluene (300 mL), 1.4-dioxane (300 mL) and water (300 mL) is added and the mixture is refluxed overnight. The raw product is purified by column chromatography. The desired product is isolated as white solid (5.0 g, 6.2 mmol, 34.5%).

[0200] Following compounds can be synthesized in analogous manner:

TABLE-US-00014 Starting material Starting material Product BB-17-b BB-16-b [00329] [00330] BB-17-c BB-16-b [00331] [00332] BB-17-d BB-16 [00333] [00334] BB-17-e BB-16 [00335] [00336] BB-17-f BB-16 [00337] [00338] BB-17-g BB-16 [00339] [00340] BB-17-h BB-16 [00341] [00342]

B) Fabrication of OLEDs

[0201] Fabrication of Vapor Processed OLED Devices

[0202] The manufacturing of the OLED devices is performed accordingly to WO 04/05891 with adapted film thicknesses and layer sequences. The following examples V1, E1, E2, E3, E4 and E5 show data of various OLED devices.

[0203] Substrate Pre-Treatment of Examples V1, E1 to E5:

[0204] Glass plates with structured ITO (50 nm, indium tin oxide) are coated with 20 nm PEDOT:PSS (Poly(3,4-ethylenedioxythiophene) poly(styrene-sulfonate, CLEVIOS™ P VP Al 4083 from Heraeus Precious Metals GmbH Germany, spin-coated from a water-based solution) to form the substrates on which the OLED devices are fabricated.

[0205] The OLED devices have in principle the following layer structure: [0206] Substrate, [0207] ITO (50 nm), [0208] Buffer (20 nm), [0209] Hole transporting layer (HTL), [0210] Interlayer (IL), [0211] Electron blocking layer (EBL), [0212] Emissive layer (EML), [0213] Electron transporting layer (ETL), [0214] Cathode.

[0215] The cathode is formed by an aluminium layer with a thickness of 100 nm. The detailed stack sequence is shown in table A. The materials used for the OLED fabrication are presented in table C.

[0216] 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=H) and an emitting dopant (emitter=D), which is mixed with the matrix material or matrix materials in a certain proportion by volume by co-evaporation. An expression such as H1:D1 (95%:5%) here means that material H1 is present in the layer in a proportion by volume of 95%, whereas D1 is present in the layer in a proportion of 5%. Analogously, the electron-transport layer may also consist of a mixture of two or more materials.

[0217] The OLED devices are characterised by standard methods. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), power efficiency (Im/W) and the external quantum efficiency (EQE, measured in % at 1000 cd/m.sup.2) are determined from current/voltage/luminance characteristic lines (IUL characteristic lines) assuming a Lambertian emission profile. The electroluminescence (EL) spectra are recorded at a luminous density of 1000 cd/m.sup.2 and the CIE 1931 x and y coordinates are then calculated from the EL spectrum. U1000 is defined as the voltage at luminous density of 1000 cd/m.sup.2. SE1000 represents the current efficiency, LE1000 the power efficiency at 1000 cd/m.sup.2. EQE1000 is defined as the external quantum efficiency at luminous density of 1000 cd/m.sup.2.

[0218] The device data of various OLED devices are summarized in table B. The example V1 represents the comparative example according to the state-of-the-art. The examples E1 to E5 show data of inventive OLED devices.

[0219] In the following section several examples are described in more detail to show the advantages of the inventive OLED devices.

[0220] Use of Inventive Compounds as Host Material in Fluorescent OLEDs

[0221] The inventive compounds are especially suitable as a host (matrix) when blended with a fluorescent blue dopant (emitter) to form the emissive layer of a fluorescent blue OLED device. The representative examples are H1, H2, H3, H4 and H5. Comparative compound for the state-of-the-art is represented by SdT (structures see table C). The use of the inventive compound as a host (matrix) in a fluorescent blue OLED device results in excellent device data, especially with respect to power efficiency (LE1000) when compared to the state-of-the-art (compare E1 to E5 versus V1, see device data see table B).

TABLE-US-00015 TABLE A device stack of vapor processed OLEDs HTL IL EBL EML ETL Ex. [nm] [nm] [nm] [nm] [nm] V1 SpA HATCN SpMA SdT:D1 ETM:LiQ 140 nm 5 nm 20 nm (95%:5%) 20 nm (50%:50%) 30 nm El SpA HATCN SpMA Hl:D1 ETM:LiQ 140 nm 5 nm 20 nm (95%:5%) 20 nm (50%:50%) 30 nm E2 SpA HATCN SpMA H2:D1 ETM:LiQ 140 nm 5 nm 20 nm (95%:5%) 20 nm (50%:50%) 30 nm E3 SpA HATCN SpMA H3:D1 ETM:LiQ 140 nm 5 nm 20 nm (95%:5%) 20 nm (50%:50%) 30 nm E4 SpA HATCN SpMA H4:D1 ETM:LiQ 140 nm 5 nm 20 nm (95%:5%) 20 nm (50%:50%) 30 nm E5 SpA HATCN SpMA H5:D1 ETM:LiQ 140 nm 20 nm 5 nm (95%:5%) 20 nm (50%:50%) 30 nm

TABLE-US-00016 TABLE B device data of vapor processed OLEDs U1000 SE1000 LE1000 EQE1000 ClE x/y at Bsp. (V) (cd/A) (Im/W) ([%]) 1000 cd/m.sup.2 V 5.5 7.2 4.1 6.0 0.13/0.14 E1 4.9 7.8 5.0 6.7 0.13/0.14 E2 5.0 8.1 5.1 6.9 0.13/0.13 E3 4.8 7.5 4.9 6.6 0.13/0.14 E4 5.1 82 5.1 7.0 0.13/0.13 E5 4.9 7.9 5.1 6.7 0.13/0.14

TABLE-US-00017 TABLE C Structural formulae of vapor processed OLED materials [00343] [00344] [00345] [00346] [00347] [00348] [00349] [00350] [00351] [00352] [00353] [00354]