MATERIALS FOR ORGANIC LIGHT EMITTING DEVICES

Abstract

The present invention describes carbazole, dibenzofuran, dibenzothiophene and fluorene derivatives which are substituted by electron-deficient heteroaryl groups, in particular for use as triplet matrix materials in organic electroluminescent devices. The invention furthermore relates to a process for the preparation of the compounds according to the invention and to electronic devices comprising these compounds.

Claims

1.-15. (canceled)

16. A mixture comprising at least one compound of the formula (1a), ##STR00674## where the following applies to the symbols and indices used: A is on each occurrence, identically or differently, CR or N, where a maximum of two groups A per ring stand for N and where A stands for C if the group comprising Y.sup.2 is bonded at this position; X is on each occurrence, identically or differently, CR or N, with the proviso that at least one group X stands for N; Ar is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R; Y.sup.1 is O, NR′, S or CR.sub.2 where R′ is phenyl; Y.sup.2 is O or S; L is on each occurrence, identically or differently, a single bond or an aromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R; R″ is phenyl; n is 0, 1, 2, 3 or 4; R is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, NO.sub.2, N(Ar.sup.1).sub.2, N(R.sup.1).sub.2, C(═O)Ar.sup.1, C(═O)R.sup.1, P(═O)(Ar.sup.1).sub.2, P(Ar.sup.1).sub.2, B(Ar.sup.1).sub.2, Si(Ar.sup.1).sub.3, Si(R.sup.1).sub.3, 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 or an alkenyl group having 2 to 20 C atoms, each of which may be substituted by one or more radicals R.sup.1, where one or more non-adjacent CH.sub.2 groups may be replaced by R.sup.1C═CR.sup.1, Si(R.sup.1).sub.2, C═O, C═S, C═NR.sup.1, P(═O)(R.sup.1), SO, SO.sub.2, NR.sup.1, O, S or CONR.sup.1 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 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1; two substituents R which are bonded to the same carbon atom or to adjacent carbon atoms may optionally form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system here, which may be substituted by one or more radicals R.sup.1; Ar.sup.1 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more non-aromatic radicals R.sup.1; two radicals Ar.sup.1 which are bonded to the same N atom, P atom or B atom may also be bridged to one another here by a single bond or a bridge selected from N(R.sup.1), C(R.sup.1).sub.2, O or S; R.sup.1 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups, each having 1 to 4 carbatoms; two or more adjacent substituents R.sup.1 may form a mono- or polycyclic, aliphatic ring system with one another here; and at least one further compound, wherein the further compound is a matrix material.

17. The mixture according to claim 16, wherein X is on each occurrence N.

18. The mixture according to claim 16, wherein Y.sup.1 is O.

19. The mixture according to claim 16, wherein Y.sup.1 is S.

20. The mixture according to claim 16, wherein Y.sup.2 is O.

21. The mixture according to claim 16, wherein Y.sup.2 is S.

22. The mixture according to claim 16, wherein the matrix material is a hole-transporting compound.

23. The mixture according to claim 22, wherein the hole transporting compound is a carbazole derivative.

24. The mixture according to claim 23, wherein the carbazole derivative is a biscarbazole.

25. The mixture according to claim 16, wherein the compound of formula (1a) is selected from the group of compounds ##STR00675## ##STR00676## ##STR00677## ##STR00678## ##STR00679## ##STR00680## ##STR00681## ##STR00682## ##STR00683## ##STR00684## ##STR00685## ##STR00686## ##STR00687## ##STR00688##

26. An organic electroluminescent device comprising the mixture according to claim 16.

27. An organic electroluminescent device comprising the mixture according to claim 24.

28. An organic electroluminescent device comprising the mixture according to claim 25.

29. An organic electroluminescent device comprising the mixture according to claim 16 wherein the mixture is employed in an emitting layer, in combination with a phosphorescent dopant.

30. An organic electroluminescent device comprising the mixture according to claim 24 wherein the mixture is employed in an emitting layer, in combination with a phosphorescent dopant.

31. An organic electroluminescent device comprising the mixture according to claim 25 wherein the mixture is employed in an emitting layer, in combination with a phosphorescent dopant.

Description

EXAMPLES

[0155] The following syntheses are carried out, unless indicated otherwise, in dried solvents under a protective-gas atmosphere. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The corresponding CAS numbers are in each case also indicated for the compounds that are known from the literature.

Synthesis Examples

a) Triazine synthesis: 2,4-Bisbiphenyl-3-yl-6-chloro-1,3,5-triazine

[0156] ##STR00162##

[0157] 5.2 g of magnesium (0.215 mol) are initially introduced in a 500 ml four-necked flask, and a solution of 50 g of bromobiphenyl (214 mmol) in 200 ml of THF is slowly added dropwise. The reaction mixture is heated at the boil for 1.5 h and subsequently cooled to room temperature. Cyanogen chloride (17.2 g, 93 mmol) in 150 ml of THF is initially introduced in a second flask and cooled to 0° C. The cooled Grignard reagent is added dropwise at this temperature, and the mixture is stirred at room temperature for 12 h. After this time, 150 ml of HCl are added to the reaction mixture, and the aqueous phase is extracted three times with dichloromethane. The combined organic phases are washed with water, dried over Na.sub.2SO.sub.4 and evaporated. The residue is recrystallised from EtOH. The yield is 32.8 g (78 mmol, 84%).

b) 4-Bromo-9-methyl-9-phenyl-9H-fluorene

[0158] ##STR00163##

[0159] 30 g (94 mmol) of 2,2′-dibromobiphenyl are dissolved in 200 ml of dried THF in a flask which has been dried by heating. The reaction mixture is cooled to −78° C. At this temperature, 37.7 ml of a 2.5 M solution of n-butyllithium in hexane (94 mmol) are slowly added dropwise (duration: about 1 h). The batch is stirred at −70° C. for a further 1 h. 11.1 ml of acetophenone (94 mmol) are subsequently dissolved in 100 ml of THF and added dropwise at −70° C. When the addition is complete, the reaction mixture is slowly warmed to room temperature, quenched with NH.sub.4Cl and subsequently concentrated in a rotary evaporator. 300 ml of acetic acid are carefully added to the concentrated solution, and 50 ml of fuming HCl are subsequently added. The batch is heated at 75° C. for 6 h, during which a white solid precipitates out. The batch is cooled to room temperature, and the solid which has precipitated out is filtered off with suction and rinsed with methanol. The residue is dried at 40° C. in vacuo. The yield is 25.3 g (75 mmol) (80% of theory).

c) 4-Bromo-9,9-diphenyl-9H-fluorene

[0160] ##STR00164##

[0161] 37 g (152 mmol) of 2,2′-dibromobiphenyl are dissolved in 300 ml of dried THF in a flask which has been dried by heating. The reaction mixture is cooled to −78° C. At this temperature, 75 ml of a 15% solution of n-butyllithium in hexane (119 mmol) are slowly added dropwise (duration: about 1 h). The batch is stirred at −70° C. for a further 1 h. 21.8 g of benzophenone (119 mmol) are subsequently dissolved in 100 ml of THF and added dropwise at −70° C. When the addition is complete, the reaction mixture is slowly warmed to room temperature, quenched with NH.sub.4Cl and subsequently concentrated in a rotary evaporator. 510 ml of acetic acid are carefully added to the concentrated solution, and 100 ml of fuming HCl are subsequently added. The batch is heated at 75° C. for 4 h, during which a white solid precipitates out. The batch is then cooled to room temperature, and the solid which has precipitated out is filtered off with suction and rinsed with methanol. The residue is dried at 40° C. in vacuo. The yield is 33.2 g (83 mmol) (70% of theory).

[0162] The following brominated compounds are prepared analogously:

TABLE-US-00001 Starting Starting material 1 material 2 Product Yield c1 [00165] [00166] [00167] 78% c2 [00168] [00169] [00170] 70% c3 [00171] [00172] [00173] 82%

d) 6-Bromo-2-fluoro 2′-methoxybiphenyl

[0163] ##STR00174##

[0164] 200 g (664 mmol) of 1-bromo-3-fluoro-2-iodobenzene, 101 g (664 mmol) of 2-methoxyphenylboronic acid and 137.5 g (997 mmol) of sodium tetraborate are dissolved in 1000 ml of THF and 600 ml of water and degassed. 9.3 g (13.3 mmol) of bis(triphenylphosphine)palladium(I1) chloride and 1 g (20 mmol) of hydrazinium hydroxide are added. The reaction mixture is subsequently stirred at 70° C. under a protective-gas atmosphere for 48 h. The cooled solution is extended with toluene, washed a number of times with water, dried and evaporated. The product is purified by column chromatography on silica gel with toluene/heptane (1:2). Yield: 155 g (553 mmol), 83% of theory.

[0165] The following compounds are prepared analogously:

TABLE-US-00002 Starting Starting material 1 material 2 Product Yield d1 [00175] [00176] [00177] 77% d2 [00178] [00179] [00180] 74% d3 [00181] [00182] [00183] 76% d4 [00184] [00185] [00186] 71% [00187]

e) 6′-Bromo-2-fluorobiphenyl-2-ol

[0166] ##STR00188##

[0167] 112 g (418 mmol) of 6-bromo-2-fluoro-2′-methoxybiphenyl are dissolved in 2 l of dichloromethane and cooled to 5° C. 41.01 ml (431 mmol) of boron tribromide are added dropwise to this solution over the course of 90 min., and stirring is continued overnight. Water is subsequently slowly added to the mixture, and the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4, evaporated in a rotary evaporator and purified by chromatography. Yield: 104 g (397 mmol), 98% of theory.

[0168] The following compounds are prepared analogously:

TABLE-US-00003 Starting material 1 Product Yield e1 [00189] [00190] 92% e2 [00191] [00192] 90% e3 [00193] [00194] 93% e4 [00195] [00196] 94% [00197]

f) 1-Bromodibenzofuran

[0169] ##STR00198##

[0170] 111 g (416 mmol) of 6′-bromo-2′-fluorobiphenyl-2-ol are dissolved in 2 l of SeccoSolv® DMF (max. 0.003% of H.sub.2O) and cooled to 5° C. 20 g (449 mmol) of sodium hydride (60% suspension in paraffin oil) are added to this solution in portions, and the mixture is stirred for a further 20 min. after the addition is complete and then heated at 100° C. for 45 min. After cooling, 500 ml of ethanol are slowly added to the mixture, which is then evaporated in a rotary evaporator and then purified by chromatography. Yield: 90 g (367 mmol), 88.5% of theory.

[0171] The following compounds are prepared analogously:

TABLE-US-00004 Starting material 1 Product Yield f1 [00199] [00200] 81% f2 [00201] [00202] 78% f3 [00203] [00204] 73% f4 [00205] [00206] 79% [00207]

g) Dibenzofuran-1-Boronic Acid and Boronic Acid Asters

[0172] ##STR00208##

[0173] 180 g (728 mmol) of 1-bromodibenzofuran are dissolved in 1500 ml of dry THF and cooled to −78° C. At this temperature, 305 ml (764 mmol/2.5 M in hexane) of n-butyllithium are added over the course of about 5 min., and the mixture is subsequently stirred at −78° C. for a further 2.5 h. At this temperature, 151 g (1456 mmol) of trimethyl borate are added as rapidly as possible, and the reaction is allowed to come slowly to room temperature (about 18 h). The reaction solution is washed with water, the solid which has precipitated out is filtered off and the organic phase are dried azeotropically with toluene. The crude product is washed by stirring with toluene/methylene chloride at about 40° C. and filtered off with suction. Yield: 146 g (690 mmol), 95% of theory.

[0174] The following compounds are prepared analogously:

TABLE-US-00005 Starting material 1 Product Yield g1  [00209] [00210] 81% g2  [00211] [00212] 78% g3  [00213] [00214] 73% g4  [00215] [00216] 79% g5  [00217] [00218] 73% g6  [00219] [00220] 70% g7  [00221] [00222] 70% g8  [00223] [00224] 78% g9  [00225] [00226] 81% g10 [00227] [00228] 86% g11 [00229] [00230] 83% g12 [00231] [00232] 85% g13 [00233] [00234] 82% g14 [00235] [00236] 80% g15 [00237] [00238] 83% g16 [00239] [00240] 82% g17 [00241] [00242] 81% g18 [00243] [00244] 84% [00245]

g19) Synthesis of 1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzofuran

[0175] ##STR00246##

[0176] 101 g (410 mmol) of 1-bromodibenzofuran are dissolved in 1500 ml of dry DMF together with 273 g (1.055 mmol) of bis(pinacolato)diborane (CAS 73183-34-3) under protective gas in a 500 ml flask and degassed for 30 minutes. 121 g (1229 mmol) of potassium acetate and 8.4 g (37 mmol) of palladium acetate are subsequently added, and the batch is heated overnight at 80° C. When the reaction is complete, the mixture is diluted with 300 ml of toluene and extracted with water. The solvent is removed in a rotary evaporator, and the product is recrystallised from heptane. Yield: 118 g (401 mmol), 98% of theory.

h) 2-Dibenzofuran-1-yl-4,6-diphenyl-1,3,5-triazine

[0177] ##STR00247##

[0178] 23 g (110.0 mmol) of dibenzofuran-1-boronic acid, 29.5 g (110.0 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine and 21 g (210.0 mmol) of sodium carbonate are suspended in 500 ml of ethylene glycol diamine ether and 500 ml of water. 913 mg (3.0 mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) of palladium(II) acetate are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 200 ml of water and subsequently evaporated to dryness. The residue is recrystallised from toluene and from dichloromethane/heptane. The yield is 37 g (94 mmol), corresponding to 87% of theory.

[0179] The following compounds are prepared analogously: Product Yield

TABLE-US-00006 Starting Starting material 1 material 2 Product Yield h1  [00248] [00249] [00250] 73% h2  [00251] [00252] [00253] 82% h3  [00254] [00255] [00256] 73% h4  [00257] [00258] [00259] 72% h5  [00260] [00261] [00262] 65% h6  [00263] [00264] [00265] 63% h7  [00266] [00267] [00268] 72% h8  [00269] [00270] [00271] 75% h9  [00272] [00273] [00274] 79% h10 [00275] [00276] [00277] 81% h11 [00278] [00279] [00280] 85% h12 [00281] [00282] [00283] 80% h13 [00284] [00285] [00286] 79% h14 [00287] [00288] [00289] 77% h15 [00290] [00291] [00292] 76% h16 [00293] [00294] [00295] 71% h17 [00296] [00297] [00298] 75% h18 [00299] [00300] [00301] 76% h19 [00302] [00303] [00304] 80% h20 [00305] [00306] [00307] 79% h21 [00308] [00309] [00310] 82% [00311]

i) 2-(8-Bromodibenzofuran-1-yl)-4,6-diphenyl-1,3,5-triazine

[0180] ##STR00312##

[0181] 70 g (190.0 mmol) of 2-dibenzofuran-1-yl-4,6-diphenyl-1,3,5-triazine are suspended in 2000 ml of acetic acid (100%) and 2000 ml of sulfuric acid (95-98%). 34 g (190 mmol) of NBS are added to this suspension in portions, and the mixture is stirred in the dark for 2 h. Water/ice are then added, and the solid is separated off and rinsed with ethanol. The residue is recrystallised from toluene. The yield is 80 g (167 mmol), corresponding to 87% of theory.

[0182] The following compounds are prepared analogously:

TABLE-US-00007 Starting material 1 Product Yield i1  [00313] [00314] 80% i2  [00315] [00316] 41% i3  [00317] [00318] 52% i4  [00319] [00320] 64% i5  [00321] [00322] 33% i6  [00323] [00324] 73% i7  [00325] [00326] 78% i8  [00327] [00328] 80% i9  [00329] [00330] 70% i10 [00331] [00332] 86% i11 [00333] [00334] 88% i12 [00335] [00336] 41% i13 [00337] [00338] 73% [00339]

[0183] In the case of the dibenzothiophene derivatives, nitrobenzene is employed instead of sulfuric acid and elemental bromine is employed instead of NBS:

TABLE-US-00008 i14 [00340] [00341] 55% i15 [00342] [00343] 52%

j) 3-[9-(4,6-Diphenyl-1,3,5-triazin-2-yl)dibenzofuran-2-yl]-9-phenyl-9H-carbazole

[0184] ##STR00344##

[0185] 75 g (156 mmol) of 2-(8-bromodibenzofuran-1-yl)-4,6-diphenyl-1,3,5-triazine, 50 g (172 mmol) of N-phenylcarbazole-3-boronic acid and 36 g (340 mmol) of sodium carbonate are suspended in 1000 ml of ethylene glycol diamine ether and 280 ml of water. 1.8 g (1.5 mmol) of tetrakis-(triphenylphosphine)palladium(0) are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 200 ml of water and subsequently evaporated to dryness. The product is purified by column chromatography on silica gel with toluene/heptane (1:2) and finally sublimed in a high vacuum (p=5×10.sup.−7 mbar) (purity 99.9%). The yield is 50 g (78 mmol), corresponding to 50% of theory.

[0186] The following compounds are prepared analogously:

TABLE-US-00009 Starting material 1 Starting material 2 Product Yield j1 [00345] [00346] [00347] 61% j2 [00348] [00349] [00350] 67% j3 [00351] [00352] [00353] 65% j4 [00354] [00355] [00356] 53% j5 [00357] [00358] [00359] 58% j6 [00360] [00361] [00362] 54% j7 [00363] [00364] [00365] 65% j8 [00366] [00367] [00368] 71% j9 [00369] [00370] [00371] 56% j10 [00372] [00373] [00374] 79% j11 [00375] [00376] [00377] 70% j12 [00378] [00379] [00380] 82% j13 [00381] [00382] [00383] 69% j14 [00384] [00385] [00386] 65% j15 [00387] [00388] [00389] 77% j16 [00390] [00391] [00392] 82% j17 [00393] [00394] [00395] 54% j18 [00396] [00397] [00398] 67% j19 [00399] [00400] [00401] 65% j20 [00402] [00403] [00404] 63% j21 [00405] [00406] [00407] 79% j22 [00408] [00409] [00410] 65% j23 [00411] [00412] [00413] 55% j24 [00414] [00415] [00416] 67% j25 [00417] [00418] [00419] 73% j26 [00420] [00421] [00422] 66% j27 [00423] [00424] [00425] 59% j28 [00426] [00427] [00428] 64% j29 [00429] [00430] [00431] 71% j30 [00432] [00433] [00434] 62% [00435]

[0187] The following compounds are prepared analogously using 0.5 equivalent of the corresponding bromide:

TABLE-US-00010 j31 cmpn. [00436] [00437] [00438] 72% j32 cmpn. [00439] [00440] [00441] 73% j33 [00442] [00443] [00444] 74% j34 [00445] [00446] [00447] 77% [00448]

k) 3-(1-Bromodibenzothiophen-3-yl)-9-phenyl-OH-carbazole

[0188] ##STR00449##

[0189] 22 g (66 mmol) of 1,3-dibromodibenzothiophene, 17 g (664 mmol) of N-phenylcarbazole-3-boronic acid and 13.7 g (100 mmol) of sodium tetraborate are dissolved in 100 ml of THF and 60 ml of water and degassed. 0.9 g (1.3 mmol) of bis(triphenylphosphine)palladium(II) chloride and 1 g (20 mmol) of hydrazinium hydroxide are added. The reaction mixture is subsequently stirred at 70° C. under a protective-gas atmosphere for 48 h. The cooled solution is extended with toluene, washed a number of times with water, dried and evaporated. The product is purified by column chromatography on silica gel with toluene/heptane (1:2). Yield: 13.2 g (26 mmol), 40% of theory.

[0190] The following compounds are prepared analogously:

TABLE-US-00011 Starting material 1 Starting material 2 Product Yield k1 [00450] [00451] [00452] 27% k2 [00453] [00454] [00455] 29% k3 [00456] [00457] [00458] 34% k4 [00459] [00460] [00461] 24% k5 [00462] [00463] [00464] 31% [00465]

l) 1-Bromo-8-iododibenzofuran

[0191] ##STR00466##

[0192] 20 g (80 mmol) of dibenzofuran-1-boronic acid, 2.06 g (40.1 mmol) of iodine, 3.13 g (17.8 mmol) of iodic acid, 80 ml of acetic acid, 5 ml of sulfuric acid, 5 ml of water and 2 ml of chloroform are stirred at 65° C. for 3 h. After cooling, water is added to the mixture, and the solid which has precipitated out is filtered off with suction and washed three times with water. The residue is recrystallised from toluene and from dichloromethane/heptane. The yield is 25.6 g (68 mmol), corresponding to 85% of theory.

[0193] The following compounds are prepared analogously:

TABLE-US-00012 Starting material 1 Product Yieid l1 [00467] [00468] 81% l2 [00469] [00470] 84% l3 [00471] [00472] 78% [00473]

m) 3-(9-Bromodibenzofuran-2-yl)-9-phenyl-9H-carbazole

[0194] ##STR00474##

[0195] 58 g (156 mmol) of 1-bromo-8-iododibenzofuran, 50 g (172 mmol) of N-phenylcarbazole-3-boronic acid and 36 g (340 mmol) of sodium carbonate are suspended in 1000 ml of ethylene glycol diamine ether and 280 ml of water. 1.8 g (1.5 mmol) of tetrakis(triphenylphosphine)palladium(0) are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 200 ml of water and subsequently evaporated to dryness. The yield is 48 g (89 mmol), corresponding to 64% of theory.

[0196] The following compounds are prepared analogously:

TABLE-US-00013 Starting Starting material 1 material 2 Product Yield m1 [00475] [00476] [00477] 60% m2 [00478] [00479] [00480] 62% m3 [00481] [00482] [00483] 54% m4 [00484] [00485] [00486] 50% m5 [00487] [00488] [00489] 55% m6 [00490] [00491] [00492] 56% m7 [00493] [00494] [00495] 57% m8 [00496] [00497] [00498] 61% m9 [00499] [00500] [00501] 52% m10 [00502] [00503] [00504] 50% m11 [00505] [00506] [00507] 48% m12 [00508] [00509] [00510] 52% m13 [00511] [00512] [00513] 54% m14 [00514] [00515] [00516] 57% m15 [00517] [00518] [00519] 48% m16 [00520] [00521] [00522] 46% [00523]

o) 8-(9-Phenyl-9H-carbazol-3-yl)dibenzofuran-1-boronic acid

[0197] ##STR00524##

[0198] 20 g (182 mmol) of 3-(9-bromodibenzofuran-2-yl)-9-phenyl-9H-carbazole are dissolved in 400 ml of dry THF and cooled to −78° C. At this temperature, 77 ml (190 mmol/2.5 M in hexane) of n-butyllithium are added over the course of about 5 min., and the mixture is subsequently stirred at −78° C. for a further 2.5 h. At this temperature, 38 g (365 mmol) of trimethyl borate are added as rapidly as possible, and the reaction is allowed to come slowly to room temperature (about 18 h). The reaction solution is washed with water, the solid which has precipitated out is filtered off and the organic phase are dried azeotropically with toluene. The crude product is washed by stirring with toluene/methylene chloride at about 40° C. and filtered off with suction. Yield: 16.7 g (690 mmol), 90% of theory.

[0199] The following compounds are prepared analogously:

TABLE-US-00014 Starting material Product Yield o1 [00525] [00526] 81% o2 [00527] [00528] 84% o3 [00529] [00530] 82% o4 [00531] [00532] 81% o5 [00533] [00534] 79% o6 [00535] [00536] 77% o7 [00537] [00538] 75% o8 [00539] [00540] 78% o9 [00541] [00542] 76% o10 [00543] [00544] 81% o11 [00545] [00546] 80% o12 [00547] [00548] 71% o13 [00549] [00550] 69% o14 [00551] [00552] 88% o15 [00553] [00554] 78% o16 [00555] [00556] 77% [00557]

p) 3-{9-[3-(4,6-Diphenyl-1,3,5-triazin-2-yl)phenyl]dibenzofuran-2-yl}-9-phenyl-9H-carbazole

[0200] ##STR00558##

[0201] 49.8 g (110.0 mmol) of 8-(9-phenyl-9H-carbazol-3-yl)dibenzofuran-1-boronic acid, 42.6 g (110.0 mmol) of 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine and 26 g (210.0 mmol) of sodium carbonate are suspended in 500 ml of ethylene glycol dimethyl ether and 500 ml of water. 913 mg (3.0 mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) of palladium(II) acetate are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 200 ml of water and subsequently evaporated to dryness. The product is purified by column chromatography on silica gel with toluene/heptane (1:2) and finally sublimed in a high vacuum (p=5×10.sup.−7 mbar) (purity 99.9%). The yield is 52 g (72 mmol), corresponding to 78% of theory.

[0202] The following compounds are prepared analogously:

TABLE-US-00015 Starting material 1 Starting material 2 Product Yield p1 [00559] [00560] [00561] 59% p2 [00562] [00563] [00564] 67% p3 [00565] [00566] [00567] 62% p4 [00568] [00569] [00570] 69% p5 [00571] [00572] [00573] 67% p6 [00574] [00575] [00576] 68% p7 [00577] [00578] [00579] 69% p8 [00580] [00581] [00582] 60% p9 [00583] [00584] [00585] 63% p10 [00586] [00587] [00588] 66% p11 [00589] [00590] [00591] 60% p12 [00592] [00593] [00594] 61% p13 [00595] [00596] [00597] 65% p14 [00598] [00599] [00600] 63% p15 [00601] [00602] [00603] 65% p16 [00604] [00605] [00606] 63% p17 [00607] [00608] [00609] 65% p18 [00610] [00611] [00612] 67% p19 [00613] [00614] [00615] 72% p20 [00616] [00617] [00618] 66% [00619]

[0203] Production of the OLEDs

[0204] The data of various OLEDs are presented in the following Examples V1 to E37 (see Tables 1 and 2).

[0205] Pro-treatment for Examples V1-E37: Glass plates coated with structured ITO (indium tin oxide) in a thickness of 50 nm are coated with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), purchased as CLEVIOS™ P VP Al 4083 from Heraeus Precious Metals GmbH Germany, applied by spin coating from aqueous solution) for improved processing. These coated glass plates form the substrates to which the OLEDs are applied. The OLEDs have in principle the following layer structure: substrate/hole-transport layer (HTL)/optional interlayer (IL)/electron-blocking layer (EBL)/emission layer (EML)/optional hole-blocking layer (HBL)/electron-transport layer (ETL)/optional electron-injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm. The precise structure of the OLEDs is shown in Table 1. The materials required for the production of the OLEDs are shown in Table 3.

[0206] All materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer here always consists of at least one matrix material (host material) and an emitting dopant (emitter), which is admixed with the matrix material or matrix materials in a certain proportion by volume by co-evaporation. An expression such as IC1:IC3:TEG1 (55%:35%:10%) here means that material IC1 is present in the layer in a proportion by volume of 55%, IC3 is present in the layer in a proportion of 35% and TEG1 is present in the layer in a proportion of 10%. Analogously, the electron-transport layer may also consist of a mixture of two materials.

[0207] The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in lm/W) and the external quantum efficiency (EQE, measured in percent) as a function of the luminous density, calculated from current/voltage/luminous density characteristic lines (IUL characteristic lines) assuming Lambert emission characteristics, and the lifetime are determined. The electroluminescence spectra are determined at a luminous density of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The term U1000 in Table 2 denotes the voltage required for a luminous density of 1000 cd/m.sup.2. CE1000 and PE1000 denote the current and power efficiency respectively which are achieved at 1000 cd/m.sup.2. Finally, EQE1000 denotes the external quantum efficiency at an operating luminous density of 1000 cd/m.sup.2. The lifetime LT is defined as the time after which the luminous density drops from the initial luminous density to a certain proportion L1 on operation at constant current. An expression of L0;j0=4000 cd/m.sup.2 and L1=70% in Table 2 means that the lifetime indicated in column LT corresponds to the time after which the initial luminous density drops from 4000 cd/m.sup.2 to 2800 cd/m.sup.2. Analogously, L0;j0=20 mA/cm.sup.2, L1=80%, means that the luminous density drops to 80% of its initial value after time LT on operation at 20 mA/cm.sup.2.

[0208] The data of the various OLEDs are summarised in Table 2. Examples V1-V6 are comparative examples in accordance with the prior art, Examples E1-E37 show data of OLEDs according to the invention.

[0209] Some of the examples are explained in greater detail below in order to illustrate the advantages of the OLEDs according to the invention.

[0210] Use of Mixtures According to the Invention in the Emission Layer of Phosphorescent OLEDs

[0211] On use as matrix materials in phosphorescent OLEDs, the materials according to the invention give rise to significant improvements over the prior art with respect to the lifetime of the components. Use of compounds EG1 to EG4 according to the invention in combination with the green-emitting dopant TEG1 enables an increase in the lifetime by more than 200% compared with the prior art to be observed (comparison of Examples V1 with E1, E6 and V2 with E2 as well as V3 with E3 and V4, V5 with E4).

TABLE-US-00016 TABLE 1 Structure of the OLEDs HTL IL EBL EML HBL ETL EIL Ex. Thickness Thickness Thickness Thickness Thickness Thickness Thickness V1 SpA1 HATCN SpMA1 SdT1:TEG1 (90%:10%) ST2 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm V2 SpA1 HATCN SpMA1 SdT2:TEG1 (90%:10%) ST2 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm V3 SpA1 HATCN SpMA1 SdT3:TEG1 (90%:10%) ST2 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm V4 SpA1 HATCN SpMA1 SdT4:TEG1 (90%:10%) ST2 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm V5 SpA1 HATCN SpMA1 SdT5:TEG1 (90%:10%) ST2 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm V6 SpA1 HATCN SpMA1 SdT6:TEG1 (90%:10%) ST2 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E1 SpA1 HATCN SpMA1 EG1:TEG1 (90%:10%) ST2 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E2 SpA1 HATCN SpMA1 EG2:TEG1 (90%:10%) ST2 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E3 SpA1 HATCN SpMA1 EG3:TEG1 (90%:10%) ST2 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E4 SpA1 HATCN SpMA1 EG4:TEG1 (90%:10%) ST2 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E5 SpA1 HATCN SpMA1 EG5:TER1 (92%:8%) — ST2:LiQ (50%:50%) — 90 nm  5 nm 130 nm 30 nm 40 nm E6 SpA1 HATCN SpMA1 EG6:TER1 (92%:8%) — ST2:LiQ (50%:50%) — 90 nm  5 nm 130 nm 30 nm 40 nm E7 SpA1 HATCN SpMA1 EG7:TEG1 (90%:10%) — ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 40 nm E8 SpA1 HATCN SpMA1 EG8:TEG1 (90%:10%) — ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 40 nm E9 SpA1 HATCN SpMA1 EG9:IC3:TEG1 (45%:45%:10%) IC1 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E10 SpA1 HATCN SpMA1 EG10:IC3:TEG1 (45%:45%:10%) IC1 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E11 SpA1 HATCN SpMA1 EG11:IC3:TEG1 (45%:45%:10%) IC1 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E12 SpA1 HATCN SpMA1 IC1:TEG1 (90%:10%) — EG12 LiQ 70 nm  5 nm  90 nm 30 nm 40 nm 3 nm E13 SpA1 HATCN SpMA1 IC1:TEG1 (90%:10%) IC1 EG13:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E14 SpA1 HATCN SpMA1 EG14:IC3:TEG1 (65%:25%:10%) IC1 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E15 SpA1 HATCN SpMA1 IC1:TEG1 (90%:10%) EG15 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E16 HATCN SpMA1 SpMA2 EG16:L1:TEY1 (45%:45%:10%) — ST1 LiQ  5 nm 70 nm  15 nm 25 nm 45 nm 3 nm E17 SpA1 HATCN SpMA1 EG17:TEG1 (90%:10%) ST2 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E18 SpA1 HATCN SpMA1 EG18:IC3:TEG1 (45%:45%:10%) IC1 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E19 HATCN SpMA1 SpMA2 EG19:L1:TEY1 (45%:45%:10%) — ST1 LiQ 5 nm 70 nm  15 nm 25 nm 45 nm 3 nm E20 SpA1 HATCN SpMA1 IC1:TEG1 (90%:10%) EG20 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E21 SpA1 HATCN SpMA1 EG21:TEG1 (90%:10%) — ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 40 nm E22 SpA1 HATCN SpMA1 EG22:TEG1 (90%:10%) — ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 30 nm E23 SpA1 HATCN SpMA1 IC1:TEG1 (90%:10%) — EG23:ST1 LiQ 70 nm  5 nm  90 nm 30 nm 40 nm 3 nm E24 SpA1 HATCN SpMA1 EG24:TEG1 (90%:10%) — ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 30 nm E25 SpA1 HATCN SpMA1 EG25:IC3:TEG1 (50%:40%:10%) ST2 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E26 SpA1 HATCN SpMA1 EG26:IC3:TEG1 (55%:35%:10%) ST2 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E27 SpA1 HATCN SpMA1 EG27:IC3:TEG1 (45%:45%:10%) ST2 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E28 SpA1 HATCN SpMA1 IC1:TEG1 (90%:10%) IC1 EG28:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E29 SpA1 HATCN SpMA1 EG29:TER1 (92%:8%) — ST2:LiQ (50%:50%) — 90 nm  5 nm 130 nm 30 nm 40 nm E30 SpA1 HATCN SpMA1 EG30:IC3:TEG1 (45%:45%:10%) ST2 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E31 SpA1 HATCN SpMA1 EG1:IC3:TEG1 (50%:40%:10%) ST2 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E32 SpA1 HATCN SpMA1 EG1:IC4:TEG1 (40%:45%:15%) ST2 ST2LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E33 SpA1 HATCN SpMA1 EG1:IC5:TEG1 (70%:25%:5%) ST2 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E34 SpA1 HATCN SpMA1 EG1:IC6:TEG1 (45%:45%:10%) ST2 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E35 SpA1 HATCN SpMA1 EG1:IC7:TEG1 (40%:50%:10%) ST2 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E36 SpA1 HATCN SpMA1 EG1:IC8:TEG1 (30%:50%:20%) ST2 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm E37 SpA1 HATCN SpMA1 EG1:L1:TEG1 (25%:55%:20%) ST2 ST2:LiQ (50%:50%) — 70 nm  5 nm  90 nm 30 nm 10 nm 30 nm

TABLE-US-00017 TABLE 2 Data of the OLEDs U1000 CE1000 PE1000 EQE CIE x/y at L1 LT Ex. (V) (cd/A) (lm/W) 1000 1000 cd/m.sup.2 L.sub.0: j.sub.0 % (h) V1 3.6 51 44 13.7% 0.33/0.63 20 mA/cm.sup.2 80 95 V2 4.2 50 37 14.3% 0.33/0.62 20 mA/cm.sup.2 80 10 V3 4.3 55 40 14.7% 0.33/0.64 20 mA/cm.sup.2 80 15 V4 3.5 48 43 12.8% 0.32/0.64 20 mA/cm.sup.2 80 190 V5 3.7 59 50 15.7% 0.33/0.64 20 mA/cm.sup.2 80 125 V6 3.4 44 41 11.8% 0.31/0.65 20 mA/cm.sup.2 80 20 E1 3.5 40 36 11.6% 0.33/0.62 20 mA/cm.sup.2 80 290 E2 4.3 51 37 14.5% 0.33/0.62 20 mA/cm.sup.2 80 20 E3 4.4 55 39 15.0% 0.33/0.63 20 mA/cm.sup.2 80 35 E4 3.6 41 35 11.9% 0.32/0.63 20 mA/cm.sup.2 80 300 E5 4.4 13 9 12.4% 0.66/0.34 4000 cd/m.sup.2 80 340 E6 4.6 11 8 11.4% 0.67/0.34 4000 cd/m.sup.2 80 370 E7 3.4 59 55 15.9% 0.33/0.63 20 mA/cm.sup.2 80 115 E8 3.6 56 49 15.2% 0.33/0.62 20 mA/cm.sup.2 80 125 E9 3.4 62 57 16.5% 0.34/0.63 20 mA/cm.sup.2 80 240 E10 3.5 60 54 16.1% 0.33/0.63 20 mA/cm.sup.2 80 350 E11 3.6 57 50 15.5% 0.33/0.63 20 mA/cm.sup.2 80 290 E12 3.3 64 61 17.1% 0.33/0.63 20 mA/cm.sup.2 80 125 E13 3.7 62 53 16.5% 0.34/0.63 20 mA/cm.sup.2 80 165 E14 3.3 60 57 16.7% 0.32/0.63 20 mA/cm.sup.2 80 270 E15 3.5 59 53 16.0% 0 34/0.63 20 mA/cm.sup.2 80 145 E16 2.9 75 81 22.4% 0.44/0.55 50 mA/cm.sup.2 90 85 E17 3.4 41 37 11.7% 0.33/0.63 20 mA/cm.sup.2 80 140 E18 3.5 60 53 16.3% 0.33/0.63 20 mA/cm.sup.2 80 260 E19 2.8 77 86 23.1% 0.45/0.55 50 mA/cm.sup.2 90 100 E20 3.7 59 50 15.8% 0.33/0.63 20 mA/cm.sup.2 80 155 E21 3.7 55 47 14.7% 0.36/0.61 20 mA/cm.sup.2 80 135 E22 3.8 58 48 15.6% 0.33/0.63 20 mA/cm.sup.2 80 140 E23 3.4 62 57 17.0% 0.31/0.64 20 mA/cm.sup.2 80 130 E24 3.8 56 46 15.3% 0.33/0.63 20 mA/cm.sup.2 80 125 E25 3.6 60 52 16.0% 0.35/0.62 20 mA/cm.sup.2 80 360 E26 3.7 57 48 15.2% 0.33/0.63 20 mA/cm.sup.2 80 275 E27 3.6 54 47 15.5% 0.34/0.61 20 mA/cm.sup.2 80 255 E28 3.6 60 52 16.4% 0.34/0.62 20 mA/cm.sup.2 80 170 E29 4.5 13 9 11.6% 0.67/0.33 4000 cd/m.sup.2 80 340 E30 3.5 58 52 15.6% 0.33/0.63 20 mA/cm.sup.2 80 270 E31 3.4 59 55 15.9% 0.32/0.64 20 mA/cm.sup.2 80 380 E32 3.4 61 56 16.2% 0.33/0.64 20 mA/cm.sup.2 80 360 E33 3.3 59 56 15.7% 0.33/0.63 20 mA/cm.sup.2 80 335 E34 3.5 61 55 16.3% 0.33/0.63 20 mA/cm.sup.2 80 355 E35 3.4 62 57 16.6% 0.31/0.64 20 mA/cm.sup.2 80 340 E36 3.4 59 55 16.1% 0.33/0.63 20 mA/cm.sup.2 80 345 E37 3.3 54 51 15.0% 0.32/0.63 20 mA/cm.sup.2 80 395

TABLE-US-00018 TABLE 3 Structural formulae of the materials for the OLEDs [00620] HATCN [00621] SpA1 [00622] SpMA1 [00623] LiQ [00624] SpMA2 [00625] TER1 [00626] L1 [00627] TEY1 [00628] IC1 [00629] ST2 [00630] IC3 [00631] TEG1 [00632] IC4 [00633] IC5 [00634] IC6 [00635] IC7 [00636] IC8 [00637] SdT1 [00638] SdT2 [00639] SdT3 [00640] SdT4 [00641] SdT5 [00642] SdT6 [00643] EG1 [00644] EG2 [00645] EG3 [00646] EG4 [00647] EG5 [00648] EG6 [00649] EG7 [00650] EG8 [00651] EG9 [00652] EG10 [00653] EG11 [00654] E12 [00655] EG13 [00656] EG14 [00657] EG15 [00658] EG16 [00659] EG17 [00660] EG18 [00661] EG19 [00662] EG20 [00663] EG21 [00664] EG22 [00665] EG23 [00666] EG24 [00667] EG25 [00668] EG26 [00669] EG27 [00670] EG28 [00671] EG29 [00672] EG30 [00673]