MATERIALS FOR ELECTRONIC DEVICES

Abstract

The invention relates to compounds comprising functional substituents in a specific spatial arrangement, devices containing same, and the preparation and use thereof.

Claims

1.-21. (canceled)

22. A compound of the general formula (1) ##STR00565## where the symbols and indices used are as follows: A and A′ are the same or different and are an aromatic or heteroaromatic ring which has 5 or 6 ring atoms and is optionally substituted by one or more R.sup.1 radicals which is optionally independent of one another; G.sup.1 is an organic electron-transporting group (ETG) of the formula E-9 or E-10 ##STR00566## Q′ is the same or different at each instance and is CR.sup.1 or N, and where the dotted bond indicates the binding positions to the Ar.sup.1 group or carbon atom of the A group; G.sup.2 is an electron-rich organic group selected from the a group of the formula (L-18)-(L-30) and L(34)-L(36): ##STR00567## ##STR00568## ##STR00569## where dotted bonds indicate the binding positions to the Ar.sup.2 group or carbon atom of the A′ group, which may be substituted by one or more independent R.sup.2 radicals; Ar.sup.1 is a bivalent aromatic ring or ring system having 6 to 60 ring atoms, where the ring or ring system is bridged neither with the ring system comprising the A and A′ rings nor with the ETG; Ar.sup.2 is, when G.sup.2 is an electron-transporting group, a bivalent aromatic ring or ring system having 6 to 60 ring atoms, where the ring or ring system is bridged neither with the ring system comprising the A and A′ rings nor with the ETG, or, when G.sup.2 is a hole-transporting group, an aromatic ring or ring system having 5 to 60 ring atoms, where the ring or ring system is bridged neither with the ring system comprising the A and A′ rings nor with the LTG; V is O; W is a single bond, C═O, C(R.sup.1).sub.2, NR.sup.1, where, in the case of a single bond, the carbon atoms of the A and A′ rings are joined directly to one another by a single bond, C(R.sup.1).sub.2, NR.sup.1, O and S; m is either 0 or 1; n is either 0 or 1, where m=n; p is either 0 or 1; q is either 0 or 1, where p+q is either 1 or 2; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(═O)R.sup.2, P(═O)(R.sup.2).sub.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy or thioalkoxy group having 3 to 40 carbon atoms, which is optionally substituted by one or more R.sup.2 radicals; where one or more nonadjacent CH.sub.2 groups is optionally replaced by R.sup.2C═CR.sup.2, C≡C, Si(R.sup.2).sub.2, Ge(R.sup.2).sub.2, Sn(R.sup.2).sub.2, C═O, C═S, C═Se, C═NR.sup.2, P(═O)(R.sup.2), SO, SO.sub.2, NR.sup.2, O, S or CONR.sup.2 and where one or more hydrogen atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms which is optionally substituted by one or more R.sup.2 radicals; or an aryloxy, arylalkoxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms which is optionally substituted by one or more R.sup.2 radicals; or a diarylamino group, diheteroarylamino group or arylheteroarylamino group which has 10 to 40 aromatic ring atoms which is optionally substituted by one or more R.sup.2 radicals, or a combination of two or more of these groups or a crosslinkable Q group; R.sup.2 is the same or different at each instance and is H, D, F, Cl, Br, I, CN, NO.sub.2, Si(R.sup.3).sub.3, B(OR.sup.3).sub.2, C(═O)R.sup.3, P(═O)(R.sup.3).sub.2, S(═O)R.sup.3, S(═O).sub.2R.sup.3, OSO.sub.2R.sup.3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy or thioalkoxy group having 3 to 40 carbon atoms, which is optionally substituted by one or more R.sup.3 radicals, where one or more nonadjacent CH.sub.2 groups is optionally replaced by R.sup.3C═CR.sup.3, C≡C, Si(R.sup.3).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, C═O, C═S, C═Se, C═NR.sup.3, P(═O)(R.sup.3), SO, SO.sub.2, NR.sup.3, O, S or CONR.sup.3 and where one or more hydrogen atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2; or an aromatic ring system which has 6 to 60 aromatic ring atoms which is optionally substituted by one or more R.sup.3 radicals; or an aryloxy, arylalkoxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms which is optionally substituted by one or more R.sup.3 radicals; or a diarylamino group, diheteroarylamino group or arylheteroarylamino group which has 10 to 40 aromatic ring atoms which is optionally substituted by one or more R.sup.3 radicals; or a combination of two or more of these groups; at the same time, two or more adjacent R.sup.2 radicals together may form a mono- or polycyclic, aliphatic or aromatic ring system; R.sup.3 is the same or different at each instance and is H, D, F or an aliphatic, or aromatic radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; at the same time, two or more R.sup.3 substituents together may also form a mono- or polycyclic aliphatic or aromatic ring system; with the proviso that not more than one R.sup.1 substituent in the A ring and not more than one R.sup.1 substituent in the A′ ring contains an aromatic or heteroaromatic group having 5 to 30 ring atoms.

23. The compound as claimed in claim 22, wherein the compound is of the general formula (2) ##STR00570## where the symbols additionally used are as follows: X is the same or different at each instance and is N or CR.sup.1; Q is the same or different at each instance and is X═X, S, O or NR.sup.1.

24. The compound as claimed in claim 22, wherein the compound is of one of the following general formulae (3) or (4): ##STR00571##

25. The compound as claimed in claim 24, wherein the compound is of the general formula (4).

26. The compound as claimed in claim 24, wherein the compound is of the general formula (4) where X is CR.sup.1 and m is 1. ##STR00572##

27. The compound as claimed in claim 24, wherein the compound is of the general formula (4) where X is CR.sup.1, m is 1, p is 0 and q is 1.

28. The compound as claimed in claim 22, wherein the compound is of the general formula (13) ##STR00573## where V is O and where the aromatic rings each have not more than one R.sup.1 substituent, s is 0 or 1 and t is 0 or 1, where s+t is 0, 1 or 2.

29. The compound as claimed in claim 22, wherein the compound is of the general formula (15) ##STR00574## wherein s is 0 or 1 and t is 0 or 1, where s+t is 0, 1 or 2.

30. The compound as claimed in claim 22, wherein the compound is of the general formula (16) ##STR00575## wherein s is 0 or 1 and t is 0 or 1, where s+t is 0, 1 or 2.

31. The compound as claimed in claim 22, wherein the compound is of the general formula (16a). ##STR00576##

32. A composition comprising at least one additional compound as claimed in claim 22 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials and hole blocker materials.

33. The composition as claimed in claim 32, wherein the additional compound is a host or matrix material.

34. The composition as claimed in claim 32, wherein the additional compound has a band gap of 2.5 eV or more.

35. A formulation comprising at least one compound as claimed in claim 22 and at least one solvent.

36. An electronic device comprising at least one compound as claimed in claim 22.

37. An electronic device comprising at least one compound as claimed in claim 22 in an emission layer (EML), electron transport layer (ETL) or in a hole blocker layer (HBL).

38. The electronic device as claimed in claim 36, wherein the device is an organic integrated circuit (OIC), an organic field-effect transistor (OFET), an organic thin-film transistor (OTFT), an organic electroluminescent device (OLED), an organic light-emitting electrochemical cell (OLEC, LEEC, LEC), an organic solar cell (OSC), an organic optical detector, or an organic photoreceptor.

39. The electronic device as claimed in claim 37, wherein the device is an organic electroluminescent device which is selected from the group consisting of organic light-emitting transistors (OLETs), organic field quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs, LECs, LEECs), organic laser diodes (O-lasers) and organic light-emitting diodes (OLEDs).

40. A process for producing an electronic device as claimed in claim 36, which comprises applying at least one organic layer by gas phase deposition or from solution.

41. The electronic device as claimed in claim 40 for use in medicine for phototherapy.

42. The compound as claimed in claim 22, wherein the compound is of the general formulae (3): ##STR00577##

43. The compound as claimed in claim 22, wherein the compound is of one of the following general formulae (5) to (11): ##STR00578## ##STR00579##

44. The compound as claimed in claim 22, wherein each R.sup.1 is independently selected from the group consisting of H and an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which is optionally substituted by one or more R.sup.2 radicals.

45. The compound as claimed in claim 22, wherein G.sup.1 is an organic electron-transporting group (ETG) of the formula E-10.

46. The compound as claimed in claim 22, wherein G.sup.1 is selected from the group consisting of quinolines, isoquinolines, and quinoxalines, which are optionally substituted by one or more R.sup.1.

47. The compound as claimed in claim 22, wherein G.sup.1 is a quinoxaline, which is optionally substituted by one or more R.sup.1.

48. The compound as claimed in claim 43, wherein the compound is of general formula (8).

Description

EXAMPLES

[0199] The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The figures in square brackets for chemical compounds known from the literature are the CAS number.

Example 1

Synthesis of 3-dibenzofuran-4-yl-9-phenyl-9H-carbazole

[0200] ##STR00220##

[0201] 28.9 g (136 mmol) of dibenzofuran-4-boronic acid, 40 g (124.1 mmol) of 3-bromo-9-phenyl-9H-carbazole and 78.9 mL (158 mmol) of Na.sub.2CO.sub.3 (2 M solution) are suspended in 120 mL of toluene, 120 mL of ethanol and 100 mL of water. 2.6 g (2.2 mmol) of Pd(PPh.sub.3).sub.4 are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 200 mL of water and then concentrated to dryness. The residue is recrystallized from toluene. The yield is 49.7 g (121 mmol), corresponding to 97% of theory.

[0202] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00002 Reactant 1 Reactant 2 Product Yield [00221] [00222] [00223] 90% [00224] [00225] [00226] 92% [00227] [00228] [00229] 89% [00230] [00231] [00232] 92% [00233] [00234] [00235] 86% [00236] [00237] [00238] 69% [00239] [00240] [00241] 72%

Example 2

Synthesis of bis(biphenyl-4-yl)dibenzofuran-4-ylamine

[0203] ##STR00242##

[0204] A degassed solution of 36.6 g (147 mmol) of 4-bromodibenzofuran and 39.5 g (123 mmol) of bis(biphenyl-4-yl)amine in 600 mL of toluene is saturated with N.sub.2 for 1 h. Added to the solution thereafter are first 2.09 mL (8.6 mmol) of P(tBu).sub.3, then 1.38 g (6.1 mmol) of palladium(II) acetate, and then 17.7 g (185 mmol) of NaOtBu in the solid state. The reaction mixture is heated under reflux for 1 h. After cooling to room temperature, 500 mL of water are added cautiously The aqueous phase is washed with 3×50 mL of toluene, dried over M.sub.gSO.sub.4, and the solvent is removed under reduced pressure. Thereafter, the crude product is purified by chromatography using silica gel with heptane/ethyl acetate (20:1).

[0205] The yield is 57.7 g (118 mmol), corresponding to 80% of theory.

[0206] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00003 Reactant 1 Reactant 2 Product Yield [00243] [00244] [00245] 90% [00246] [00247] [00248] 87% [00249] [00250] [00251] 83% [00252] [00253] [00254] 57% [00255] [00256] [00257] 93%

Example 3

Synthesis of 9-phenyl-3-(6-trimethylsilanyldibenzofuran-4-yl)-9H-carbazole

[0207] ##STR00258##

[0208] To a solution, cooled to 20° C., of 49 g (121 mmol) of 3-dibenzofuran-4-yl-9-phenyl-9H-carbazole and 28 g (242 mmol) of TMEDA in 1000 mL of THE are added dropwise 127 mL (225.4 mmol) of n-butyllithium (2.5 M in hexane). The reaction mixture is stirred at room temperature for 3 h, then cooled down to 0° C., and 26 g (242 mmol) of chlorotrimethylsilane are added dropwise within 30 minutes and the mixture is stirred at room temperature for 8 h. Subsequently, the solvent is removed under reduced pressure and the residue is purified by chromatography using silica gel with chloroform as eluent. Yield: 34 g (72 mmol), 60% of theory.

[0209] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00004 Reactant 1 Product Yield [00259] [00260] 81% [00261] [00262] 83% [00263] [00264] 88% [00265] [00266] 84% [00267] [00268] 88% [00269] [00270] 70% [00271] [00272] 86% [00273] [00274] 79% [00275] [00276] 75% [00277] [00278] 72% [00279] [00280] 65% [00281] [00282] 64% [00283] [00284] 63%

Example 4

Synthesis of B-[6-(phenyl-9H-carbazol-3-yl)-4-dibenzofuranyl]boronic acid

[0210] ##STR00285##

[0211] Under protective gas, 21 g (86 mmol) of bromine tribromide are added dropwise to a solution of 34 g (72 mmol) of N-phenyl-3-(6-trimethylsilanyldibenzofuran-4-yl)-9H-carbazole in 500 mL of dichloromethane and the mixture is stirred at room temperature for 10 h. Thereafter, a little water is added gradually to the mixture and the precipitated residue is filtered off and washed with heptane. The yield is 28 g (62 mmol), corresponding to 86% of theory.

[0212] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00005 Reactant 1 Product Yield [00286] [00287] 84% [00288] [00289] 84% [00290] [00291] 81% [00292] [00293] 87% [00294] [00295] 86% [00296] [00297] 79% [00298] [00299] 78% [00300] [00301] 83% [00302] [00303] 85% [00304] [00305] 81% [00306] [00307] 78% [00308] [00309] 69% [00310] [00311] 78% [00312] [00313] 78%

Example 5

Synthesis of B-[6-(phenyl-9H-carbazol-3-yl)-4-dibenzofuranyl]boronic acid

[0213] ##STR00314##

[0214] 9 g (32 mmol) of B,B′-4,6-dibenzofurandiylbisboronic acid, 15 g (31.6 mmol) of 3-bromo-9-phenyl-9H-carbazole and 31 mL (63 mmol) of Na.sub.2CO.sub.3 (2 M solution) are suspended in 120 mL of toluene and 120 mL of ethanol. 0.73 g (0.63 mmol) of Pd(PPh.sub.3).sub.4 are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 200 mL of water and then concentrated to dryness. The residue is recrystallized from toluene. The yield is 11.1 g (24 mmol), corresponding to 70% of theory.

[0215] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00006 Reactant 1 Reactant 2 Product Yield [00315] [00316] [00317] 85% [00318] [00319] [00320] 69% [00321] [00322] [00323] 74%

Example 6

Synthesis of 3-(6-bromodibenzofuran-4-yl)-9-phenyl-9H-carbazole

[0216] ##STR00324##

[0217] 10.43 g (32 mmol) of B-(9-phenyl-9H-carbazol-3-yl)boronic acid, 8.9 g (31.6 mmol) of 4,6-dibromodibenzofuran and 31 mL (63 mmol) of Na.sub.2CO.sub.3 (2 M solution) are suspended in 120 mL of toluene and 120 mL of ethanol. 0.73 g (0.63 mmol) of Pd(PPh.sub.3).sub.4 is added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 200 mL of water and then concentrated to dryness. The residue is recrystallized from toluene. The yield is 11.4 g (23 mmol), corresponding to 73% of theory.

[0218] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00007 Reactant 1 Reactant 2 Product Yield [00325] [00326] [00327] 51% [00328] [00329] [00330] 65% [00331] [00332] [00333] 69% [00334] [00335] [00336] 67% [00337] [00338] [00339] 62% [00340] [00341] [00342] 62% [00343] [00344] [00345] 61% [00346] [00347] [00348] 64% [00349] [00350] [00351] 66% [00352] [00353] [00354] 56%

[0219] In an analogous manner, it is also possible to obtain the following compounds by a second addition with the appropriate boronic acids: The residue is recrystallized from toluene and finally sublimed under high vacuum (p=5×10.sup.−5 mbar).

TABLE-US-00008 Reactant 1 Reactant 2 Product Yield [00355] [00356] [00357] 80% [00358] [00359] [00360] 79% [00361] [00362] [00363] 68% [00364] [00365] [00366] 78% [00367] [00368] [00369] 87% [00370] [00371] [00372] 89% [00373] [00374] [00375] 87% [00376] [00377] [00378] 83% [00379] [00380] [00381] 80% [00382] [00383] [00384] 79% [00385] [00386] [00387] 79%

Example 7

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

[0220] ##STR00388##

[0221] 32.1 g (70 mmol) of B-[6-(phenyl-9H-carbazol-3-yl)-4-dibenzofuranyl]boronic acid, 27 g (70 mmol) of 2-(3-bromophenyl)-4,6-diphenyl-[1,3,5]triazine and 78.9 mL (158 mmol) of Na.sub.2CO.sub.3 (2 M solution) are suspended in 120 mL of ethanol and 100 mL of water. 1.3 g (1.1 mmol) of Pd(PPh.sub.3).sub.4 are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, dichloromethane is added to the mixture, and the organic phase is removed and filtered through silica gel. The yield is 44 g (61 mmol), corresponding to 87% of theory. The residue is recrystallized from toluene and finally sublimed under high vacuum (p=5×10.sup.−5 mbar). The purity is 99.9%.

[0222] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00009 Reactant 1 Reactant 2 [00389] [00390] [00391] [00392] [00393] [00394] [00395] [00396] [00397] [00398] [00399] [00400] [00401] [00402] [00403] [00404] [00405] [00406] [00407] [00408] [00409] [00410] [00411] [00412] [00413] [00414] [00415] [00416] [00417] [00418] [00419] [00420] [00421] [00422] [00423] [00424] [00425] [00426] [00427] [00428] [00429] [00430] [00431] [00432] Product Yield [00433] 79% [00434] 83% [00435] 86% [00436] 89% [00437] 80% [00438] 79% [00439] 84% [00440] 79% [00441] 77% [00442] 78% [00443] 79% [00444] 75% [00445] 74% [00446] 59% [00447] 67% [00448] 68% [00449] 70% [00450] 71% [00451] 78% [00452] 78% [00453] 73% [00454] 79%

Example 8

Synthesis of 9,9′-diphenyl-8-(3-{4-phenyl-6-[(E)-((Z)-1-propenyl)-buta-1,3-dienyl]-[1,3,5]triazin-2-yl}-phenyl)-9H,9′H-[1,2′]bicarbazolyl

[0223] ##STR00455##

[0224] 50 g (70.58 mmol) of 8-[3-(4,6-diphenyl-[1,3,5]triazin-2-yl)-phenyl]-9′-phenyl-9H,9′H-[1,2′]bicarbazolyl and 16.4 g (105.87 mmol) of bromobenzene are dissolved in toluene and degassed by means of introduction of protective gas. This is followed by addition of 7 mL (7 mmol, 1 M solution in toluene) of tri-tert-butylphosphine, 633.8 mg (2.82 mmol) of Pd(OAc).sub.2 and 10.2 g (105.87 mmol) of NaOtBu. The solids are degassed beforehand, and the reaction mixture is post-degassed and then stirred under reflux for 3 h. The warm reaction solution is filtered through Alox B (activity level 1), washed with water, dried and concentrated. The yield is 42 g (53 mmol), corresponding to 77% of theory. The residue is recrystallized from toluene and finally sublimed under high vacuum (p=5×10.sup.−5 mbar). The purity is 99.9%.

[0225] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00010 Reactant 1 Reactant 2 Product Yield [00456] [00457] [00458] 79% [00459] [00460] [00461] 80% [00462] [00463] [00464] 80%

Example 9

Synthesis of 2-{6-[4-(2,6-diphenylpyridin-4-yl)phenyl]dibenzofuran-4-yl}-4,6-diphenyl[1,3,5]triazine

[0226] ##STR00465##

[0227] 9 g (32 mmol) of B,B′-4,6-dibenzofurandiylbisboronic acid, 6.5 g (31.6 mmol) of 2-chloro-4,6-diphenyl[1,3,5]triazine and 31 mL (63 mmol) of Na.sub.2CO.sub.3 (2 M solution) are suspended in 120 mL of toluene and 120 mL of ethanol. 0.73 g (0.63 mmol) of Pd(PPh.sub.3).sub.4 is added to this suspension, and the reaction mixture is heated under reflux for 8 h. Subsequently, 6.5 g (31.6 mmol) of 4-(4-bromophenyl)-2,6-diphenylpyridine are added and the mixture is heated under reflux for a further 8 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 200 mL of water and then concentrated to dryness. The residue is recrystallized from toluene. The yield is 19.1 g (26 mmol), corresponding to 77% of theory.

[0228] In an analogous manner, it is possible to obtain the following compounds:

[0229] In the case of a symmetric compound, first 0.5 eq of reactant 2 and then 0.5 eq of reactant 3 are added.

TABLE-US-00011 Reactant 1 Reactant 2 Reactant 3 1 eq. 0.5 eq. 0.5 eq. [00466] [00467] [00468] [00469] [00470] [00471] [00472] [00473] [00474] [00475] [00476] [00477] [00478] [00479] [00480] [00481] [00482] [00483] [00484] [00485] [00486] [00487] [00488] [00489] [00490] [00491] [00492] [00493] [00494] [00495] [00496] [00497] [00498] Product Yield [00499] 83% [00500] 79% [00501] 69% [00502] 71% [00503] 60% [00504] 59% [00505] 65% [00506] 76% [00507] 65% [00508] 56% [00509] 61%

Example 10

Synthesis of 2-{6-[4-(2,6-diphenyl-[1,3,4]triazin-4-yl)phenyl]-dibenzofuran-4-yl}-4,6-diphenyl-[1,3,5]triazine

a) Preparation of 2-(6-bromodibenzofuran-4-yl)-4,6-diphenyl-[1,3,5]triazine

[0230] ##STR00510##

[0231] 80 g (245 mmol) of 4,6-dibromodibenzofuran are dissolved in a baked-out flask in 500 mL of dried THF. The reaction mixture is cooled to −78° C. At this temperature, 57 mL of a 1.9 M solution of n-phenyllithium in dibutyl ether (115 mmol) are slowly added dropwise. The mixture is stirred at −73° C. for a further 1 hour. Subsequently, 65 g of 2-chloro-4,6-diphenyl-1,3,5-triazine (245 mmol) are dissolved in 150 mL of THE and added dropwise at −70° C. After the addition has ended, the reaction mixture is warmed gradually to room temperature, stirred at room temperature overnight, quenched with water and then concentrated on a rotary evaporator. During this time, a white solid precipitates out. The mixture is then cooled to room temperature, and the precipitated solid is filtered off with suction and washed with methanol. The yield is 40 g (84 mmol), corresponding to 34% of theory.

b) Preparation of 2-{6-[4-(2,6-diphenyl-[1,3,4]triazin-4-yl)phenyl]-dibenzofuran-4-yl}-4,6-diphenyl-[1,3,5]triazine

[0232] ##STR00511##

[0233] 33.4 g (70 mmol) of 2-(6-bromodibenzofuran-4-yl)-4,6-diphenyl-[1,3,5]triazine, 24.7 g (70 mmol) of 4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenylboronic acid and 78.9 mL (158 mmol) of Na.sub.2CO.sub.3 (2 M solution) are suspended in 120 mL of ethanol and 100 mL of water. 1.3 g (1.1 mmol) of Pd(PPh.sub.3).sub.4 are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, dichloromethane is added to the mixture, and the organic phase is removed, filtered through silica gel and recrystallized from toluene. The yield is 42 g (59 mmol), corresponding to 85% of theory.

Example 11

Preparation of 2-(4-dibenzofuran-3-yl-phenyl)-4,6-diphenyl-[1,3,5]triazine

[0234] ##STR00512##

[0235] 24 g (70 mmol) of 4-(4,6-diphenyl-1,3,5-triazin-2-ylphenyl)boronic acid, 17.3 g (70 mmol) of 3-bromodibenzofuran and 78.9 mL (158 mmol) of Na.sub.2CO.sub.3 (2 M solution) are suspended in 120 mL of ethanol and 100 mL of water. 1.3 g (1.1 mmol) of Pd(PPh.sub.3).sub.4 are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, dichloromethane is added to the mixture, and the organic phase is removed, filtered through silica gel and recrystallized from toluene. The yield is 28 g (58 mmol), corresponding to 86% of theory.

[0236] In an analogous manner, it is possible to prepare the following compound:

TABLE-US-00012 Reactant 1 Reactant 2 Product Yield [00513] [00514] [00515] 87%

Example 12

Preparation of 2,4-diphenyl-6-[4-(6-trimethylsilanyl-dibenzofuran-3-yl)phenyl]-[1,3,5]triazine

[0237] ##STR00516##

[0238] To a solution, cooled to 20° C., of 57.4 g (121 mmol) of 2-(4-dibenzofuran-3-yl-phenyl)-4,6-diphenyl-[1,3,5]triazine and 28 g (242 mmol) of TMEDA in 1000 mL of THE are added dropwise 127 mL (225.4 mmol) of n-butyllithium (2.5 M in hexane). The reaction mixture is stirred at room temperature for 3 h, then cooled down to 0° C., and 26 g (242 mmol) of chlorotrimethylsilane are added dropwise within 30 min. The mixture is stirred at room temperature for 8 h. Subsequently, the solvent is removed under reduced pressure and the residue is purified by chromatography using silica gel with chloroform as eluent. Yield: 41 g (74 mmol), 63% of theory.

[0239] In an analogous manner, it is possible to prepare the following compound:

TABLE-US-00013 Reactant 1 Product Yield [00517] [00518] 87%

Example 13

Preparation of 3-[4-(4,6-diphenyl-[1,3,5]triazin-2-yl)phenyl]-dibenzofuran-6-boronic acid

[0240] ##STR00519##

[0241] Under protective gas, 21 g (86 mmol) of bromine tribromide are added dropwise to a solution of 39 g of 2,4-diphenyl-6-[4-(6-trimethylsilanyldi-benzofuran-3-yl)phenyl]-[1,3,5]triazine in 500 mL of dichloromethane and the mixture is stirred at room temperature for 10 h. Thereafter, a little water is added gradually to the mixture and the precipitated residue is filtered off and washed with heptane. The yield is 32 g (62 mmol), corresponding to 87% of theory.

[0242] In an analogous manner, it is possible to prepare the following compound:

TABLE-US-00014 Reactant 1 Product Yield [00520] [00521] 90%

Example 14

Preparation of 3-{7-[4-(4,6-diphenyl-[1,3,5]triazin-2-yl)phenyl]dibenzofuran-4-yl}-9-phenyl-9H-carbazole

[0243] ##STR00522##

[0244] 36 g (70 mmol) of 3-[4-(4,6-diphenyl-[1,3,5]triazin-2-yl)phenyl]-dibenzofuran-6 boronic acid, 22.5 g (70 mmol) of 3-bromodibenzo-furan and 78.9 mL (158 mmol) of Na.sub.2CO.sub.3 (2 M solution) are suspended in 120 mL of ethanol and 100 mL of water. 1.3 g (1.1 mmol) of Pd(PPh.sub.3).sub.4 are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, dichloromethane is added to the mixture, and the organic phase is removed, filtered through silica gel and recrystallized from toluene. The residue is recrystallized from toluene and finally sublimed under high vacuum (p=5×10.sup.−5 mbar). The yield is 39 g (54 mmol), corresponding to 80% of theory.

[0245] In an analogous manner, it is possible to prepare the following compound:

TABLE-US-00015 Reactant 1 Reactant 2 Product Yield [00523] [00524] [00525] 87%

Example 15

Production and Characterization of the OLEDs

[0246] In examples C1 to 122 which follow (see tables 1 and 2), the data of various OLEDs are presented. Cleaned glass plaques (cleaning in laboratory glass washer, Merck Extran detergent) coated with structured ITO (indium tin oxide) of thickness 50 nm, for improved processing, 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 Deutschland, spun on from aqueous solution). These coated glass plaques form the substrates to which the OLEDs are applied.

[0247] The OLEDs basically have the following layer structure: substrate/hole transport layer (HTL)/interlayer (IL)/electron blocker layer (EBL)/emission layer (EML)/optional hole blocker layer (HBL)/electron transport layer (ETL)/optional electron injection layer (EIL) and finally a cathode. The cathode is formed by an aluminum layer of thickness 100 nm. The exact structure of the OLEDs can be found in table 1. The materials required for production of the OLEDs are shown in table 3.

[0248] All materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the emission layer always consists of at least one matrix material (host material) and an emitting dopant (emitter) which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as INV-1:IC3:TEG1 (60%:35%:5%) mean here that the material INV-1 is present in the layer in a proportion by volume of 60%, IC3 in a proportion of 35% and TEG1 in a proportion of 5%. Analogously, the electron transport layer may also consist of a mixture of two materials.

[0249] The OLEDs are characterized in a standard manner. 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) are determined as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian radiation characteristics. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y color coordinates are calculated therefrom. The parameter U1000 in table 2 refers to the voltage which is required for a luminance of 1000 cd/m.sup.2. CE1000 and PE1000 respectively refer to the current and power efficiencies which are achieved at 1000 cd/m.sup.2. Finally, EQE1000 refers to the external quantum efficiency at an operating luminance of 1000 cd/m.sup.2.

[0250] The data for the various OLEDs are collated in table 2. Examples C1-C8 are comparative examples and show OLEDs containing materials according to the prior art. Examples I1-I22 show data for OLEDs comprising materials of the invention.

[0251] Some of the examples are elucidated in detail hereinafter, in order to illustrate the advantages of the compounds of the invention. However, it should be pointed out that this is merely a selection of the data shown in table 2. As can be inferred from the table, even when the compounds of the invention that have not been specifically detailed are used, distinct improvement over the prior art are achieved, in some cases in all parameters, but in some cases only an improvement in efficiency or voltage is observed. However, improvement in one of the parameters mentioned is already a significant advance because various applications require optimization with regard to different parameters.

[0252] Use of Compounds of the Invention as Electron Transport Materials

[0253] Compared to an OLED in which the material VG-6 according to the prior art is used in the ETL, a distinct improvement in voltage and efficiency is observed when the materials INV-5, INV-7, INV-15, INV-21 and INV-20 of the invention are used. Especially when the substance INV-5 is used, a voltage improved by 1.5 V compared to VG-6 is obtained, for instance a 35% better external quantum efficiency and more than double the power efficiency (examples C6, I5).

[0254] Use of Compounds of the Invention as Matrix Materials in Phosphorescent OLEDs

[0255] By inserting a phenyl ring between pyrimidine and dibenzofuran, it is possible to improve the EQE by 15% and the voltage by 0.1 V (examples C1, I1). This is true in an analogous manner of compounds comprising triazine (examples C2, I2, I3).

[0256] In addition, it is advantageous when a triazine or carbazole group is bonded face-to-face with respect to the dibenzofuran (examples C4, I2, I3). This is true in an analogous manner when the connecting group between carbazole and triazine is not a dibenzofuran but a carbazole (examples C5, I4).

TABLE-US-00016 TABLE 1 Structure of the OLEDs HTL IL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness C1 SpA1 HATCN SpMA1 VG-1:TEG1 ST2 ST2:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm C2 SpA1 HATCN SpMA1 VG-2:TEG1 ST2 ST2:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm C3 SpA1 HATCN SpMA1 IC1:TEG1 — VG-7 LiQ 70 nm 5 nm 90 nm (90%:10%) 30 nm 40 nm 3 nm C4 SpA1 HATCN SpMA1 VG-4:TEG1 ST2 ST2:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm C5 SpA1 HATCN SpMA1 VG-5:TER1 — ST2:LiQ — 90 nm 5 nm 130 nm (92%:8%) 40 nm (50%:50%) 40 nm C6 SpA1 HATCN SpMA1 IC1:TEG1 — VG-6 LiQ 70 nm 5 nm 90 nm (90%:10%) 30 nm 40 nm 3 nm I1 SpA1 HATCN SpMA1 INV-1:TEG1 ST2 ST2:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm I2 SpA1 HATCN SpMA1 INV-2:TEG1 ST2 ST2:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm I3 SpA1 HATCN SpMA1 INV-3:TEG1 ST2 ST2:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm I4 SpA1 HATCN SpMA1 INV-4:TER1 — ST2:LiQ — 90 nm 5 nm 130 nm (92%:8%) 40 nm (50%:50%) 40 nm I5 SpA1 HATCN SpMA1 IC1:TEG1 — INV-5 LiQ 70 nm 5 nm 90 nm (90%:10%) 30 nm 40 nm 3 nm I6 SpA1 HATCN SpMA1 INV-10:TEG1 ST2 ST2:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm I7 SpA1 HATCN SpMA1 INV-6:TEG1 ST2 ST2:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm I8 SpA1 HATCN SpMA1 INV-7:TEG1 ST2 ST2:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm I9 SpA1 HATCN SpMA1 IC1:TEG1 — INV-7 LiQ 70 nm 5 nm 90 nm (90%:10%) 30 nm 30 nm 3 nm I10 SpA1 HATCN SpMA1 INV-8:TER1 — ST2:LiQ — 90 nm 5 nm 130 nm (92%:8%) 40 nm (50%:50%) 40 nm I11 SpA1 HATCN SpMA1 INV-9:IC3:TEG1 IC1 ST2:LiQ — 70 nm 5 nm 90 nm (60%:35%:5%) 30 nm 10 nm (50%:50%) 30 nm I12 SpA1 HATCN SpMA1 INV-11:IC2:TEG1 IC1 ST2:LiQ — 70 nm 5 nm 90 nm (45%:45%:10%) 30 nm 10 nm (50%:50%) 30 nm I13 SpA1 HATCN SpMA1 INV-12:TEG1 ST2 ST2:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm I14 SpA1 HATCN SpMA1 INV-13:TEG1 ST2 ST2:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm I15 SpA1 HATCN SpMA1 INV-14:TEG1 ST2 ST2:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm I16 SpA1 HATCN SpMA1 IC1:TEG1 — INV-15 LiQ 70 nm 5 nm 90 nm (90%:10%) 30 nm 40 nm 3 nm I17 SpA1 HATCN SpMA1 INV-16:TEG1 ST2 ST2:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm I18 SpA1 HATCN SpMA1 INV-17:TEG1 ST2 ST2:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm I19 SpA1 HATCN SpMA1 IC1:TEG1 INV-18 ST1:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm I20 SpA1 HATCN SpMA1 IC2:TEG1 INV-19 ST2:LiQ — 70 nm 5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm I21 SpA1 HATCN SpMA1 IC1:TEG1 — INV-20 LiQ 70 nm 5 nm 90 nm (90%:10%) 30 nm 40 nm 3 nm I22 SpA1 HATCN SpMA1 IC2:TEG1 — INV-21 LiQ 70 nm 5 nm 90 nm (90%:10%) 30 nm 40 nm 3 nm

TABLE-US-00017 TABLE 2 Data of the OLEDs U1000 CE1000 PE1000 EQE CIE x/y at Ex. (V) (cd/A) (lm/W) 1000 1000 cd/m.sup.2 C1 3.7 50 43 13.7% 0.33/0.62 C2 3.6 53 45 14.4% 0.34/0.62 C3 3.6 56 49 15.5% 0.34/0.62 C4 3.4 52 49 14.1% 0.33/0.62 C5 4.8 9.4 6.1 10.1% 0.67/0.33 C6 4.4 45 31 12.4% 0.34/0.62 I1 3.6 58 51 15.8% 0.33/0.62 I2 3.4 61 57 16.7% 0.33/0.62 I3 3.5 57 51 15.6% 0.34/0.62 I4 4.6 10.5 7.1 11.3% 0.67/0.33 I5 2.9 62 68 16.9% 0.34/0.63 I6 3.7 63 54 17.6% 0.33/0.63 I7 3.1 59 59 16.4% 0.34/0.62 I8 4.3 50 36 14.0% 0.39/0.59 I9 4.0 56 45 15.2% 0.33/0.62 I10 4.2 12.3 9.1 12.4% 0.67/0.33 I11 3.2 61 60 17.1% 0.34/0.62 I12 3.6 47 41 13.1% 0.32/0.63 I13 3.2 51 50 14.4% 0.33/0.62 I14 3.6 59 52 16.6% 0.34/0.62 I15 3.6 56 49 15.8% 0.33/0.62 I16 2.8 58 65 16.2% 0.32/0.63 I17 3.4 56 51 15.5% 0.34/0.62 I18 3.7 53 46 15.0% 0.33/0.63 I19 3.6 58 51 16.1% 0.32/0.63 I20 3.4 49 46 13.7% 0.35/0.61 I21 3.8 55 45 15.5% 0.35/0.62 I22 3.0 49 51 14.5% 0.35/0.61

TABLE-US-00018 TABLE 3 Materials used [00526] HATCN [00527] SpA1 [00528] LiQ [00529] TEG1 [00530] SpMA1 [00531] IC1 [00532] ST1 [00533] ST2 [00534] IC2 [00535] IC3 [00536] TER1 [00537] VG-1 [00538] VG-2 [00539] VG-3 [00540] VG-4 [00541] VG-5 [00542] VG-6 [00543] VG-7 [00544] INV-1 [00545] INV-2 [00546] INV-3 [00547] INV-4 [00548] INV-5 [00549] INV-6 [00550] INV-7 [00551] INV-8 [00552] INV-9 [00553] INV-10 [00554] INV-11 [00555] INV-12 [00556] INV-13 [00557] INV-14 [00558] INV-15 [00559] INV-16 [00560] INV-17 [00561] INV-18 [00562] INV-19 [00563] INV-20 [00564] INV-20