MATERIALS FOR ELECTRONIC DEVICES

Abstract

The present invention relates to compounds, compositions and formulations comprising same and to opto-electronic devices comprising the compounds and compositions according to the invention.

Claims

1-20. (canceled)

21. A compound comprising a skeleton of formula (GK-1), at least one group of formula (G-2), and at least one group of formula (G-3), wherein the skeleton and groups of formulae (G-2) and (G-3) are covalently bonded to one another: ##STR00401## wherein R1 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, N(Ar1).sub.2, C(═O)Ar1, P(═O)(Ar1).sub.2, S(═O)Ar1, S(═O).sub.2Ar1, CR2=CR2Ar1, CN, NO.sub.2, Si(R2).sub.3, B(OR2).sub.2, B(R2).sub.2, B(N(R2).sub.2).sub.2, OSO.sub.2R2, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl, or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R2, wherein one or more CH.sub.2 groups are optionally replaced by R2C═CR2, C≡C, Si(R2).sub.2, Ge(R2).sub.2, Sn(R2).sub.2, C═O, C═S, C═Se, C═NR2, P(═O)(R2), SO, SO.sub.2, NR2, O, S, or CONR2 and wherein one or more H atoms is optionally 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 in each case is optionally substituted by one or more radicals R2, an aryloxy or hetero-aryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R2, or a combination of these systems; and wherein two or more adjacent substituents R1 optionally define a mono- or polycyclic, aliphatic or aromatic ring system with one another; R2 is, identically or differently on each occurrence, H, D, F, Cl, Br, I, N(R3).sub.2, CN, NO.sub.2, Si(R3).sub.3, B(OR3).sub.2, C(═O)R3, P(═O)(R3).sub.2, S(═O)R3, S(═O).sub.2R3, OSO.sub.2R3, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy, or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R3, wherein one or more non-adjacent CH.sub.2 groups are optionally replaced by R3C═CR3, C≡C, Si(R3).sub.2, Ge(R3).sub.2, Sn(R3).sub.2, C═O, C═S, C═Sc, C═NR3, P(═O)(R3), SO, SO.sub.2, NR3, O, S, or CONR3 and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO.sub.2, or aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which in each case is optionally substituted by one or more radicals R3, an aryloxy, arylalkoxy, or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R3, a diarylamino group, diheteroarylamino group, or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R3, or a combination of two or more of these groups; and wherein two or more adjacent radicals R2 optionally define a mono- or polycyclic, aliphatic or aromatic ring system with one another; R3 is, identically or differently on each occurrence, H, D, F or an aliphatic, aromatic, and/or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, wherein one or more H atoms is optionally replaced by F; and wherein two or more substituents R3 optionally define a mono- or polycyclic, aliphatic or aromatic ring system with one another; R5 is on each occurrence, identically or differently, F, Cl, Br, I, CHO, N(Ar1).sub.2, C(═O)Ar1, P(═O)(Ar1).sub.2, S(═O)Ar1, S(═O)2Ar1, CR2=CR2Ar1, CN, NO.sub.2, Si(R2).sub.3, B(OR2).sub.2, B(R2).sub.2, B(N(R2).sub.2).sub.2, OSO.sub.2R2, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R2, wherein one or more CH.sub.2 groups are optionally replaced by R2C═CR2, C≡C, Si(R2).sub.2, Ge(R2).sub.2, Sn(R2).sub.2, C═O, C═S, C═Se, C═NR2, P(═O)(R2), SO, SO.sub.2, NR2, O, S or CONR2 and wherein one or more H atoms is optionally 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 in each case is optionally substituted by one or more radicals R2, an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R2, or a combination of these systems; and wherein two or more adjacent substituents R5 cannot form a mono- or polycyclic, aliphatic or aromatic ring system with one another; R4 and R6 are on each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, N(Ar1).sub.2, C(═O)Ar1, P(═O)(Ar1).sub.2, S(═O)Ar1, S(═O).sub.2Ar1, CR2═CR2Ar1, CN, NO.sub.2, Si(R2).sub.3, B(OR2).sub.2, B(R2).sub.2, B(N(R2).sub.2).sub.2, OSO.sub.2R2, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R2, wherein one or more CH.sub.2 groups is optionally replaced by R2C═CR2, C≡C, Si(R2).sub.2, Ge(R2).sub.2, Sn(R2).sub.2, C═O, C═S, C═Se, C═NR2, P(═O)(R2), SO, SO.sub.2, NR2, O, S, or CONR2 and wherein one or more H atoms is optionally 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 in each case is optionally substituted by one or more radicals R2, an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R2, or a combination of these systems; and wherein two or more adjacent substituents R4 cannot form a mono- or polycyclic, aliphatic or aromatic ring system with one another; and wherein two or more adjacent substituents R6 optionally define a mono- or polycyclic, aliphatic or aromatic ring system with one another; Q is C═O, C═S, S, C(R2).sub.2, NR.sub.2, or O; n is 0 or 1, wherein n=0 means that the two aromatic rings A and B are not linked to one another via the group Q, but instead by a single bond; p is 0, 1, 2, 3, or 4; q is 0, 1, 2, 3, or 4; r is 0, 1, 2, 3, or 4; X is, identically or differently on each occurrence, N or CR1, wherein at least one X is equal to N; Ar1 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R2; wherein two of the radicals Ar1 are optionally linked to one another by a single bond or a bridge selected from the group consisting of B(R2), C(R2).sub.2, Si(R2).sub.2, C═O, C═NR2, C═C(R2).sub.2, O, S, S═O, SO.sub.2, N(R2), P(R2) and P(═O)R2.

22. The compound according to claim 21, wherein the compound is a small molecule having a molecular weight of at most 3000 g/mol.

23. The compound according to claim 21, wherein the compound has the formula (33): ##STR00402##

24. The compound according to claim 21, wherein the compound has the formula (1): ##STR00403## wherein Q′ is, identically to or differently from one another, C═O, C═S, S, C(R2).sub.2, NR2, or O; A is 0, 1, 2, 3, or 4; B is 0, 1, 2, 3, or 4; a+b is always less than or equal to 7; m is 0 or 1, wherein m=0 means that the two aromatic rings are not linked to one another via the group Q′, but instead by a single bond; V is a divalent group; U is a divalent group; V is 0 or 1, where v=0 means that the ring D is connected directly to the remainder of the compound via a single covalent bond; U is 0 or 1, where u=0 means that the ring C is connected directly to the remainder of the compound via a single covalent bond.

25. The compound according to claim 21, wherein the compound has the formula (4): ##STR00404##

26. The compound according to claim 21, wherein the compound has the formula (5): ##STR00405##

27. The compound according to claim 21, wherein the compound has the formula (14): ##STR00406##

28. The compound according to claim 21, wherein the compound has the formula (24): ##STR00407##

29. The compound according to claim 21, wherein two or more adjacent substituents R1 do not form a mono- or polycyclic, aliphatic or aromatic ring system with one another.

30. The compound according to claim 21, wherein the compound has the formula (34): ##STR00408##

31. The compound according to claim 21, wherein the compound has the formula (35): ##STR00409##

32. The compound according to claim 21, wherein the compound has the formula (44): ##STR00410##

33. A composition comprising at least one compound of claim 21 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, matrix materials, electron-transport materials, electron-injection materials, hole-conductor materials, hole-injection materials, electron-blocking materials, hole-blocking materials, wide band gap materials, and n-dopants.

34. The composition of claim 33, wherein the additional compound is an electron-transport material or matrix material.

35. A formulation comprising at least one compound of claim 21 and at least one solvent.

36. A formulation comprising at least one composition of claim 33 and at least one solvent.

37. An electronic device comprising at least one compound of claim 21.

38. An electronic device comprising at least one composition of claim 33.

39. The electronic device of claim 37, wherein the device is selected from the group consisting of organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic electroluminescent devices, organic solar cells, organic optical detectors, and organic photoreceptors.

40. The electronic device of claim 37, wherein the device is selected from the group consisting of organic light-emitting transistors, organic field-quench devices, organic light-emitting electrochemical cells, organic laser diodes, and organic light-emitting diodes.

41. The electronic device of claim 38, wherein the device is selected from the group consisting of organic light-emitting transistors, organic field-quench devices, organic light-emitting electrochemical cells, organic laser diodes, and organic light-emitting diodes.

42. A process for producing an electronic device according to claim 37, comprising applying at least one organic layer by gas-phase deposition or from solution.

43. A process for producing an electronic device according to claim 38, comprising applying at least one organic layer by gas-phase deposition or from solution.

Description

EXAMPLES

Example 1

Synthesis of 2-[3-[7′-(4,6-diphenyl-1,3,5-triazin-2-yl)-9,9′-spirobi[fluoren]-2′-yl]phenyl]-1-phenylbenzimidazole 6a

[0205] ##STR00096## ##STR00097##

Synthesis of 2-[3-(7′-bromo-9,9′-spirobi[fluoren]-2′-yl)phenyl]-1-phenylbenzimidazole (3a)

Variant A

[0206] 50.0 g (105 mmol, 1.00 eq.) of 2,7-dibromo-9,9′-spirobifluorene 1a, 41.7 g (105 mmol, 1.00 eq.) of 1-phenyl-2-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1H-benzimidazole 2a and 36.4 g (263 mmol, 2.50 eq.) of potassium carbonate in 400 ml of toluene, 400 ml of 1,4-dioxane and 200 ml of DI water are initially introduced in a 2 l four-necked flask under protective gas and degassed. 1.22 g (1.05 mmol, 0.01 eq.) of tetrakis(triphenylphosphine)palladium(0) are subsequently added, and the mixture is heated under reflux overnight. When the reaction is complete, the batch is cooled, filtered through Celite and diluted with 1 l of toluene. The solution is washed 3× with 300 ml of semi-saturated sodium chloride solution in each case and, after drying over sodium sulfate, evaporated to about 200 ml in a rotary evaporator. The solid which has precipitated out is filtered off and dried in vacuo. The disubstituted by-product is separated off by means of sublimation, giving 22.0 g (33.1 mmol, 32%) of the desired product 3a.

Variant B

[0207] The procedure is carried out analogously to that of variant A, where tetrakis(triphenylphosphine)palladium(0) is replaced by 0.01 eq. of palladium(II) acetate and 0.01 eq. of dicyclohexyl-(2′,6′-dimethoxybiphenyl-2-yl)phosphine (SPhos).

[0208] The following are reacted analogously:

TABLE-US-00001 Starting Starting No. material 1 material 2 Product 3 Var. Yield 3b [00098] [00099] [00100] A 54% 3c [00101] [00102] [00103] A 35% 3d [00104] [00105] [00106] B 41% 3e [00107] [00108] [00109] A 59% 3f [00110] [00111] [00112] B 32% 3g [00113] [00114] [00115] B 62% 3h [00116] [00117] [00118] B 44% 3i [00119] [00120] [00121] A 21% 3j [00122] [00123] [00124] B 15% 3k [00125] [00126] [00127] A 64% 3l [00128] [00129] [00130] A 38% 3m [00131] [00132] [00133] B 32% 3n [00134] [00135] [00136] B 53% 3o [00137] [00138] [00139] A 41% 3p [00140] [00141] [00142] B 58% 3q [00143] [00144] [00145] B 17% 3r [00146] [00147] [00148] A 39% 3s [00149] [00150] [00151] B 28% Var.—variant

Synthesis of 1-phenyl-2-[3-[7′-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9′-spirobi[fluoren]-2′-yl]phenyl]benzimidazole 4a

[0209] 22.0 g (33.1 mmol, 1.00 eq.) of 2-[3-(7′-bromo-9,9′-spirobi[fluoren]-2′-yl)phenyl]-1-phenylbenzimidazole 3a, 8.84 g (30.1 mmol, 0.91 eq.) of bis(pinacolato)diboron and 26.0 g (265 mmol, 8.00 eq.) of potassium acetate in 500 ml of dried 1,4-dioxane are initially introduced in a 1 l four-necked flask and degassed for 30 minutes. 812 mg (0.995 mmol, 0.0300 eq.) of 1,1-bis(diphenylphosphino)ferrocenepalladium(II) dichloride complex with DCM are subsequently added, and the mixture is heated to an internal temperature of 80° C. After stirring overnight, the batch is cooled, and the solid which has precipitated out is filtered off with suction. The filtrate is evaporated to about 50 ml in a rotary evaporator, and the solid which has precipitated out is likewise filtered off with suction. The solids are combined and dried, giving 21.0 g (29.5 mmol, 89%) of the boronic ester 4a.

[0210] The following are reacted analogously:

TABLE-US-00002 No. Starting material 3 Product 4 Yield 4b [00152] [00153] 95% 4c [00154] [00155] 87% 4d [00156] [00157] 97% 4e [00158] [00159] 94% 4f [00160] [00161] 88% 4g [00162] [00163] 47% 4h [00164] [00165] 81% 4i [00166] [00167] 79% 4j [00168] [00169] 74% 4k [00170] [00171] 55% 4l [00172] [00173] 47% 4m [00174] [00175] 85% 4n [00176] [00177] 82% 4o [00178] [00179] 87% 4p [00180] [00181] 66% 4q [00182] [00183] 58% 4r [00184] [00185] 84% 4s [00186] [00187] 77%

Synthesis of 2-[3-[7′-(4,6-diphenyl-1,3,5-triazin-2-yl)-9,9′-spirobi[fluoren]-2′-yl]phenyl]-1-phenylbenzimidazole 6a

Variant A

[0211] 21.0 g (29.5 mmol, 1.00 eq.) of 1-phenyl-2-[3-[7′-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9′-spirobi[fluoren]-2′-yl]phenyl]benzimidazole 4a and 7.90 g (29.5 mmol, 1.00 eq.) of 2-chloro-4,6-diphenyl-1,3,5-triazine 5a together with 3.75 g (35.4 mmol, 1.20 eq.) of sodium carbonate in 200 ml of toluene, 200 ml of 1,4-dioxane and 100 ml of DI water are initially introduced in a 1 l three-necked flask and degassed for 20 minutes. After addition of 1.02 g (0.885 mmol, 0.0300 eq.) of tetrakis(triphenylphosphine)palladium(0), the batch is heated under reflux for 2 days and cooled when the reaction is complete. The solid which has precipitated out is filtered off with suction, washed with water and a little toluene and subsequently recrystallised a number of times from toluene/heptane until an HPLC purity of >99.9% is achieved. Sublimation gives 11.5 g (14.0 mmol, 43%) of a colourless solid 6a.

Variant B

[0212] The procedure is carried out analogously to that of variant A, where tetrakis(triphenylphosphine)palladium(0) is replaced by 0.01 eq. of palladium(II) acetate and 0.04 eq. of tri(o-tolyl)phosphine.

Variant C

[0213] The procedure is carried out analogously to that of variant A, where tetrakis(triphenylphosphine)palladium(0) is replaced by 0.01 eq. of palladium(II) acetate and 0.01 eq. of dicyclohexyl-(2′,6′-dimethoxy-biphenyl-2-yl)phosphine (SPhos).

[0214] The following are prepared analogously:

TABLE-US-00003 Starting Starting No. material 4 material 5 6b [00188] [00189] 6c [00190] [00191] 6d [00192] [00193] 6e [00194] [00195] 6f [00196] [00197] 6g [00198] [00199] 6h [00200] [00201] 6i [00202] [00203] 6j [00204] [00205] 6k [00206] [00207] 6l [00208] [00209] 6m [00210] [00211] 6n [00212] [00213] 6o [00214] [00215] 6p [00216] [00217] 6q [00218] [00219] 6r [00220] [00221] [00222] [00223] No. Product 6 Var. Yield 6b [00224] B 57% 6c [00225] A 38% 6d [00226] A 42% 6e [00227] C 61% 6f [00228] B 37% 6g [00229] C 39% 6h [00230] C 31% 6i [00231] A 48% 6j [00232] A 24% 6k [00233] B 51% 6l [00234] B 38% 6m [00235] C 34% 6n [00236] C 44% 6o [00237] A 53% 6p [00238] C 42% 6q [00239] B 31% 6r [00240] B 35% [00241] B 39% Var.—variant

Example 2

2-(3-[1-Phenyl-1H-benzimidazol-2-yl]phenyl)-4-phenyl-6-(9,9′-spirobi[9H-fluoren]-2-yl)-1,3,5-triazine 11a

[0215] ##STR00242##

Synthesis of 2-chloro-4-phenyl-6-(9,9′-spirobi[9H-fluoren]-2-yl)-1,3,5-triazine 9a

Variant A

[0216] 24.5 g (67.9 mmol, 1.00 eq.) of 9,9′-spirobifluoren-2′-ylbrononic acid 7a, 15.4 g (68.3 mmol, 1.01 eq.) of 2,4-dichloro-6-phenyl-1,3,5-triazine 8a and 9.04 g (85.3 mmol, 1.26 eq.) of sodium carbonate in 300 ml of toluene, 300 ml of 1,4-dioxane and 300 ml of DI water are initially introduced in a 2 l four-necked flask under protective gas and degassed. 0.850 g (0.736 mmol, 0.01 eq.) of tetrakis(triphenylphosphine)palladium(0) is subsequently added, and the mixture is heated under reflux for 24 hours. When the reaction is complete, the batch is cooled and diluted with 100 ml of ethyl acetate. The phases are separated in a separating funnel, the aqueous phase is extracted three times with ethyl acetate, and the combined organic phases are washed once more with water. The mixture is subsequently dried over sodium sulfate, and the solution is evaporated until a brownish solid precipitates out. The solid is filtered off, washed by stirring with hot ethanol and, after re-filtration, dried in vacuo. The product is purified by means of column chromatography using heptane/dichloromethane 5:1 as eluent, giving 9.90 g (19.6 mmol, 29%) of a colourless solid.

Variant B

[0217] The procedure is carried out analogously to that of variant A, where tetrakis(triphenylphosphine)palladium(0) is replaced by 0.01 eq. of palladium(II) acetate and 0.04 eq. of tri(o-tolyl)phosphine.

Variant C

[0218] The procedure is carried out analogously to that of variant A, where tetrakis(triphenylphosphine)palladium(0) is replaced by 0.01 eq. of palladium(II) acetate and 0.01 eq. of dicyclohexyl-(2′,6′-dimethoxybiphenyl-2-yl)phosphine (SPhos).

Variant D

[0219] The procedure is carried out analogously to that of variant A, where tetrakis(triphenylphosphine)palladium(0) is replaced by 0.02 eq. of 1,1-bis(diphenylphosphino)ferrocenepalladium(II) dichloride complex with DCM and dried toluene is used as solvent.

[0220] The following are prepared analogously:

TABLE-US-00004 Starting Starting No. material 7 material 8 Product 9 Var. Yield 9b [00243] [00244] [00245] A 34% 9c [00246] [00247] [00248] B 29% 9d [00249] [00250] [00251] B 41% 9e [00252] [00253] [00254] C 17% 9f [00255] [00256] [00257] A 26% 9g [00258] [00259] [00260] A 11% 9h [00261] [00262] [00263] B 25% 9i [00264] [00265] [00266] D 18% 9j [00267] [00268] [00269] B 54% 9k [00270] [00271] [00272] C 41% 9l [00273] [00274] [00275] B 31% 9m [00276] [00277] [00278] A 19% 9n [00279] [00280] [00281] B 38% 9o [00282] [00283] [00284] C 42% 9p [00285] [00286] [00287] A 51% 9q [00288] [00289] [00290] A 24% 9r [00291] [00292] [00293] D 18% 9s [00294] [00295] [00296] A 36% 9t [00297] [00298] [00299] B 47% 9u [00300] [00301] [00302] B 27% 9v [00303] [00304] [00305] D 42% Var.—variant

Synthesis of 2-(3-[1-phenyl-1H-benzimidazol-2-yl]phenyl)-4-phenyl-6-(9,9′-spirobi[9H-fluoren]-2-yl)-1,3,5-triazine 11a

Variant A

[0221] 9.90 g (19.6 mmol, 1.00 eq.) of 2-chloro-4-phenyl-6-(9,9′-spirobi[9H-fluoren]-2-yl)-1,3,5-triazine 9a, 8.53 g (21.5 mmol, 1.10 eq.) of 1-phenyl-2-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1H-benzimidazole 10a and 4.57 g (43.1 mmol, 2.20 eq.) of sodium carbonate in 35 ml of toluene, 35 ml of 1,4-dioxane and 35 ml of DI water are initially introduced in a 250 ml three-necked flask under protective gas and degassed. 1.13 g (0.980 mmol, 0.05 eq.) of tetrakis(triphenylphosphine)palladium(0) are subsequently added, and the mixture is heated under reflux for 48 hours. When the reaction is complete, the batch is cooled, and the solid which has precipitated out is filtered off with suction. The crude product obtained is purified by means of extraction, triple recrystallisation from heptane/toluene and sublimation, giving 4.83 g (6.54 mmol, 33%) of a solid having an HPLC purity >99.9%.

Variant B

[0222] The procedure is carried out analogously to that of variant A, where tetrakis(triphenylphosphine)palladium(0) is replaced by 0.02 eq. of 1,1-bis(diphenylphosphino)ferrocenepalladium(II) dichloride complex with DCM and dried toluene is used as solvent.

Variant C

[0223] 4.15 ml (24.4 mmol, 1.10 eq.) of diisopropylethylamine (Hünig base) are added to a solution of 10.2 g (22.2 mmol, 1.00 eq.) of 2-biphenyl-3-yl-4-chloro-6-(9,9-dimethyl-9H-fluoren-2-yl)-1,3,5-triazine 9k and 4.31 g (22.2 mmol, 1.00 eq.) of 2-phenyl-1H-benzimidazole 10k in 150 ml of THF at room temperature. The reaction mixture is stirred overnight, and, when the reaction is complete, the solvent is removed in vacuo. After addition of 200 ml of dichloromethane, the solution is extracted three times with water, dried over sodium sulfate, and the solvent is removed in a rotary evaporator. The purification is carried out analogously to variant A, giving 5.57 g (9.02 mmol, 41%) of the desired product 11k.

[0224] The following are prepared analogously:

TABLE-US-00005 No. Starting material 9 Starting material 10 11b [00306] [00307] 11c [00308] [00309] 11d [00310] [00311] 11e [00312] [00313] 11f [00314] [00315] 11g [00316] [00317] 11h [00318] [00319] 11i [00320] [00321] 11j [00322] [00323] 11k [00324] [00325] 11l [00326] [00327] 11m [00328] [00329] 11n [00330] [00331] 11o [00332] [00333] 11p [00334] [00335] 11q [00336] [00337] 11r [00338] [00339] 11s [00340] [00341] 11t [00342] [00343] 11u [00344] [00345] 11v [00346] [00347] No. Product 11 Var. Yield 11b [00348] B 71% 11c [00349] B 43% 11d [00350] B 55% 11e [00351] A 29% 11f [00352] B 47% 11g [00353] C 63% 11h [00354] A 47% 11i [00355] A 31% 11j [00356] B 36% 11k [00357] B 41% 11l [00358] A 58% 11m [00359] A 26% 11n [00360] B 74% 11o [00361] A 42% 11p [00362] A 37% 11q [00363] B 32% 11r [00364] A 21% 11s [00365] A 62% 11t [00366] B 33% 11u [00367] A 29% 11v [00368] A 58%

Example 3

Production and Characterisation of the OLEDs

[0225] The data of various OLEDs are presented in the following Examples V1 to E16 (see Tables 1 and 2).

[0226] Pre-treatment for Examples V1-E16: 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 AI 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.

[0227] 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.

[0228] 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 coevaporation. 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.

[0229] 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.

[0230] The data of the various OLEDs are summarised in Table 2. Examples V1-V3 are comparative examples in accordance with the prior art, Examples E1-E16 show data of OLEDs according to the invention.

[0231] Some of the examples are explained in greater detail below in order to illustrate the advantages of the OLEDs according to the invention.

Use of Mixtures According to the Invention in the Electron-Transport Layer (ETL or EIL) of OLEDs

[0232] On use in the electron-injection and electron-transport layer in OLEDs, the materials according to the invention give rise to significant improvements over the prior art with respect to the lifetime of the components and/or the efficiency. The use of compound EG1 according to the invention enables an increase in the lifetime of between 20% and 40% to be observed compared with the prior art (comparison of Examples V1 and V2 with E1, and comparison of V3 with E2). A further technical advantage of the compounds according to the invention is an increased efficiency by about 10% compared with the prior art (comparison of experiment V1 with E1).

TABLE-US-00006 TABLE 1 Structure of the OLEDs HTL/IL (HATCN: 5 nm)/EBL/EML/HBL/ETL/EIL HTL EBL EML HBL ETL EIL Ex. Thickness Thickness Thickness Thickness Thickness Thickness V1 SpA1 SpMA1 IC1:IC3:TEG1 — SdT1:LiQ — 70 nm 90 nm (40%:40%:20%) 30 nm (50%:50%) 40 nm V2 SpA1 SpMA1 IC1:IC3:TEG1 — SdT2:LiQ — 70 nm 90 nm (40%:40%:20%) 30 nm (50%:50%) 40 nm V3 SpA1 SpMA1 IC1:TEG1 — SdT3:LiQ LiF 70 nm 90 nm (90%:10%) 30 nm 40 nm 1 nm E1 SpA1 SpMA1 IC1:IC3:TEG1 — EG1:LiQ — 70 nm 90 nm (40%:40%:20%) 30 nm (50%:50%) 40 nm E2 SpA1 SpMA1 IC1:TEG1 — EG2 LiF 70 nm 90 nm (90%:10%) 30 nm 40 nm 1 nm E3 SpA1 SpMA1 IC1:TEG1 IC1 EG3:LiQ — 70 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm E4 SpA1 SpMA1 IC1:TEG1 IC1 EG4 LiF 70 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm 1 nm E5 SpA1 SpMA1 IC1:TEG1 EG5 EG5:LiQ — 70 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm E6 SpA1 SpMA1 IC1:TEG1 IC1 EG6 LiQ 70 nm 90 nm (90%:10%) 30 nm 10 nm 30 nm 3 nm E7 SpA1 SpMA1 IC1:IC3:TEG1 IC1 EG7:LiQ LiQ 70 nm 90 nm (60%:30%:10%) 30 nm 10 nm (50%:50%) 30 nm 1 nm E8 SpA1 20 nm (95%:5%) 20 nm (50%:50%) 30 nm E9 SpA1 SpMA1 H1:SEB — EG9 LiQ 140 nm  20 nm (95%:5%) 20 nm (50%:50%) 30 nm 3 nm E10 SpA1 SpMA1 H1:SEB — EG10:LiQ — 140 nm  20 nm (95%:5%) 20 nm (50%:50%) 30 nm E141 SpA1 SpMA1 H1:SEB — EG11:LiQ — 140 nm  20 nm (95%:5%) 20 nm (50%:50%) 30 nm E12 SpA1 SpMA1 H1:SEB — EG12:LiQ — 140 nm  20 nm (95%:5%) 20 nm (50%:50%) 30 nm E13 SpA1 SpMA1 EG13:IC3:TEG1 — ST2:LiQ — 70 nm 90 nm (45%:45%:10%) 30 nm (50%:50%) 40 nm E14 SpA1 SpMA1 IC5:TER3 — EG14:LiQ — 90 nm 130 nm  (92%:8%) 40 nm (50%:50%) 40 nm E15 SpA1 SpMA1 IC5:TER3 — EG15:LiQ — 90 nm 130 nm  (92%:8%) 40 nm (50%:50%) 40 nm E16 SpA1 SpMA1 IC5:TER3 — EG16:LiQ — 90 nm 130 nm  (92%:8%) 40 nm (50%:50%) 40 nm

TABLE-US-00007 TABLE 2 Data of the OLEDs U1000 CE1000 PE1000 EQE CIE x/y at LT Ex. (V) (cd/A) (lm/W) 1000 1000 cd/m.sup.2 L.sub.0; j.sub.0 L1 % (h) V1 3.4 55 51 15.1% 0.33/0.63 20 mA/cm.sup.2 80 180 V2 3.3 60 57 16.5% 0.33/0.62 20 mA/cm.sup.2 80 160 V3 3.2 61 60 16.8% 0.34/0.62 20 mA/cm.sup.2 80 125 E1 3.3 59 56 16.4% 0.33/0.62 20 mA/cm.sup.2 80 220 E2 3.2 62 61 16.7% 0.33/0.63 20 mA/cm.sup.2 80 155 E3 3.4 57 53 16.2% 0.34/0.62 20 mA/cm.sup.2 80 135 E4 3.5 60 54 16.5%  032/0.64 20 mA/cm.sup.2 80 130 E5 3.6 59 51 16.0% 0.33/0.63 20 mA/cm.sup.2 80 120 E6 3.2 60 59 16.1% 0.31/0.64 20 mA/cm.sup.2 80 105 E7 3.6 61 53 16.6% 0.33/0.63 20 mA/cm.sup.2 80 235 E8 4.6 8.1 5.5 7.2% 0.13/014  6000 cd/m.sup.2   80 50 E9 4.5 7.8 5.2 6.7% 0.14/015  6000 cd/m.sup.2   80 25 E13 4.9 7.4 4.7 6.9% 0.14/0.13 6000 cd/m.sup.2   80 45 E11 4.7 8.3 5.5 7.5% 0.14/013  6000 cd/m.sup.2   80 40 E12 5.2 8.5 5.1 7.7% 0.14/013  6000 cd/m.sup.2   80 35 E13 3.4 58 54 15.4% 0.32/0.63 20 mA/cm.sup.2 80 105 E14 4.9 11.3 7.2 12.1% 0.67/0.33 4000 cd/m.sup.2   80 390 E15 4.3 11.3 8.3 12.3% 0.66/0.34 4000 cd/m.sup.2   80 360 E16 4.5 12.2 8.5 12.8% 0.67/0.33 4000 cd/m.sup.2   80 410

TABLE-US-00008 TABLE 3 Structural formulae of the materials for the OLEDs [00369] HATCN [00370] SpA1 [00371] SpMA1 [00372] LiQ [00373] SpMA2 [00374] TER1 [00375] IC1 [00376] ST2 [00377] IC3 [00378] TEG1 [00379] H1 [00380] SEB [00381] IC5 [00382] SdT1 [00383] SdT2 [00384] SdT3 [00385] EG1 [00386] EG2 [00387] EG3 [00388] EG4 [00389] EG5 [00390] EG6 [00391] EG7 [00392] EG8 [00393] EG9 [00394] EG10 [00395] EG11 [00396] EG12 [00397] EG13 [00398] EG14 [00399] EG15 [00400] EG16