MATERIALS FOR ORGANIC ELECTROLUMINESCENT DEVICES

Abstract

The present invention relates to compounds of formula (1) which are suitable for use in electronic devices, especially in organic electroluminescent devices.

Claims

1.-13. (canceled)

14. A compound of formula (1) ##STR00428## where the symbols and indices used are as follows: X is the same or different at each instance and is CR.sup.1 or N; Ar.sup.2 is the same or different at each instance and is a bivalent aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals; Ar.sup.1 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may in each case also be substituted by one or more R.sup.2 radicals; where Ar.sup.1 and/or Ar.sup.2 radicals bonded to the same nitrogen atom may be joined via at least one K group; K is the same or different at each instance and is a single bond or a bivalent bridge selected from N(R.sup.2), B(R.sup.2), O,C═O, C(R.sup.2).sub.2, Si(R.sup.2).sub.2, C═C(R.sup.2).sub.2, S═O, P(R.sup.2), P(═O)R.sup.2 and S; W is the same or different at each instance and is a single bond or a bivalent bridge selected from N(R.sup.2), B(R.sup.2), O, C═O, C(R.sup.2).sub.2, Si(R.sup.2).sub.2, S and R.sup.2C═CR.sup.2; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system, preferably an aryl or heteroaryl group, which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, C(═O)Ar, P(═O)Ar.sub.2, S(═O)Ar, S(═O).sub.2Ar, CR.sup.2═CR.sup.2Ar, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.2C═CR.sup.2, C═C, Si(R.sup.2).sub.2, C═O, 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 may be 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, each of which may be substituted by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or an aralkyl or heteroaralkyl group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or a combination of these systems; at the same time, two or more R.sup.2 substituents together with the atoms to which they are bonded and also with one another, or two R.sup.1 substituents, may form a mono- or polycyclic, aliphatic or aromatic ring system; R.sup.2 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R.sup.3).sub.2, N(Ar).sub.2, C(═O)Ar, P(═O)Ar.sub.2, S(═O)Ar, S(═O).sub.2Ar, CR.sup.3═CR.sup.3Ar, CN, NO.sub.2, Si(R.sup.3).sub.3, B(OR.sup.3).sub.2, OSO.sub.2R.sup.3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.3 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.3C═CR.sup.3, C≡C, Si(R.sup.3).sub.2, C═O, 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 may be 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, each of which may be substituted by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or an aralkyl or heteroaralkyl group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or a combination of these systems; at the same time, two or more R.sup.3 substituents together with the atoms to which they are bonded and also with one another, or two R.sup.2 substituents, 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, Cl, Br, I, C(═O)Ar, P(═O)Ar.sub.2, S(═O)Ar, S(═O).sub.2Ar, CR.sup.4═CR.sup.4Ar, CN, NO.sub.2, Si(R.sup.4).sub.3, B(OR.sup.4).sub.2, OSO.sub.2R.sup.4, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.4 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.4C═CR.sup.4, C≡C, Si(R.sup.4).sub.2, C═O, C═NR.sup.4, P(═O)(R.sup.4), SO, SO.sub.2, NR.sup.4, O, S or CONR.sup.4 and where one or more hydrogen atoms may be 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, each of which may be substituted by one or more R.sup.4 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.4 radicals, or an aralkyl or heteroaralkyl group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.4 radicals, or a combination of these systems; at the same time, two or more R.sup.4 substituents together with the atoms to which they are bonded and also with one another, or two R.sup.3 substituents, may form a mono- or polycyclic, aliphatic or aromatic ring system; R.sup.4 is the same or different at each instance and is H, D, F or an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms or an aryl or heteroaryl group which has 5 to 40 ring atoms and may be substituted by one or more R.sup.5 radicals, or a combination of these groups; R.sup.5 is the same or different at each instance and is H, D, or an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms; m is 0 or 1, where m=0 means that no W group is bonded at this position, and the carbon atoms in question that bind to W are each replaced by an X group; and p, q, r, s, t are the same or different at each instance and are 0, 1 or 2; a, b, c, d, e are the same or different at each instance and are 0, 1 or 2; where p+q+r+s+t is greater than 1; and, if r is greater than or equal to 1 and s is greater than or equal to 1 and m is equal to 0, and c and d for at least one (Ar.sup.2).sub.cN(Ar.sup.1).sub.2 group and at least one (Ar.sup.2).sub.dN(Ar.sup.1).sub.2 group are 0, these two N(Ar.sup.1).sub.2 groups are not arranged in the respective para positions to the quaternary carbon atom of the base skeleton.

15. The compound according to claim 14, wherein W is a single bond.

16. The compound according to claim 14, wherein the sum total of the values of the indices p, q, r, s and t is 1.

17. The compound according to claim 14, wherein the index r is 1, and the indices p, q, s and t are each 0, or characterized in that the index s is 1 and the indices p, q, r and t are each 0.

18. The compound according to claim 14, wherein the compound corresponds to formula (2) ##STR00429## where the further symbols and indices used have the definitions given in claim 14.

19. The compound according to claim 14, wherein the compound is a compound of one of the formulae (4) and (5): ##STR00430## where the symbols and indices used have the definitions given in claim 14.

20. The compound according to claim 14, wherein the compound is a compound of one of the formulae (6) to (11): ##STR00431## ##STR00432## where the symbols and indices used have the definitions given in claim 14.

21. A process for preparing a compound according to claim 14, wherein the compound of the formula (1) is formed by one or more coupling reactions and/or cyclizations.

22. The mixture comprising at least one compound according to claim 14 and at least one fluorescent or phosphorescent dopant.

23. A formulation comprising at least one compound according to claim 14 and one or more solvents.

24. A formulation comprising the mixture according to claim 22 and one or more solvents.

25. The formulation as claimed in claim 23, wherein the formulation is a solution, a suspension or a miniemulsion.

26. An electronic device comprising the compound according to claim 14.

27. An electronic device comprising the mixture according to claim 22.

28. An electronic device selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic dye-sensitized solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes and organic plasmon emitting devices, comprising at least one compound according to claim 14.

29. An organic electroluminescent device comprising the compound according to claim 14 is used as matrix material for a fluorescent or phosphorescent compound in an emitting layer and/or in a hole transport layer and/or in a hole injection layer and/or in an electron blocker layer.

Description

WORKING EXAMPLES

[0156] The tribenzocycloheptene-fluorene spiro base skeleton is preferably formed analogously to the conventional spiro synthesis. Starting materials used are 9H-tribenzo[a,c,e]cyclohepten-9-one (CAS Na: 68089-73-6) and 2-bromobiphenyl derivatives. It is possible here to obtain different substitution patterns on the base skeleton through the use of correspondingly substituted biphenylenes (Scheme 1). The synthesis of 9H-tribenzo[a,c,e]cyclohepten-9-one is described in Chem. Sci., 2011, 2, 2029.

##STR00136##

[0157] In this scheme, W represents a bridge between the phenyl groups and X is a halide such as chlorine, bromine or iodine and Y is a reactive leaving group or a substituent. It is then possible to introduce further groups via Y.

[0158] The synthesis of the inventive compounds can be conducted by the methods and reaction types known in the prior art. In particular, it is possible to synthesize the compounds from a correspondingly halogen-substituted base skeleton by introduction of the amino group, as shown in Scheme 2. It is possible here either first to introduce a primary amine having an Ar.sup.1 substituent and to introduce the further Ar.sup.1 group in a further coupling reaction, as shown in Scheme 2 a). It is likewise possible to introduce the secondary amine Ar.sup.1Ar.sup.1NH directly in one step, as shown in Scheme 2 b). Suitable Y groups in the base skeleton are reactive leaving groups, for example Cl, Br, I, triflate or tosylate. Suitable coupling reactions are, for example, coupling reactions according to Hartwig-Buchwald or according to Ullmann. The reaction conditions which can be used for these coupling reactions are known to those skilled in the art of organic synthesis.

##STR00137##

[0159] For compounds having a linker, the Ar.sup.2-NAr.sup.1Ar.sup.1 group can likewise be introduced via a metal-catalysed coupling reaction, for example via a Suzuki coupling or a Stille coupling (Scheme 3).

##STR00138##

[0160] Y and X here are reactive leaving groups. Scheme 3 a) and Scheme 3 b) show two different routes for coupling of a triarylamine to the base skeleton.

[0161] Synthesis of Compound (1-1)

##STR00139##

[0162] Synthesis of Compound (I-1)

[0163] 26.7 g (85.8 mmol) of 2,2′-dibromobiphenyl are dissolved in a baked-out flask in 300 ml of dried THF. The reaction mixture is cooled to −78° C. At this temperature, 34.3 ml of a 2.5 M solution of n-BuLi in hexane (85.8 mmol) are slowly added dropwise. The mixture is stirred at −70° C. for a further 1 h. Subsequently, 20.0 g of tribenzocyclohepten-9-one (CAS No.: 68089-73-6) (78 mmol) are dissolved in 100 ml of THF and added dropwise at −70° C. After the addition has ended, the reaction mixture is warmed gradually to room temperature, quenched with NH.sub.4Cl and then concentrated on a rotary evaporator. 500 ml of acetic acid are added cautiously to the concentrated solution and then 90 ml of fuming HCl are added. The mixture is heated to 75° C. and kept at this temperature for 5 h. 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 residue is dried at 40° C. under reduced pressure. The yield is 29 g (62 mmol), 79% of theory.

[0164] Analogously, the following compounds (I-2) to (I-12) are prepared.

TABLE-US-00001 Ex. Reactant 1 Reactant 2 Product Yield I-2  [00140] 59080-32-9 [00141] 68089-73-6 [00142] 78% I-3  [00143] 154407-17-7 [00144] [00145] 63% [00146] I-4  [00147] 2052-07- [00148] [00149] 87% I-5  [00150] 70728-93-75 [00151] [00152] 75% I-6  [00153] 947188-01-4 [00154] [00155] 60% I-7  [00156] 7025-06-1 [00157] [00158] 63% I-8  [00159] 51452-87-0 [00160] [00161] 45% I-9  [00162] 24535-55-5 [00163] [00164] 64% I-10 [00165] 21848-84-0 [00166] [00167] 67% I-11 [00168] [00169] [00170] 71% I-12 [00171] 2052-07-5 [00172] 19713-54-3 [00173] 77%

[0165] Synthesis of Compound (1-1)

[0166] 7.9 g of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine (22 mmol) and 10.6 g of the bromo derivative (I-1) (22 mmol) are dissolved in 200 mL of THF. The solution is degassed and saturated with N.sub.2. Thereafter, 1.1 ml (1.1 mmol) of a 1 M tri-tert-butylphosphine solution and 0.12 g (55 mmol) of palladium(II) acetate are added thereto. Subsequently, 5.3 g of sodium tert-butoxide (55 mmol) are added. The reaction mixture is heated to boiling under a protective atmosphere for 3 h. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and concentrated by rotary evaporation. After the crude product has been filtered through silica gel with toluene, the remaining residue is recrystallized from heptane/toluene and finally sublimed under high vacuum. The purity is 99.9%. The yield is 13.2 g (80% of theory).

[0167] Analogously, the following compounds (1-2) to (1-24) are prepared.

TABLE-US-00002 Ex. Reactant 1 Reactant 2 Product Yield 1-2 [00174] [00175] 32228-99-2 [00176] 79% 1-3 [00177] [00178] 102113-98-4 [00179] 84% 1-4 [00180] [00181] 1448185-87-2 [00182] 92% 1-5 [00183] [00184] 500717-23-7 [00185] 77% 1-6 [00186] [00187] [00188] 81% 1-7 [00189] [00190] [00191] 85% 1-8 [00192] [00193] 955959-89-4 [00194] 81% 1-9 [00195] [00196] 1198395-24-2 [00197] 77% 1-10 [00198] [00199] [00200] 76% 1300028-94-7 1-11 [00201] [00202] 897921-59-4 [00203] 69% 1-12 [00204] [00205] [00206] 74% 1-13 [00207] [00208] [00209] 80% 1-14 [00210] [00211] [00212] 61% 102113-98-4 1-15 [00213] [00214] [00215] 60% 500717-23-7 1-16 [00216] [00217] [00218] 71% 1-17 [00219] [00220] [00221] 69% 1-18 [00222] [00223] [00224] 40% 1-19 [00225] [00226] [00227] 70% 1-20 [00228] [00229] [00230] 78% 1-21 [00231] [00232] [00233] 81% 1-22 [00234] [00235] [00236] 77% 1-23 [00237] [00238] [00239] 67% 1-24 [00240] [00241] [00242] 81%

Example 2

[0168] Synthesis of Compound (2-1)

##STR00243##

[0169] Synthesis of Compound (II-1)

[0170] 40 g (255 mmol) of bromophenol are dissolved in a baked-out flask in 600 ml of dried THF. The reaction mixture is cooled to −78° C. At this temperature, 102 ml of a 2.5 M solution of n-BuLi in hexane (255 mmol) are slowly added dropwise. The mixture is stirred at −70° C. for a further 0.5 h. Subsequently, 65.3 g of tribenzocyclohepten-9-one (CAS No.: 68089-73-6) (255 mmol) are dissolved in 200 ml of THF and added dropwise at −70° C. After the addition has ended, the reaction mixture is warmed gradually to room temperature, quenched with NH.sub.4Cl and then concentrated on a rotary evaporator. The crude product is stirred with 500 ml of heptane at 80° C. for a further 2 h. After cooling, the precipitated solid is filtered off with suction and washed once with 100 ml of heptane and twice with 100 ml each time of ethanol. Yield: 66.5 g, 78%.

[0171] In an analogous manner, the following compounds are obtained:

TABLE-US-00003 Ex. Reactant 1 Reactant 2 Product Yield II-2 [00244] [00245] [00246] 85% II-3 [00247] [00248] [00249] 70% II-4 [00250] [00251] [00252] 67% II-5 [00253] [00254] [00255] 83% II-6 [00256] [00257] [00258] 81%

[0172] Synthesis of Compound (2-1)

[0173] A mixture of 20 g (60 mmol) of compound II-1 and 26.17 g (60 mmol) of bis(biphenyl-4-yl)phenylamine [122215-84-3], trifluoromethanesulphonic acid [1493-13-6] 18 g (120 mmol, 10.5 ml) and 400 ml of dioxane is heated under reflux for 24 h. After cooling, 200 ml of water are added, the mixture is stirred for a further 30 min, the organic phase is removed and the latter is filtered through a short Celite bed and then the solvent is removed under reduced pressure. The residue is recrystallized from toluene/heptane and finally sublimed under high vacuum. The purity is 99.9%. The yield is 32.9 g (73% of theory).

[0174] Analogously, the following compounds (2-2) to (2-11) are prepared.

TABLE-US-00004 Ex. Reactant 1 Reactant 2 Product: Yield 2-2 [00259] [00260] [00261] 85% 2-3 [00262] [00263] [00264] 74% 2-4 [00265] [00266] [00267] 70% 2-6 [00268] [00269] [00270] 58% 2-7 [00271] [00272] [00273] 64% 2-8 [00274] [00275] [00276] 46% 2-9 [00277] [00278] [00279] 79% 2-10 [00280] [00281] [00282] 72% 2-11 [00283] [00284] [00285] 65%

Example 3

[0175] Synthesis of Compound (3-1)

##STR00286##

[0176] 9.16 g of biphenyl-4-yl(9,9-dimethyl-9H-fluoren-2-yl)amine (25 mmol) and 12 g of the bromo derivative (2-6) (25 mmol) are dissolved in 200 mL of toluene. The solution is degassed and saturated with N.sub.2. Thereafter, 1.27 ml (1.27 mmol) of a 1 M tri-tert-butylphosphine solution and 0.14 g (0.63 mmol) of palladium(II) acetate are added thereto. Subsequently, 6.1 g of sodium tert-butoxide (63.4 mmol) are added. The reaction mixture is heated to boiling under a protective atmosphere for 8 h. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water, dried over Na.sub.2SO.sub.4 and concentrated by rotary evaporation. After the crude product has been filtered through silica gel with toluene, the remaining residue is recrystallized from heptane/toluene and finally sublimed under high vacuum. The purity is 99.9%. The yield is 15 g (78% of theory).

[0177] Synthesis of Compound (3-2) to (3-8)

[0178] Analogously, the following compounds (3-2) to (3-8) are prepared,

TABLE-US-00005 Ex. Reactant 1 Reactant 2 3-2 [00287] [00288] 3-3 [00289] [00290] 3-4 [00291] [00292] 3-5 [00293] [00294] 3-6 [00295] [00296] 3-7 [00297] [00298] 3-8 [00299] [00300] Ex. Product Yield 3-2 [00301] 79% 3-3 [00302] 84% 3-4 [00303] 85% 3-5 [00304] 80% 3-6 [00305] 71% 3-7 [00306] 81% 3-8 [00307] 87%

Example 4

[0179] Synthesis of Compound 4-1

##STR00308##

[0180] Intermediate: Boronic Ester Derivative (IV-1)

[0181] 10 g (21.2 mmol) of the bromo derivative, 6.6 g (25.4 mmol) of bis(pinacolato)diborane and 6.3 g (63.6 mmol) of potassium acetate are suspended in 200 ml of DMF. To this suspension is added 0.52 g (0.64 mmol) of 1,1-bis(diphenylphosphino)ferrocenedichloropalladium(II) complex with DCM. The reaction mixture is heated under reflux for 6 h.

[0182] After cooling, the organic phase is removed, washed three times with 300 mL of water and then concentrated to dryness. The residue is recrystallized from toluene (10.3 g, 94% yield).

[0183] Analogously, the following compounds (IV-2) to (IV-13) are prepared.

TABLE-US-00006 Ex. Reactant 1 Product Yield IV-2 [00309] [00310] 90% IV-3 [00311] [00312] 67% IV-4 [00313] [00314] 88% IV-5 [00315] [00316] 88% IV-6 [00317] [00318] 92% IV-7 [00319] [00320] 84% IV-8 [00321] [00322] 87% IV-9 [00323] [00324] 80% IV-10 [00325] [00326] 72% IV-11 [00327] [00328] 92% IV-12 [00329] [00330] 88% IV-13 [00331] [00332] 90%

[0184] Precursor: Biphenyl-4-yl(4-chlorophenyl)(4-dibenzofuran-4-ylphenyl)amine (V-1)

##STR00333##

[0185] 17 g of biphenyl-4-yl(4-dibenzofuran-4-ylphenyl)amine (41 mmol) and 14.8 g of 4-chloroiodobenzene (62 mmol) are dissolved in 260 ml of toluene. The solution is degassed and saturated with N.sub.2. Thereafter, 1.6 ml (1.6 mmol) of a 1 M tri-tert-butylphosphine solution and 0.19 g (0.83 mmol) of palladium(II) acetate are added thereto, and then 6.0 g of sodium tert-butoxide (62 mmol) are added. The reaction mixture is heated to boiling under a protective atmosphere for 5 h. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water and dried over Na.sub.2SO.sub.4 and concentrated by rotary evaporation. After the crude product has been filtered through silica gel with toluene, the remaining residue is recrystallized from heptane/toluene. The yield is 16 g (75% of theory).

[0186] Analogously, the following compounds (V-2) to (V-8) are prepared.

TABLE-US-00007 Ex. Reactant 1 Reactant 2 Product Yield V-2 [00334] [00335] [00336] 78% V-3 [00337] [00338] [00339] 83% V-4 [00340] [00341] [00342] 81% V-5 [00343] [00344] [00345] 91% V-6 [00346] [00347] [00348] 85% V-7 [00349] [00350] [00351] 75% V-8 [00352] [00353] [00354] 88%

[0187] Synthesis of Compound 4-1

[0188] 12 g (23.1 mmol) of pinacolboronic ester derivative (IV-1) and 12.1 g (23.1 mmol) of chloro derivative (V-1) are suspended in 1750 ml of dioxane and 7.0 g of caesium fluoride (46.3 mmol). 2.05 g (2.8 mmol) of bis(tricyclohexylphosphine)palladium dichloride are added to this suspension, and the reaction mixture is heated under reflux for 20 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 100 mL of water and then concentrated to dryness. After the crude product has been filtered through silica gel with toluene, the remaining residue is recrystallized from heptane/toluene and finally sublimed under high vacuum; purity is 99.9%. The yield is 16.2 g (80% of theory).

[0189] Synthesis of Compounds (4-2) to (4-10)

[0190] Analogously to the synthesis of compound (2-1) described in Example 1, the following compounds (4-2) to (4-10) are also prepared.

TABLE-US-00008 Ex. Reactant 1 Reactant 2 4-2 [00355] [00356] 4-3 [00357] [00358] 4-4 [00359] [00360] 4-5 [00361] [00362] 4-6 [00363] [00364] 4-7 [00365] [00366] 4-8 [00367] [00368] 4-9 [00369] [00370] 410 [00371] [00372] 4-11 [00373] [00374] 4-12 [00375] [00376] 4-13 [00377] [00378] 4-14 [00379] [00380] 4-15 [00381] [00382] 4-16 [00383] [00384] 4-17 [00385] [00386] 4-18 [00387] [00388] 4-19 [00389] [00390] 4-20 [00391] [00392] 4-21 [00393] [00394] Ex. Product Yield 4-2 [00395] 78% 4-3 [00396] 71% 4-4 [00397] 82% 4-5 [00398] 89% 4-6 [00399] 69% 4-7 [00400] 80% 4-8 [00401] 77% 4-9 [00402] 71% 4-10 [00403] 60% 4-11 [00404] 77% 4-12 [00405] 70% 4-13 [00406] 79% 4-14 [00407] 66% 4-15 [00408] 65% 4-16 [00409] 76% 4-17 [00410] 82% 4-18 [00411] 83% 4-19 [00412] 90% 4-20 [00413] 61% 4-21 [00414] 77%

B) Device Examples

[0191] OLEDs of the invention and OLEDs according to the prior art are produced by a general method according to WO 04/058911, which is adapted to the circumstances described here (e.g. materials).

[0192] In the inventive examples which follow, the data for various OLEDs are presented. Substrates used are glass plates coated with structured ITO (indium tin oxide) of thickness 50 nm. The OLEDs have the following layer structure: substrate/p-doped hole transport layer (HIL1)/hole transport layer (HTL)/p-doped hole transport layer (HTL2)/electron blocker layer (EBL)/emission layer (EML)/electron transport layer (ETL)/electron injection layer (EIL) and finally a cathode. The cathode is formed by an aluminum layer of thickness 100 nm. The materials required for production of the OLEDs are shown in Table 1.

[0193] All materials are applied by thermal vapour 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 H1:SEB(5%) mean here that the material H1 is present in the layer in a proportion by volume of 95% and SEB in a proportion by volume of 5%. Analogously, the electron transport layers or the hole injection layers may also consist of a mixture of two or more materials.

[0194] The OLEDs are characterized in a standard manner. For this purpose, the external quantum efficiency (EQE, measured in percent) is determined as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian radiation characteristics, and the lifetime. The parameter EQE @ 10 mA/cm.sup.2 refers to the external quantum efficiency at a current density of 10 mA/cm.sup.2. LD80 @ 60 mA/cm.sup.2 is the lifetime before the OLED, given a starting brightness at constant current of 60 mA/cm.sup.2, has fallen to 80% of the starting intensity.

TABLE-US-00009 TABLE 1 Structures of the materials used [00415] [00416] [00417] [00418] [00419] [00420] [00421] [00422] [00423] [00424] [00425] [00426] [00427]

[0195] Samples HTM1, HTM2, HTM3, HTM4 and HTM5 were compared with one another in a blue-fluorescing OLED. The structure of the stack is as follows: HIM:F4TCNQ(5%)(20 nm)/HIM(155 nm)/HTM_x: F4TCNQ(5%)(20 nm)/HTM_x(20 nm)/H1:SEB(5%)(20 nm)/ETM:LiQ(50%)(30 nm)/LiQ(1 nm). HTM_x in each case is the inventive material HTM1, HTM2, HTM3, HTM4 or HTM5. If, in the third layer, for example, the doped HTM1 is used in place of HTM_x, it is necessary to use HTM1 in the subsequent layer as well. A cross-combination of doped HTM1 and undoped HTM2 is not considered here.

[0196] The evaluation of the external quantum efficiencies at 10 mA/cm.sup.2 for the experiments conducted shows the following results: HTM1 achieves 8.6% EQE, whereas HTM2 achieves 8.2%, HTM3 8.1%, HTM4 7.8% and HTM5 8.0%. The lifetimes of the devices produced before a decline to 80% of the starting intensity at a constant current of 60 mA/cm.sup.2 are 310 hours for HTM1, 400 hours for HTM2, 420 hours for HTM3, 350 hours for HTM4 and 410 hours for HTM5.

[0197] The same two materials are used to produce a triplet green component having the following structure: HIM:F4TCNQ(5%)(20 nm)/HIM(210 nm)/HTM_x:F4TCNQ(5%)(20 nm)/HTM_x(20 nm)/H2:TEG(10%)(30 nm)/ ETM:LiQ(50%)(40 nm)/LiQ(1 nm). HTM_x in each case is the inventive material HTM1, HTM2, HTM3, HTM4 or HTM5. If, in the third layer, for example, the doped HTM1 is used in place of HTM_x, it is necessary to use HTM1 in the subsequent layer as well. A cross-combination of, for example, doped HTM1 and undoped HTM2 is not considered here.

[0198] The external quantum efficiencies show a similar trend to the above-described blue-fluorescing OLED. The external quantum efficiency for HTM1 at 2 mA/cm.sup.2 in this experiment is 18.3%. The components containing HTM2 achieve 18.2%, HTM3 17.2%, HTM4 17.5% and HTM5 18.0%. The lifetimes are similarly high to the blue-fluorescing OLED: HTM1 at 20 mA/cm.sup.2 has a lifetime before a decline to 80% of the starting intensity of 155 hours. HTM2 has an LD80 of 210 hours, HTM3 of 220 hours, HTM4 of 190 hours and HTM5 of 210 hours.