MATERIALS FOR ORGANIC ELECTTROLUMINESCENT DEVICES

Abstract

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

Claims

1.-9. (canceled)

10. A compound of formula (1) ##STR00475## where the symbols and indices used are as follows: Ar.sup.1 are the same or different at each instance and are an aromatic or heteroaromatic ring system which has 6 to 60 aromatic ring atoms and may in each case also be substituted by one or more R.sup.2 radicals, where, in the case that q>0, at least the two Ar.sup.1 may be joined and/or Ar.sup.1 may be joined to Ar.sup.2 via at least one bridge K; 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, CO, C(R.sup.2).sub.2, Si(R.sup.2).sub.2, and S; Ar.sup.2 is the same or different at each instance and is a bivalent aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals; X is the same or different at each instance and is N or CR.sup.1; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, CHO, C(O)Ar, P(O)(Ar).sub.2, S(O)Ar, S(O).sub.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 Si(R.sup.2).sub.2, Ge(R.sup.2).sub.2, Sn(R.sup.2).sub.2, CO, CS, CSe, P(O)(R.sup.2), SO, SO.sub.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 40 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 a combination of these systems; at the same time, two or more adjacent R.sup.1 substituents may also together form a mono- or polycyclic, aliphatic or aromatic ring system; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 6 to 60 aromatic ring atoms and may in each case also be substituted by one or more R.sup.2 radicals; R.sup.2 is the same or different at each instance and is H, D, F, Cl, Br, I, CHO, C(O)R.sup.3, P(O) (R.sup.3).sub.2, S(O) R.sup.3, S(O).sub.2 R.sup.2, 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 CC, Si(R.sup.3).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, CO, CS, CSe, P(O)(R.sup.3), SO, SO.sub.2, 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 a combination of these systems; at the same time, two or more adjacent R.sup.2 substituents may also together 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, N(R.sup.4).sub.2, C(O)Ar, P(O)Ar.sub.2, S(O)Ar, S(O).sub.2Ar, CR.sup.4CR.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.4CCR.sup.4, CC, Si(R.sup.4).sub.2, CO, CNR.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 adjacent R.sup.3 substituents may also together 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, F or an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms; q is 0, 1 or 2; where Ar.sup.2 in the case of a heteroaromatic ring system may be joined to the phenanthridine base skeleton via a CC bond; and, R.sup.1 in the case of a heteroaromatic ring system may be joined to the phenanthridine base skeleton via a CC bond.

11. The compound according to claim 10, corresponding to formula (2) ##STR00476## where the symbols and indices have the definitions given in claim 10.

12. The compound according to claim 11, corresponding to one of the formulae (3) to (8): ##STR00477## ##STR00478## where the symbols and indices have the definitions given in claim 11 and, in addition, the two Ar.sup.1 are not joined to one another and Ar.sup.1 is not joined to Ar.sup.2 by further K groups and, in the formulae (4), (5), (6), (7) and (8), q>0.

13. A process for preparing a compound according to claim 10, wherein the compound of the formula (1) is formed by one or more coupling reactions and/or cyclizations.

14. A mixture comprising at least one compound according to claim 10 and at least one fluorescent or phosphorescent dopant.

15. A formulation, a solution, a suspension or a miniemulsion, comprising at least one compound according to claim 10 and one or more solvents.

16. A method comprising utilizing the compound according to claim 10 in an electronic device.

17. An electronic device comprising at least one compound according to claim 10, wherein the electronic devise is 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.

18. The electronic device according to claim 17, wherein the device is an organic electroluminescent device and the compound 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 an electron blocker layer.

Description

WORKING EXAMPLES

[0130] ##STR00115##

[0131] Scheme 1 shows one possible synthesis route. R is any radical and Ar is a heteroaromatic ring system of the formula (Ar.sup.2).sub.qN(Ar.sup.1).sub.2, or Ar.sup.1 in the case of Buchwald coupling. Rather than Br, it is also possible for another group suitable for coupling to be present, such as a chlorine or iodine or a sulfonic acid group. Proceeding from fluorenone, via a Beckmann rearrangement, it is possible to obtain 5H-phenanthridin-6-one. From this, with PBr.sub.3, it is possible to obtain 6-bromophenanthridine. This compound can be converted to the compounds of the invention by organometallic couplings such as Suzuki or Buchwald couplings.

[0132] Unless stated otherwise, the syntheses which follow are conducted under a protective gas atmosphere. The reactants can be sourced from ALDRICH or ABCR (palladium(II) acetate, tri-o-tolylphosphine, inorganic substances, solvents).

Example 1: 3-Bromo-9-[1,1;3,1]terphenyl-5-yl-9H-carbazole

[0133] ##STR00116##

[0134] 10 g (41 mmol) of 3-bromo-9H-carbazole (CAS 86-74-8) and 16 g (45 mmol, 1.1 eq) of 5-iodo-[1,1;3,1]terphenyl are dissolved together with 9.2 g (160 mmol, 4 eq) of potassium hydroxide, 300 mg (1.6 mmol, 0.04 eq) 1,10-phenanthroline and 160 mg (1.6 mmol, 0.04 eq) of copper(I) iodide in 250 ml of p-xylene, and the mixture is heated under reflux. After the reaction has ended, the mixture is extracted three times with water and the organic phase is dried over sodium sulfate, the solvent is removed under reduced pressure and the solids obtained are purified by means of column chromatography (ethyl acetate/heptane). 17 g (36 mmol, 88%) of the desired product are obtained.

[0135] In an analogous manner, it is possible to obtain the following compounds

TABLE-US-00001 Yield Ex. Reactant 1 Reactant 2 Product [%] 1a [00117] [00118] [00119] 94 1b [00120] [00121] [00122] 91

Example 2: 9-(9,9-Dimethyl-9H-fluoren-2-yl)-9H-carbazole-3-boronic Acid

[0136] ##STR00123##

[0137] 22.3 g (51 mmol) of 3-bromo-9-(9,9-dimethyl-9H-fluoren-2-yl)-9H-carbazole are dissolved in 600 ml of dry THF and cooled to 78 C. At this temperature, 26.2 ml (65.7 mmol/2.5 M in hexane) of n-BuLi are added within about 5 min. and then the mixture is stirred at 78 C. for 2.5 h. At this temperature, 7.3 ml (65.7 mmol) of trimethyl borate are added very rapidly and the reaction is allowed to come gradually to RT (about 18 h). The reaction solution is washed with water and the precipitated solids and the organic phase are subjected to azeotropic drying with toluene. The crude product is extracted by stirring from toluene/methylene chloride at about 40 C. and filtered with suction. 17.5 g (85%) of the product are obtained as a white solid.

[0138] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00002 Yield Ex. Reactant 1 Product [%] 2a [00124] [00125] 79

Example 3: 3-(5-Bromobiphenyl-3-yl)-9-phenyl-9H-carbazole

[0139] ##STR00126##

[0140] 15.5 g (43.3 mmol) of 3-bromo-5-iodobiphenyl and 13.7 g (48 mmol) of (9-phenyl-9H-carbazol-3-yl)boronic acid are dissolved in 80 ml of toluene and degassed. 281 ml of a degassed 2 M K.sub.2CO.sub.3 solution and 2.5 g (2.2 mmol) of Pd(OAc).sub.2 are added. The reaction mixture is then stirred at 80 C. under a protective gas atmosphere for 48 h. The cooled solution is diluted with toluene, washed repeatedly with water, dried and concentrated. The product is purified via column chromatography on silica gel with toluene/heptane (1:2). The purity is 98%. Yield: 17.6 g (37 mmol, 78%) of theory.

[0141] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00003 Yield Ex. Reactant 1 Reactant 2 Product [%] 3a [00127] [00128] [00129] 70 3b [00130] [00131] [00132] 69 3c [00133] [00134] [00135] 68 3d [00136] [00137] [00138] 83

Example 4: 3-(5-boronic acid-biphenyl-3-yl)-9-phenyl-9H-carbazole

[0142] ##STR00139##

[0143] To a solution, cooled to 78 C., of 128 g (270 mmol) of 3-(5-bromobiphenyl-3-yl)-9-phenyl-9H-carbazole in 1500 ml of diethyl ether are added dropwise 110 ml (276 mmol) of n-butyllithium (2.5 M in hexane). The reaction mixture is stirred at 78 C. for 30 minutes. The mixture is allowed to come to room temperature and cooled again to 78 C., and then a mixture of 40 ml (351 mmol) of trimethyl borate in 50 ml of diethyl ether is added rapidly. After warming to 10 C., hydrolysis is effected with 135 ml of 2 N hydrochloric acid. The organic phase is removed, washed with water, dried over sodium sulfate and concentrated to dryness. The residue is taken up in 300 ml of n-heptane, and the colourless solids are filtered off with suction, washed with n-heptane and dried under reduced pressure. Yield: 112 g (256 mmol), 95% of theory.

[0144] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00004 Yield Ex. Reactant 1 Product [%] 4a [00140] [00141] 59 4b [00142] [00143] 60 4e [00144] [00145] 59 4f [00146] [00147] 83

Example 5: 6-(9-Phenyl-9H-carbazol-3-yl)phenanthridine

[0145] ##STR00148##

[0146] 28.9 g (43.3 mmol) of 6-bromophenanthridine and 13.7 g (48 mmol) of 9-phenyl-9H-carbazole-3-boronic acid are dissolved in 80 ml of toluene and degassed. 281 ml of a degassed solution of 2 M K.sub.2CO.sub.3 and 2.5 g (2.2 mmol) of Pd(OAc).sub.2 are added. The reaction mixture is then stirred under a protective gas atmosphere at 80 C. for 48 h. The cooled solution is supplemented with toluene, washed repeatedly with water, dried and concentrated. The product is purified via column chromatography on silica gel with toluene/heptane (1:2) and finally sublimed under high vacuum (p=510.sup.7 mbar). The purity is 99.9%. Yield: 28 g (31 mmol), 80% of theory.

[0147] In an analogous manner, it was possible to obtain the following compounds:

TABLE-US-00005 Yield Ex. Reactant 1 Reactant 2 Product [%] 5a [00149] [00150] [00151] 59 5b [00152] [00153] [00154] 60 5c [00155] [00156] [00157] 67 5d [00158] [00159] [00160] 69 5e [00161] [00162] [00163] 71 5f [00164] [00165] [00166] 73 5g [00167] [00168] [00169] 66 5h [00170] [00171] [00172] 75 5i [00173] [00174] [00175] 78 5j [00176] [00177] [00178] 81 5k [00179] [00180] [00181] 82 5l [00182] [00183] [00184] 84 5m [00185] [00186] [00187] 80 5n [00188] [00189] [00190] 84 5o [00191] [00192] [00193] 79 5p [00194] [00195] [00196] 78 5q [00197] [00198] [00199] 77 5r [00200] [00201] [00202] 89 5r1 [00203] [00204] [00205] 82

[0148] In an analogous manner, it is possible to obtain the following compounds with 0.5 eq. of phenanthridine:

TABLE-US-00006 Yield Ex. Reactant 1 Reactant 2 Product [%] 5s [00206] [00207] [00208] 69

Example 6: (9,9-Dimethyl-9H-fluoren-2-yl)-{4-[(Z)-1-eth-(E)-ylidene-penta-2,4-dienyl]phenyl}amine

[0149] ##STR00209##

[0150] 24.0 g (142 mmol, 1.2 eq.) of 4-aminobiphenyl 1a (CAS 92-67-1) are initially charged together with 32.0 g (117 mmol, 1.0 eq) of 2-bromo-9,9-dimethylfluorene 2a (CAS 28320-31-2) in 950 ml of toluene, and the mixture is saturated with argon for 30 minutes. Subsequently, 1.0 g (1.8 mmol, 0.02 eq) of 1,1-bis(diphenylphosphino)ferrocene (CAS 12150-46-8), 350 mg (1.6 mmol, 0.01 eq) of palladium(II) acetate (CAS 3375-31-3) and 29 g (300 mmol, 2.6 eq) of sodium tert-butoxide (CAS 865-48-5) are added and heated under reflux overnight. After the reaction has ended, the mixture is diluted with 300 ml of toluene and extracted with water. The organic phase is dried over sodium sulfate and the solvent is removed by rotary evaporator. The brown oil is admixed with 50 ml of ethyl acetate and added to a mixture of heptane/ethyl acetate 20:1. The resultant solids are filtered off with suction and washed with heptane. After drying, 29 g (80 mmol, 69%) of the desired product 3a are obtained with an HPLC purity of 99.1%.

[0151] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00007 Yield Ex. Reactant 1 Reactant 2 Product [%] 6a [00210] [00211] [00212] 71 6b [00213] [00214] [00215] 61 6c [00216] [00217] [00218] 78 6d [00219] [00220] [00221] 82 6e [00222] [00223] [00224] 62 6f [00225] [00226] [00227] 47 6g [00228] [00229] [00230] 92 6h [00231] [00232] [00233] 75 6i [00234] [00235] [00236] 84 6j [00237] [00238] [00239] 62 6k [00240] [00241] [00242] 78 6l [00243] [00244] [00245] 74 6m [00246] [00247] [00248] 62 6n [00249] [00250] [00251] 67 6o [00252] [00253] [00254] 93 6p [00255] [00256] [00257] 88 6q [00258] [00259] [00260] 74

Example 7: Biphenyl-4-yl-(3-bromobiphenyl-3-yl)-(9,9-dimethyl-9H-fluoren-2-yl)amine

[0152] ##STR00261##

[0153] 29 g (80 mmol, 1.0 eq) of the intermediate 3a are dissolved together with 25 g (80 mmol, 1.0 eq) of 3,3-dibromo-1,1-biphenyl 4a (CAS 16400-51-4) in 600 ml of toluene and degassed for 30 minutes. Subsequently, 45 g (240 mmol, 3.0 eq) of sodium tert-butoxide, 890 mg (0.40 mmol, 0.050 eq) of palladium(II) acetate and 8 ml (8.0 mmol, 0.10 eq.) of a 1M tri-tert-butylphosphine solution are added. The mixture is heated under reflux overnight and, after the reaction has ended, filtered twice through alumina with toluene. After the solvent has been removed by rotary evaporator, the oil is dissolved in a little THF and introduced into heptane. The resultant solids are filtered off with suction and purified by means of hot extraction in heptane/toluene 1:1. 16.6 g (28 mmol, 35%) of the desired product 5a are obtained.

[0154] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00008 Yield Ex. Reactant 3 Reactant 4 Product [%] 7a [00262] [00263] [00264] 49 7b [00265] [00266] [00267] 37 7c [00268] [00269] [00270] 72 7d [00271] [00272] [00273] 28 7e [00274] [00275] [00276] 82 7f [00277] [00278] [00279] 32 7g [00280] [00281] [00282] 46 7h [00283] [00284] [00285] 41 7i [00286] [00287] [00288] 31 7j [00289] [00290] [00291] 27 7k [00292] [00293] [00294] 38 7l [00295] [00296] [00297] 56 7m [00298] [00299] [00300] 33 7n [00301] [00302] [00303] 47 7o [00304] [00305] [00306] 24 7p [00307] [00308] [00309] 81 7q [00310] [00311] [00312] 57 7r [00313] [00314] [00315] 29 7s [00316] [00317] [00318] 36

Example 8: Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-[3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)biphenyl-3-yl]amine

[0155] ##STR00319##

[0156] In a 500 ml flask, under protective gas, 16.6 g (28 mmol, 35%) of the bromide 5a are dissolved together with 8.5 g (34 mmol, 1.2 eq) of bis-(pinacolato)diborane (CAS 73183-34-3) in 120 ml of dry DMF and degassed for 30 minutes. Subsequently, 8.2 g (84 mmol, 3.0 eq) of potassium acetate and 690 mg (0.84 mmol, 3 mol %) of [1,1-bis(diphenylphosphino)ferrocene]-dichloropalladium(II) complex are added together with dichloromethane (CAS 95464-05-4), and the mixture is heated at 90 C. overnight. After the reaction has ended, the mixture is diluted with 300 ml of toluene and the mixture is extracted with water. The solvent is removed by rotary evaporator and the solids obtained (14.7 g (23 mmol, 82%)) are dried. The boronic ester 6a is converted without further purification.

[0157] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00009 Yield Ex. Reactant 5 Product 6 [%] 8a [00320] [00321] 88 8b [00322] [00323] 81 8c [00324] [00325] 75 8d [00326] [00327] 67 8e [00328] [00329] 79 8f [00330] [00331] 93 8g [00332] [00333] 44 8h [00334] [00335] 87 8i [00336] [00337] 28 8j [00338] [00339] 35 8k [00340] [00341] 77 8l [00342] [00343] 38 8m [00344] [00345] 55 8n [00346] [00347] 41 8o [00348] [00349] 67 8p [00350] [00351] 82 8q [00352] [00353] 91 8r [00354] [00355] 87 8s [00356] [00357] 96

Example 9

[0158] ##STR00358##

[0159] Analogously to Example 5, it is possible to prepare the following molecules:

TABLE-US-00010 Yield Ex. Reactant 1 Reactant 2 Product [%] 9a [00359] [00360] [00361] 70 9b [00362] [00363] [00364] 71 9c [00365] [00366] [00367] 74 9d [00368] [00369] [00370] 80 9e [00371] [00372] [00373] 74 9f [00374] [00375] [00376] 57 9g [00377] [00378] [00379] 72 9h [00380] [00381] [00382] 75 9i [00383] [00384] [00385] 83 9j [00386] [00387] [00388] 60 9k [00389] [00390] [00391] 77 9l [00392] [00393] [00394] 72 9m [00395] [00396] [00397] 73 9n [00398] [00399] [00400] 66 9o [00401] [00402] [00403] 87 9p [00404] [00405] [00406] 84 9q [00407] [00408] [00409] 73 9r [00410] [00411] [00412] 78 9s [00413] [00414] [00415] 91 9t [00416] [00417] [00418] 85 9u [00419] [00420] [00421] 79

Example 10: Biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)phenanthridin-6-ylamine

[0160] ##STR00422##

[0161] 29 g (80 mmol, 1.0 eq) of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine are dissolved together with 20 g (80 mmol, 1.0 eq) of 6-bromophenanthridine in 600 ml of toluene and degassed for 30 minutes. Subsequently, 45 g (240 mmol, 3.0 eq) of sodium tert-butoxide, 890 mg (0.40 mmol, 0.050 eq) of palladium(II) acetate and 8 ml (8.0 mmol, 0.10 eq.) of a 1M tri-tert-butylphosphine solution are added. The mixture is heated under reflux overnight and, after the reaction has ended, filtered twice through an alumina with toluene. After the solvent has been removed on a rotary evaporator, the oil is dissolved in a little THF and introduced into heptane. The product is purified via column chromatography on silica gel with toluene/heptane (1:2) and finally sublimed under high vacuum (p=510.sup.7 mbar). 29 g (28 mmol, 69%) of the desired product with purity <99.9% are obtained.

[0162] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00011 Yield Ex. Reactant 1 Reactant 2 Product [%] 10a [00423] [00424] [00425] 49% 10b [00426] [00427] [00428] 53 10c [00429] [00430] [00431] 68 10d [00432] [00433] [00434] 69 10e [00435] [00436] [00437] 58 10f [00438] [00439] [00440] 63 10g [00441] [00442] [00443] 65 10h [00444] [00445] [00446] 72 10i [00447] [00448] [00449] 67 10m [00450] [00451] [00452] 77 10p [00453] [00454] [00455] 70

Example 11: Production of the OLEDs

[0163] In the examples 11 to 110 which follow (see tables 1 and 2), the data of various OLEDs are presented. Clean glass plaques (cleaning in a laboratory glass washer, detergent: Merck Extran) which have been coated with structured ITO (indium tin oxide) of thickness 50 nm are pretreated with UV ozone for 25 minutes (PR-100 UV ozone generator, from UVP) and, within 20 min, for improved processing, coated with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulphonate), purchased as CLEVIOS P VP Al 4083 from Heraeus Precious Metals GmbH Deutschland, spun on from aqueous solution) and then baked at 180 C. for 10 min. These coated glass plaques form the substrates to which the OLEDs are applied.

[0164] The OLEDs have the following basic layer structure: substrate/hole transport layer (HTL)/interlayer (IL)/electron blocker layer (EBL) emission layer (EML)/optional hale blacker layer (HBL)/electron transport layer (ETL) and finally a cathode. The cathode is formed by an aluminium layer of thickness 100 nm. The exact structure of the OLEDs can be found in Table 1. A reference such as 5a in the table relates to the materials shown in the tables for examples 4-10. The further materials required for production of the OLEDs are shown in table 3.

[0165] All materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer always consists of at least one matrix material (host material) and an emitting dopant (emitter) which is admixed with the matrix material(s) by coevaporation in a particular proportion by volume. Details given in such a form as IC2:5c:TEG1 (60%:30%:10%) here mean that the material IC2 is present in the layer in a proportion by volume of 60%, 5c in a proportion of 30% and TEG1 in a proportion of 10%. Analogously, the electron transport layer may also consist of a mixture of two materials.

[0166] 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 Im/W) and the external quantum efficiency (EQE, measured in percent) as a function of the luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian radiation characteristics, and the lifetime are determined. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2 and these are used to calculate the CIE 1931 x and y colour coordinates. The FIGURE U1000 in Table 2 refers to the voltage which is required for a luminance of 1000 cd/m.sup.2. SE1000 and LE1000 refer respectively to the current efficiency and power efficiency that are attained at 1000 cd/m.sup.2. Finally, EQE1000 refers to the external quantum efficiency at an operating luminance of 1000 cd/m.sup.2.

[0167] The data of the various OLEDs are summarized in table 2.

TABLE-US-00012 TABLE 1 Structure of the OLEDs HTL IL EBL HBL thick- thick- thick- EML thick- ETL Ex. ness ness ness thickness ness thickness I1 SpA1 HATC SpMA1 IC1:TEG1 IC1 5r1:LiQ 70 nm N 5 nm 90 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm I2 SpA1 HATC SpMA1 5r1:TEG1 IC1 ST1:LiQ 70 nm N 5 nm 90 nm (90%:15%) 10 nm (50%:50%) 30 nm 30 nm I3 SpA1 HATC SpMA1 5r1:TER1 ST1:LiQ 90 nm N 5 nm 130 nm (90%:10%) (50%:50%) 40 nm 40 nm I4 SpA1 HATC SpMA1 IC2:5a:TEG1 IC1 ST1:LiQ 70 nm N 5 nm 90 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm I5 SpA1 HATC SpMA1 IC2:5c:TEG1 IC1 ST1:LiQ 70 nm N 5 nm 90 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm I6 SpA1 HATC SpMA1 IC2:5i:TEG1 ST1 ST1:LiQ 70 nm N 5 nm 90 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm I7 SpA1 HATC 9 IC2:TEG1 ICI ST1:LiQ 70nm N 5nm 90 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm I8 SpA1 HATC 9j IC1:TEG1 IC1 ST1:LiQ 70 nm N 5 nm 90 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm I9 SpA1 HATC 9s IC1:TEG1 IC1 ST1:LiQ 70 nm N 5 nm 90 nm (90%:10%) 10 nm (50%:50%) 30 nm 30nm I10 SpA1 HATC SpMA1 IC1:9c:TEG1 IC1 ST1:LiQ 70 nm N 5 nm 90 nm (55%:35%:10%) 10 nm (50%:50%) 30 nm 30 nm

TABLE-US-00013 TABLE 2 Data of the OLEDs U1000 SE1000 LE1000 EQE CIE x/y at Ex. (V) (cd/A) (lm/W) 1000 1000 cd/m.sup.2 I1 4.8 55 36 15.3% 0.34/0.62 I2 3.6 57 49 15.8% 0.33/0.63 I3 4.9 12.2 7.8 13.2% 0.67/0.33 I4 3.5 55 49 15.4% 0.33/0.62 I5 3.7 50 42 13.7% 0.33/0.63 I6 3.2 57 55 15.9% 0.34/0.62 I7 3.3 47 45 13.3% 0.34/0.62 I8 3.4 60 55 16.8% 0.34/0.62 I9 3.5 61 55 17.2% 0.34/0.62 I10 3.4 64 59 18.0% 0.34/0.62

TABLE-US-00014 TABLE 3 Structural formulae of the materials for the OLEDs [00456] [00457] SpA1 [00458] [00459] ST1 [00460] TEG1 [00461] TEG2 [00462] IC1 [00463] SpMA1 [00464] TER1 [00465] BIC1 [00466] IC2 [00467] 5a [00468] 5c [00469] 5i [00470] 5r1 [00471] 9 [00472] 9c [00473] 9j [00474] 9s