MATERIALS FOR ORGANIC ELECTROLUMINESCENT DEVICES

Abstract

The present invention relates to compounds which are suitable for use in electronic devices, and to electronic devices, in particular organic electroluminescent devices, containing these compounds.

Claims

1.-14. (canceled)

15. A compound of formula (1) ##STR00826## where the R radicals may also occur more than once and the symbols used are: Z is O or S; R* is a group of the formula (2), where the dotted bond represents the bond to the base skeleton in the formula (1), ##STR00827## X is the same or different at each instance and is CR or N; or two adjacent X groups are a group of the following formula (3), (4) or (5), with the proviso that at least two and at most three X groups are N, ##STR00828## where the dotted bonds indicate the linkage of this group in the formula (2); Y is the same or different at each instance and is CR or N; A is NR, O, S or CR.sub.2; L is a single bond or an aromatic or heteroaromatic ring system which has 5 to 24 aromatic ring atoms and may be substituted by one or more R radicals; R is the same or different at each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OR.sup.1, SR.sup.1, COOR.sup.1, C(O)N(R.sup.1).sub.2, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(O)R.sup.1, P(O)(R.sup.1).sub.2, S(O)R.sup.1, S(O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sup.1).sub.2, CO, NR.sup.1, O, S or CONR.sup.1, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, and may be substituted in each case by one or more R.sup.1 radicals; at the same time, two R radicals together may also form an aliphatic or heteroaliphatic ring system; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, CN, NO.sub.2, OR.sup.2, SR.sup.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 group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may each 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, CO, NR.sup.2, O, S or CONR.sup.2 and where one or more hydrogen atoms in the alkyl, alkenyl or alkynyl group may be replaced by D, F, Cl, Br, I or CN, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.2 radicals; at the same time, two or more R.sup.1 radicals together may form an aliphatic ring system; and R.sup.2 is the same or different at each instance and is H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F.

16. The compound as claimed in claim 15, wherein the compound is selected from the compounds of the formulae (6a), (6b), (7a) and (7b) ##STR00829## where the R radicals may also occur more than once, and the symbols have the definitions given in claim 15.

17. The compound as claimed in claim 15, characterized in that Z is O.

18. The compound as claimed in claim 15, characterized in that not more than two substituents R are a group other than H or D.

19. The compound as claimed in claim 15, wherein the compound is selected from the formulae (6a-1) to (7b-4) ##STR00830## ##STR00831## ##STR00832## where the symbols have the definitions given in claim 15.

20. The compound as claimed in claim 15, characterized in that L is a single bond or a bivalent aromatic ring system which has 6 to 12 aromatic ring atoms and may be substituted by one or more R radicals, or a dibenzofuran or dibenzothiophene group that may be substituted by one or more R radicals.

21. The compound as claimed in claim 15, characterized in that L, when L is an aromatic or heteroaromatic ring system, is selected from the structures of the formulae (L-1) to (L-26) ##STR00833## ##STR00834## ##STR00835## ##STR00836## where the symbols have the meanings given in claim 15 and the dotted bonds represent the bonds to the heteroaryl group in the group of the formula (2) and to the base skeleton of the compound of the formula (1).

22. The compound as claimed in claim 15, characterized in that the group of the formula (2) is selected from the structures of the formulae (8) to (18): ##STR00837## ##STR00838## where the symbols used have the definitions given in claim 15 and, in formula (8), two or three X are N and R is the same or different at each instance and is an aromatic heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals, and where, in the formulae (9) to (18), exactly two X are N and R may also occur repeatedly.

23. The compound as claimed in claim 15, characterized in that the group of the formula (2) is selected from the groups of the formulae (8a) to (18a): ##STR00839## ##STR00840## ##STR00841## where the symbols have the definitions given in claim 15 and R is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals.

24. A process for preparing the compound as claimed in claim 15, characterized by the steps of: a) synthesizing the base skeleton that bears a reactive leaving group rather than the R* group; and b) introducing the substituent R* by a coupling reaction.

25. A formulation comprising at least one compound as claimed in claim 15 and at least one further compound and/or solvent.

26. An electronic device comprising at least one compound as claimed in claim 15.

27. An organic electroluminescent device comprising the compound as claimed in claim 15 wherein the compound is used in an emitting layer as matrix material for phosphorescent or fluorescent emitters or for emitters that exhibit TADF (thermally activated delayed fluorescence), and/or in an electron transport layer and/or in a hole blocker layer.

Description

EXAMPLES

[0110] 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. For the compounds known from the literature, the corresponding CAS numbers are also reported in each case.

##STR00564##

[0111] An initial charge under an inert atmosphere is formed by DMSO (50 ml), K.sub.3PO.sub.4 (53.08 g, 250 mmol), pyridine-2-carboxylic acid (1.53 g, 12.44 mmol) and CuI (1.19 g, 6.22 mmol). Subsequently, 3-chlorophenol (19.20 g, 150 mmol) [108-43-0] and 3-bromo-1-chlorobenzene (23.93 g, 125 mmol) [108-37-2] are gradually added successively, and the reaction mixture is heated at 85 C. for 16 h. After cooling, the reaction mixture is worked up by extraction with aqueous ammonia solution and methyl tert-butyl ether. The organic phase is washed five times with water and twice with saturated NaCl solution, the combined organic phases are dried over Na.sub.2SO.sub.4, and the solvent is drawn off on a rotary evaporator. The crude product is purified further via fractional distillation. Yield: 26.88 g (106 mmol), 85%; purity; 96% by .sup.1H NMR

[0112] The following compounds can be prepared analogously: Purification can be effected not only by distillation but also using column chromatography, or recrystallization can be effected using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone etc.

TABLE-US-00002 Reactant 1 Reactant 2 Product Yield [00565] [00566] [00567] 80% [00568] [00569] [00570] 86% [00571] [00572] [00573] 74% [00574] [00575] [00576] 75% [00577] [00578] [00579] 68%

##STR00580##

[0113] An initial charge of S1a (23.90 g, 100 mmol) in THF (150 ml) under an inert atmosphere is cooled down to 75 C. Subsequently, n-butyllithium (2.5 mol/l in hexane, 80 ml, 200 mmol) is added dropwise in such a way that the internal temperature does not exceed 65 C. The mixture is left to stir 75 C. for a further 4 h, and then bromine (5.6 ml, 109.3 mmol) is added in such a way that the internal temperature does not exceed 65 C. After the addition has ended, the mixture is stirred at 75 C. for 1 h, then allowed to warm up gradually to 10 C. within 1 h and stirred at 10 C. for 1 h. This is followed by cooling to 0 C. and cautious quenching of the mixture with saturated Na.sub.2SO.sub.3 solution (50 ml). The mixture is worked up by extraction with toluene and water, the combined organic phases are washed three times with water and once with saturated NaCl solution and dried over Na.sub.2SO.sub.4, and the solvent is removed on a rotary evaporator. The crude product is twice extracted by stirring with 2-propanol under reflux. Yield: 24.21 g (86 mmol, 86%), purity: 97% by .sup.1H NMR.

[0114] The following compounds can be prepared analogously: Purification can be effected not only by extractive stirring but also by distillation, or recrystallization can be effected using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone etc.

TABLE-US-00003 Reactant Product Yield [00581] [00582] [00583] 70% [00584] [00585] 79% [00586] [00587] [00588] 79% [00589] [00590] [00591] 74% [00592] [00593] 53% [00594]

##STR00595##

[0115] An initial charge of S1b (39.19 g, 140.0 mmol), 4-methoxyphenylboronic acid (22.79 g, 150.0 mmol) [5720-07-0] and K.sub.2CO.sub.3 (38.70 g, 280.0 mmol) in THF (70 ml) and water (170 ml) is inertized for 30 min. Subsequently, tetrakis(triphenylphosphine)palladium [14221-01-3] (1.78 mg, 1.54 mmol) is added and the reaction mixture is stirred under reflux for 20 h. The mixture is worked up by extraction with toluene and water, the combined organic phases are washed with water and saturated NaCl solution and dried over Na.sub.2SO.sub.4, and the solvent is drawn off on a rotary evaporator. The crude product is recrystallized from ethanol. Yield: 33.7 g (109 mmol, 78%), 96% by .sup.1H NMR.

[0116] The following compounds can be prepared analogously: Purification can be effected by column chromatography, or recrystallization can be effected using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl pyrrolidone etc.

TABLE-US-00004 Reactant 1 Reactant 2 Product Yield [00596] [00597] [00598] [00599] [00600] 64% [00601] [00602] [00603] [00604] [00605] 69% [00606] [00607] [00608] 62% [00609] [00610] [00611] [00612] [00613] 59% [00614] [00615] [00616] [00617] [00618] 51% [00619] [00620] [00621] 56% [00622] [00623] [00624] 36% [00625] [00626] [00627] 75%

##STR00628##

[0117] To an initial charge of S1c (30.88 g, 100 mmol) and K.sub.2CO.sub.3 (41.46 g, 300 mmol) under an inert atmosphere is added DMAc (450 ml), and the mixture is inertized for 30 min. Subsequently, Pd(OAc).sub.2 (447 mg, 1.99 mmol) and 1,3-bis(2,6-diisopropylphenyl)-3H-imidazol-1-ium chloride (1.69 g, 3.98 mmol) are added, and the reaction mixture is stirred at 150 C. for 16 h. After cooling, the mixture is poured into ethanol/water (1:1, 600 ml) and stirred for a further 30 min. The precipitated solids are filtered off with suction and washed five times with water and three times with ethanol. The crude product is extracted by stirring under reflux with 2-propanol, and the solids are filtered off with suction after cooling. Yield: 22.9 g (84 mmol, 84%), 98% by 1H NMR.

[0118] The following compounds can be prepared analogously: It is possible here to use not only 1,3-bis(2,6-diisopropylphenyl)-3H-imidazol-1-ium chloride but also tri-tert-butylphosphine or tricyclohexylphosphine, or as Pd source to use not only Pd(OAc).sub.2 but also Pd.sub.2(dba).sub.3. Purification can be effected by column chromatography, or recrystallization can be effected using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone etc.

TABLE-US-00005 Reactant Product Yield [00629] [00630] 75% [00631] [00632] [00633] 73% [00634] [00635] [00636] 78% [00637] [00638] [00639] 80% [00640] [00641] 63% [00642] [00643] [00644] 46% [00645] [00646] 25% [00647] [00648] 81%

##STR00649##

[0119] An initial charge of S1d (27.23 g, 100 mmol) in dichloromethane (620 ml) is cooled in an ice bath to 0 C. Subsequently, BBr.sub.3 (6.0 ml, 63.2 mmol) is cautiously added dropwise. After the addition has ended, the mixture is allowed to warm up to room temperature. On completion of conversion, the mixture is cooled again to 0 C. and quenched cautiously with MeOH (150 ml). The solvent is drawn off on a rotary evaporator. Subsequently, each of three additions of 300 ml of MeOH to the mixture is followed by removal thereof on a rotary evaporator. Another 200 ml of MeOH is added, and the solids are filtered off with suction. The crude product is dried and used in the next stage without further purification. Yield: 17.05 g (66 mmol, 66%).

[0120] The following compounds can be prepared analogously: Purification can be effected by column chromatography, or recrystallization can be effected using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone etc.

TABLE-US-00006 Reactant Product Yield [00650] [00651] 64% [00652] [00653] 71% [00654] [00655] 72% [00656] [00657] 63% [00658] [00659] 49% [00660] [00661] 57% [00662] [00663] 55%

##STR00664##

[0121] An initial charge of S1e (12.91 g, 50.0 mmol) and triethylamine (20.8 ml, 150 mmol) in dichloromethane (700 ml) is cooled to 0 C. in an ice bath. Subsequently, trifluoromethanesulfonic anhydride (10.9 ml, 65.0 mmol) is slowly added dropwise. After the addition has ended, the mixture is allowed to warm up to room temperature. On completion of conversion, the mixture is subjected to extractive workup with dichloromethane and water, the combined organic phases are dried over Na.sub.2SO.sub.4, and the solvent is removed on a rotary evaporator. The residue is taken up in 300 ml of cyclohexane, and the mixture is stirred at room temperature for 30 min. The solids are filtered off with suction and dried in a vacuum drying cabinet. Yield 13.74 g (35.2 mmol, 70%).

[0122] The following compounds can be prepared analogously: Purification can be effected by column chromatography, or recrystallization can be effected using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone etc.

TABLE-US-00007 Reactant Product Yield [00665] [00666] 76% [00667] [00668] 79% [00669] [00670] 67% [00671] [00672] 64% [00673] [00674] 50% [00675] [00676] 56% [00677] [00678] 47%

##STR00679##

[0123] An initial charge of S9c (24.23 g, 100 mmol) in 300 ml of THF is cooled to 75 C. Subsequently, hexyllithium (44.0 ml, c=2.5 mol/l, 110 mmol) is added in such a way that the temperature does not rise above 65 C. After the addition has ended, the mixture is stirred at 75 C. for 1 h. Subsequently, the reaction mixture is allowed to warm up gradually to room temperature and stirred at room temperature for 1 h. Subsequently, the reaction mixture is cooled back down to 75 C., and trimethyl borate (15.59 g, 150.0 mmol) is added dropwise in such a way that the temperature does not rise above 65 C. The mixture is allowed to come to room temperature overnight and quenched cautiously the next day with HCl (c=5 mol/l, 50 ml). The mixture is worked up by extraction with water, and the organic phase is washed three times with water. The THF is removed by rotary evaporation down to 50 ml, then 150 ml of n-heptane is added, and the precipitated solids are filtered off with suction and washed with n-heptane. Yield: 24.03 g (84.2 mmol, 84%), 96% by 1H NMR.

##STR00680##

[0124] An initial charge of S1f (11.71 g, 30.0 mmol), bis(pinacolato)diboron (9.40 g, 36.3 mmol) and KOAc (8.90 g, 90.68 mmol) in 1,4-dioxane (200 ml) is inertized with argon for 30 min. Subsequently, Pd(dppf)Cl.sub.2 (740 mg, 0.91 mmol) is added, and the mixture is stirred under reflux for 20 h. After cooling, the solvent is removed on a rotary evaporator, and the residue is worked up by extraction with dichloromethane and water. The combined organic phases are dried over Na.sub.2SO.sub.4, ethanol (150 ml) is added, and the dichloromethane is drawn off on a rotary evaporator. The precipitated solids are filtered off with suction and dried in a vacuum drying cabinet. The crude product is used in the next stage without further purification. Yield: 9.06 g (24.6 mmol, 82%), purity 95% by 1H NMR.

[0125] The following compounds can be prepared analogously: As an alternative, the catalyst system used may also be Pd(PCy.sub.3).sub.2Cl.sub.2 or Pd.sub.2(dba).sub.3 with S-Phos (1:3). Purification can be effected not only by column chromatography but also by hot extraction, or recrystallization or hot extraction using other standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, or recrystallization using high boilers such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl pyrrolidone, etc.

TABLE-US-00008 Reactant Product Yield [00681] [00682] 80% [00683] [00684] 85% [00685] [00686] 74% [00687] [00688] 70% [00689] [00690] 37% [00691] [00692] 65%

Preparation of the Compounds of the Invention

[0126] ##STR00693##

[0127] An initial charge of S1f (13.00 g, 33.30 mmol), 2,4-diphenyl-6-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)[1,1-biphenyl]-3-yl]-1,3,5-triazine (17.88 g, 34.97 mmol) [1802232-96-7] and K.sub.3PO.sub.4 (14.14 g, 66.61 mmol) in toluene (200 ml), dioxane (200 ml) and water (100 ml) is inertized with argon for 30 min. Subsequently, Pd.sub.2(dba).sub.3 (305 mg, 0.33 mmol) and triphenylphosphine (175 mg, 0.67 mmol) are added successively, and the reaction mixture is heated to reflux for 18 h. After cooling, the precipitated solids are filtered off with suction and washed with water and ethanol. The crude product is subjected to hot extraction once with toluene and three times with o-xylene, and finally sublimed under high vacuum. Yield: 12.92 g (20.7 mmol; 62%).

[0128] The following compounds can be prepared analogously: The catalyst system used may not only be Pd.sub.2(dba).sub.3 with triphenylphosphine but also S-Phos or X-Phos with Pd(OAc).sub.2 or Pd.sub.2(dba).sub.3. Purification can be effected using column chromatography, hot extraction or recrystallization. Recrystallization or hot extraction can be effected using standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, or recrystallization using high boilers such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

TABLE-US-00009 Reactant 1 Reactant 2 Product Yield [00694] [00695] [00696] 58% [00697] [00698] [00699] 54% [00700] [00701] [00702] 45% [00703] [00704] [00705] 38% [00706] [00707] [00708] 41% [00709] [00710] [00711] 17% [00712] [00713] [00714] 40% [00715] [00716] [00717] 33% [00718] [00719] [00720] 55% [00721] [00722] [00723] 61% [00724] [00725] [00726] 62% [00727] [00728] [00729] 37% [00730] [00731] [00732] 44%

##STR00733##

[0129] An initial charge of S1g (28.61 g, 100 mmol), 2-[1,1-biphenyl]-4-yl-4-chloro-6-(3-dibenzofuranyl)triazine (43.49 g, 100 mmol) [2170887-83-7] and K.sub.3PO.sub.4 (63.79 g, 300 mmol) in THF (1200 ml) and water (300 ml) is inertized with argon for 30 min. Subsequently, Pd(OAc).sub.2 (224 mg, 1.00 mmol) and X-Phos (1.00 g, 2.00 mmol) are added successively, and the mixture is stirred under reflux for 9 h. After cooling, the precipitated solids are filtered off with suction and washed with water and ethanol. The crude product is subjected to basic hot extraction twice with toluene and twice with n-butyl acetate over aluminum oxide, and finally sublimed under high vacuum. Yield: 32.7 g, (51.2 mmol, 51%), purity>99.9% by HPLC

[0130] The following compounds can be prepared analogously: The catalyst system used may not only be X-Phos but also S-Phos with not only Pd(OAc).sub.2 but also Pd.sub.2(dba).sub.3, or Pd(PPh.sub.3).sub.2Cl.sub.2 or Pd(PPh.sub.3).sub.4. Purification can be effected using column chromatography, hot extraction or recrystallization. Recrystallization or hot extraction can be effected using standard solvents such as ethanol, butanol, acetone, ethyl acetate, acetonitrile, toluene, xylene, dichloromethane, methanol, tetrahydrofuran, n-butyl acetate, 1,4-dioxane, or recrystallization using high boilers such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

TABLE-US-00010 Reactant 1 Reactant 2 Product Yield [00734] [00735] [00736] 45% [00737] [00738] [00739] 33% [00740] [00741] [00742] 38% [00743] [00744] [00745] 28% [00746] [00747] [00748] 32% [00749] [00750] [00751] 54% [00752] [00753] [00754] 44% [00755] [00756] [00757] 44% [00758] [00759] [00760] 34% [00761] [00762] [00763] 17% [00764] [00765] [00766] 42% [00767] [00768] [00769] 33% [00770] [00771] [00772] 15% [00773] [00774] [00775] 57% [00776] [00777] [00778] 39% [00779] [00780] [00781] 33% [00782] [00783] [00784] 53% [00785] [00786] [00787] 34% [00788] [00789] [00790] 42% [00791] [00792] [00793] 48% [00794] [00795] [00796] 55% [00797] [00798] [00799] 36% [00800] [00801] [00802] 31% [00803] [00804] [00805] 40% [00806] [00807] [00808] 44%

[0131] Production of the OLEDs

[0132] The examples which follow (see tables 1 to 7) present the use of the compounds of the invention in OLEDs by comparison with materials from the prior art.

[0133] Pretreatment for Examples V1 to V7 and E1a to E7b:

[0134] Glass plates coated with structured ITO (indium tin oxide) of thickness 50 nm are treated prior to coating, first with an oxygen plasma, followed by an argon plasma. These plasma-treated glass plates form the substrates to which the OLEDs are applied.

[0135] The OLEDs basically have the following layer structure: substrate/hole injection layer (HIL)/hole transport layer (HTL)/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 tables 1, 3 and 5. The materials required for production of the OLEDs, if they have not already been described before, are shown in table 7. The device data of the OLEDs are listed in tables 2, 4 and 6. Examples V1 to V7 are comparative examples. Examples E1a-g, E2a-g, E3a-f, E4a-f E5a-e, E6a-c, E7a, E7b show data of inventive OLEDs.

[0136] All materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the emission layer always consists of at least two matrix materials 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 P1a:H1:TE2 (32%:60%:8%) mean here that the material P1a is present in the layer in a proportion by volume of 32%, H1 in a proportion by volume of 60% and TE2 in a proportion by volume of 8%. Analogously, the electron transport layer may also consist of a mixture of two materials.

[0137] 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 color coordinates. The parameter U10 in tables 2 and 6 refers to the voltage which is required for a current density of 10 mA/cm.sup.2. EQE10 denotes the external quantum efficiency which is attained at 10 mA/cm.sup.2. The lifetime LD is defined as the time after which luminance, measured in cd/m.sup.2 in forward direction, drops from the starting luminance to a certain proportion L1 in the course of operation with constant current density j.sub.0. A figure of L1=80% in table 2 means that the lifetime reported in the LD column corresponds to the time after which luminance in cd/m.sup.2 falls to 80% of its starting value.

[0138] The parameter U1000 in table 4 refers to the voltage which is required for a luminance of 1000 cd/m.sup.2. EQE1000 denotes the external quantum efficiency which is attained at 1000 cd/m.sup.2. The lifetime LT is defined as the time after which the luminance drops from the starting luminance to a certain proportion L1 in the course of operation with constant current density j.sup.0. A figure of L1=95% in table 4 means that the lifetime reported in the LT column corresponds to the time after which the luminance falls to 95% of its starting value.

[0139] Use of Compounds of the Invention in OLEDs

[0140] The inventive materials are used in examples E1a-g, E2a-g, E3a-f, E4a-f E5a-e as matrix materials in the emission layer of green- or red-phosphorescent OLEDs, in examples E6a-c as hole blocker material in the hole blocker layer of blue-fluorescent OLEDs, and in examples E7a and E7b as electron transport materials in the electron transport layer of blue-fluorescent OLEDs. As a comparison from the prior art, materials SdT1, SdT2, SdT3 and SdT4 are used in combination with the host materials H1, H2 and H3 in comparative examples V1 to V5. In the comparison of the inventive examples with the corresponding comparative examples, it is clearly apparent that the inventive examples each show a distinct benefit in the lifetime of the OLED and, for the blue-fluorescent OLEDs in examples 6a-c, 7a und b by comparison with V6 and V7, a benefit in operating voltage and efficiency with otherwise comparable performance data of the OLED.

TABLE-US-00011 TABLE 1 Structure of the OLEDs for green emission HIL HTL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness V1 SpMA1:PD1 SpMA1 SpMA2 SdT1:H1:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E1a SpMA1:PD1 SpMA1 SpMA2 P1a:H1:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E1b SpMA1:PD1 SpMA1 SpMA2 P1a:H2:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E1c SpMA1:PD1 SpMA1 SpMA2 P4a:H1:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E1d SpMA1:PD1 SpMA1 SpMA2 P10a:H1:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E1e SpMA1:PD1 SpMA1 SpMA2 P12a:H1TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E1f SpMA1:PD1 SpMA1 SpMA2 P5b:H1:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E1g SpMA1:PD1 SpMA1 SpMA2 P7b:H1:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm V2 SpMA1:PD1 SpMA1 SpMA2 SdT2:H1:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (38%:50%:12%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E2a SpMA1:PD1 SpMA1 SpMA2 P1a:H1:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (38%:50%:12%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E2b SpMA1:PD1 SpMA1 SpMA2 P1a:H2:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (38%:50%:12%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E2c SpMA1:PD1 SpMA1 SpMA2 P7a:H2:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (38%:50%:12%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E2d SpMA1:PD1 SpMA1 SpMA2 P1b:H2:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (38%:50%:12%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E2e SpMA1:PD1 SpMA1 SpMA2 P8b:H1:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (38%:50%:12%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E2f SpMA1:PD1 SpMA1 SpMA2 P9b:H1:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:50%:12%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E2g SpMA1:PD1 SpMA1 SpMA2 P19b:H1:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:50%:12%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm V3 SpMA1:PD1 SpMA1 SpMA2 SdT3:H1:TE1 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E3a SpMA1:PD1 SpMA1 SpMA2 P1a:H1:TE1 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E3b SpMA1:PD1 SpMA1 SpMA2 P2a:H1:TE1 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E3c SpMA1:PD1 SpMA1 SpMA2 P2b:H2:TE1 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E3d SpMA1:PD1 SpMA1 SpMA2 P14b:H1:TE1 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E3e SpMA1:PD1 SpMA1 SpMA2 P3ab:H2:TE1 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E3f SpMA1:PD1 SpMA1 SpMA2 P12b:H2:TE1 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm V4 SpMA1:PD1 SpMA1 SpMA2 SdT4:H1:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E4a SpMA1:PD1 SpMA1 SpMA2 P11a:H2:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E4b SpMA1:PD1 SpMA1 SpMA2 P15b:H1:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E4c SpMA1:PD1 SpMA1 SpMA2 P17b:H2:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E4d SpMA1:PD1 SpMA1 SpMA2 P18b:H2:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E4e SpMA1:PD1 SpMA1 SpMA2 P25b:H2:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm E4f SpMA1:PD1 SpMA1 SpMA2 P26b:H2:TE2 ST2 ST2:LiQ LiQ (95%:5%) 200 nm 20 nm (32%:60%:8%) 5 nm (50%:50%) 1 nm 20 nm 40 nm 30 nm

TABLE-US-00012 TABLE 2 Data of the OLEDs for green emission U10 EQE10 CIE x/y at j.sub.0 L1 LD Ex. (V) (%) 1000 cd/m.sup.2 (mA/cm.sup.2) (%) (h) V1 4.4 20.5 0.34/0.63 40 80 200 E1a 4.2 23.0 0.34/0.63 40 80 650 E1b 4.4 22.5 0.34/0.63 40 80 770 E1c 4.2 22.0 0.34/0.63 40 80 810 E1d 4.2 22.3 0.34/0.63 40 80 500 E1e 4.3 23.2 0.35/0.63 40 80 880 E1f 4.1 23.5 0.34/0.63 40 80 630 E1g 4.3 22.2 0.34/0.63 40 80 720 V2 5.0 16.8 0.34/0.63 40 80 180 E2a 4.1 21.9 0.35/0.63 40 80 845 E2b 4.2 21.5 0.35/0.63 40 80 970 E2c 4.3 22.0 0.35/0.63 40 80 745 E2d 4.2 21.7 0.35/0.63 40 80 770 E2e 4.1 21.9 0.35/0.63 40 80 1220 E2f 4.3 20.9 0.35/0.63 40 80 1060 E2g 4.3 21.1 0.34/0.63 40 80 715 V3 6.0 13.0 0.34/0.62 40 80 140 E3a 4.9 19.2 0.34/0.62 40 80 490 E3b 4.7 18.8 0.33/0.62 40 80 690 E3c 4.9 19.0 0.33/0.62 40 80 975 E3d 4.6 18.8 0.33/0.62 40 80 785 E3e 4.6 18.2 0.33/0.62 40 80 955 E3f 4.5 18.6 0.33/0.62 40 80 810 V4 4.7 21.2 0.34/0.63 40 80 310 E4a 4.4 21.7 0.35/0.63 40 80 1020 E4b 4.2 21.9 0.34/0.63 40 80 1090 E4c 4.1 23.5 0.34/0.63 40 80 675 E4d 4.4 23.0 0.34/0.63 40 80 520 E4e 4.2 22.5 0.35/0.63 40 80 1170 E4f 4.3 23.3 0.35/0.63 40 80 965

TABLE-US-00013 TABLE 3 Structure of the OLEDs for red emission HIL HTL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness V5 SpMA1:PD1 SpMA1 SpMA2 SdT1:H3:TER1 ST2 ST2:LiQ LiQ (95%:5%) 110 nm 10 nm (57%:40%:3%) 10 nm (50%:50%) 1 nm 20 nm 35 nm 30 nm E5a SpMA1:PD1 SpMA1 SpMA2 P4b:H3:TER1 ST2 ST2:LIQ LiQ (95%:5%) 110 nm 10 nm (57%:40%:3%) 10 nm (50%:50%) 1 nm 20 nm 35 nm 30 nm E5b SpMA1:PD1 SpMA1 SpMA2 P6b:H1:TER1 ST2 ST2:LiQ LiQ (95%:5%) 110 nm 10 nm (57%:40%:3%) 10 nm (50%:50%) 1 nm 20 nm 35 nm 30 nm E5c SpMA1:PD1 SpMA1 SpMA2 P11b:H2:TER1 ST2 ST2:LiQ LiQ (95%:5%) 110 nm 10 nm (57%:40%:3%) 10 nm (50%:50%) 1 nm 20 nm 35 nm 30 nm E5d SpMA1:PD1 SpMA1 SpMA2 P13b:H2:TER1 ST2 ST2:LiQ LiQ (95%:5%) 110 nm 10 nm (57%:40%:3%) 10 nm (50%:50%) 1 nm 20 nm 35 nm 30 nm E5e SpMA1:PD1 SpMA1 SpMA2 P16b:H2:TER1 ST2 ST2:LiQ LiQ (95%:5%) 110 nm 10 nm (57%:40%:3%) 10 nm (50%:50%) 1 nm 20 nm 35 nm 30 nm

TABLE-US-00014 TABLE 4 Data of the OLEDs for red emission U1000 EQE 1000 CIE x/y at j.sub.0 L1 LD Ex. (V) (%) 1000 cd/m.sup.2 (mA/cm.sup.2) (%) (h) V5 3.7 24.1 0.66/0.33 60 95 12 E5a 3.4 25.5 0.66/0.33 60 95 110 E5b 3.3 26.0 0.67/0.33 60 95 70 E5c 3.4 26.1 0.67/0.33 60 95 65 E5d 3.4 25.2 0.66/0.33 60 95 57 E5e 3.2 26.1 0.66/0.33 60 95 49

TABLE-US-00015 TABLE 5 Structure of the OLEDs for blue emission HIL HTL EBL EML HBL ETL EIL Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Ex. nm nm nm nm nm nm nm V6 SpMA1:PD1(5%) SpMA1 SpMA2 H5:SEB(5%) SdT1 ST2:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 10 nm 20 nm 1 nm E6a SpMA1:PD1(5%) SpMA1 SpMA2 H5:SEB(5%) P1a ST2:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 10 nm 20 nm 1 nm E6b SpMA1:PD1(5%) SpMA1 SpMA2 H5:SEB(5%) P8b ST2:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 10 nm 20 nm 1 nm E6c SpMA1:PD1(5%) SpMA1 SpMA2 H5:SEB(5%) ST2 P11b:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 10 nm 20 nm 1 nm V7 SpMA1:PD1(5%) SpMA1 SpMA2 H5:SEB(5%) SdT1 SdT1:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 10 nm 20 nm 1 nm E7a SpMA1:PD1(5%) SpMA1 SpMA2 H5:SEB(5%) P1a P1a:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 10 nm 20 nm 1 nm E7b SpMA1:PD1(5%) SpMA1 SpMA2 H5:SEB(5%) P8a P8a:LiQ(50%) LiQ 20 nm 180 nm 10 nm 20 nm 10 nm 20 nm 1 nm

TABLE-US-00016 TABLE 6 Data of the OLEDs for blue emission Ex. U10 [V] EQE10 [%] V6 5.2 4.5 E6a 4.0 7.0 E6b 4.4 6.6 E6c 4.4 6.3 V7 6.2 4.3 E7a 5.0 6.7 E7b 5.4 6.0

TABLE-US-00017 TABLE 7 Structural formulae of the materials of the OLEDs used, if not already described before: [00809] PD1 (CAS Reg. No. 1224447-88-4) [00810] SpMA1 [00811] SpMA2 [00812] ST2 [00813] LiQ [00814] TE1 [00815] TE2 [00816] TER1 [00817] H1 [00818] H2 [00819] H3 [00820] SEB [00821] H5 [00822] SdT1 (WO 2012/048781) [00823] SdT2 (WO 2012/048781) [00824] SdT3 (WO 2012/048781) [00825] SdT4 (WO 2012/048781)