MATERIALS FOR ORGANIC ELECTROLUMINESCENT DEVICES

Abstract

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

Claims

1.-10. (canceled)

11. A compound of formula (1) ##STR00688## where the symbols and indices used are as follows: X is the same or different at each instance and is CR or N, with the proviso that not more than two X groups per cycle are N, and also with the proviso that two adjacent X groups that are part of the same six-membered ring are CR, where the adjacent R radicals form an aromatic or heteroaromatic ring system which has 4 to 8 ring atoms, is fused onto the cycle and may be substituted by one or more R radicals; Y is the same or different at each instance and is a BR, C(R).sub.2, CO, Si(R).sub.2, NR, NAr.sup.1, O, S, Se, SO, SO.sub.2, PR or P(O)R, where, in the case that m or n is 0, the carbon atoms that bind to Y are each X; m and n are 0 or 1, where m+n is 1; Ari is an aromatic ring system which has 6 to 40 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals, or a heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; R is the same or different at each instance and is H, D, F, Cl, Br, I, N(Ar).sub.2, N(R.sup.1).sub.2, OAr, SAr, B(OR.sup.1).sub.2, CHO, C(O)R.sup.1, CR.sup.1C(R.sup.1).sub.2, CN, C(O)OR.sup.1, C(O)NR.sup.1, Si(R.sup.1).sub.3, NO.sub.2, P(O)(R.sup.1).sub.2, OSO.sub.2R.sup.1, OR, S(O)R.sup.1, S(O).sub.2R.sup.1, SR.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 be substituted in each case by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.1CCR.sup.1, CC, Si(R.sup.1).sub.2, NR.sup.1, CONR.sup.1, CO, CS, C(O)O, P(O)(R), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and may be substituted in each case by one or more R.sup.1 radicals, where two or more R radicals bonded to the same cycle may together form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R.sup.1 radicals, and where two R radicals bonded to the same carbon or silicon atom may together form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R.sup.1 radicals; Ar 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; R.sup.1 is the same or different at each instance and is H, D, F, I, B(OR.sup.2).sub.2, N(R.sup.2).sub.2, CHO, C(O)R.sup.2, CR.sup.2C(R.sup.2).sub.2, CN, C(O)OR.sup.2, Si(R.sup.2).sub.3, NO.sub.2, P(O)(R.sup.2).sub.2, OSO.sub.2R.sup.2, SR.sup.2, OR.sup.2, S(O)R.sup.2, S(O).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 in each case be substituted by one or more R.sup.2 radicals and where one or more CH.sub.2 groups in the abovementioned groups may be replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, CO, CS, C(O)O, NR.sup.2, CONR.sup.2, P(O)(R.sup.2), O, S, SO or SO.sub.2, and where one or more hydrogen atoms in the abovementioned groups 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 30 aromatic ring atoms and may be substituted in each case by one or more R.sup.2 radicals, where two or more R.sup.1 radicals together may form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system; 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 D or F; at the same time, two or more R.sup.2 substituents may be joined to one another and may form a ring.

12. The compound as claimed in claim 11, comprising a structure of the formula (2) ##STR00689## where the symbols and indices used have the definitions given in claim 11 and in addition: X is the same or different at each instance and is CR or N, with the proviso that not more than two X groups per cycle are N; and two adjacent X groups that are part of the same cycle are C, at which a group of the formula (2), via the bonds identified by *, form an aromatic or heteroaromatic ring system fused onto the cycle; Q is the same or different at each instance and is CR.sup.1 or N, with the proviso that at most two Q groups per ring are N.

13. The compound as claimed in claim 11, selected from the compounds of the formulae (3) and (4) ##STR00690## where the symbols and indices used have the definitions given in claim 11 and in addition: X is the same or different at each instance and is CR or N, with the proviso that not more than two X groups per cycle are N; and two adjacent X groups that are part of the same cycle are C; Q is the same or different at each instance and is CR.sup.1 or N, with the proviso that at most two Q groups per ring are N.

14. The compound as claimed in claim 11, selected from the compounds of the formulae (5) to (8) ##STR00691## where the symbols and indices used have the definitions given in claim 11 and in addition: X is the same or different at each instance and is CR or N, with the proviso that not more than two X groups per cycle are N; and two adjacent X groups that are part of the same cycle are C; Q is the same or different at each instance and is CR.sup.1 or N, with the proviso that at most two Q groups per ring are N.

15. The compound as claimed in claim 11, selected from the compounds of the formulae (5-1) to (8-1) ##STR00692## where the symbols used have the definitions given in claim 11.

16. The compound as claimed in claim 11, wherein Y is NAr.sup.1, O or S.

17. A formulation comprising at least one compound as claimed in claim 11 and at least one further compound and/or at least one solvent.

18. A method comprising providing the compound as claimed in claim 11 and incorporating the compound in an electronic device.

19. An electronic device comprising at least one compound as claimed in claim 11.

20. The electronic device as claimed in claim 19 which is an organic electroluminescent device, 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), or in an electron transport layer and/or in a hole blocker layer and/or in a hole transport layer and/or in an exciton blocker layer.

Description

EXAMPLES

[0126] The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The respective figures in square brackets or the numbers quoted for individual compounds relate to the CAS numbers of the compounds known from the literature.

[0127] Preparation of the Synthons:

##STR00208##

[0128] Trifluoromethanesulfonic acid (73 g, 482 mmol) is added dropwise to a solution of 2-iodo-1,1-biphenyl (45 g, 160 mmol) and 3-chlorobenzoic acid (55.5 g, 241 mmol) in DCM (700 mL) at 0 C. over a period of 30 min. Subsequently, the reaction is allowed to warm up to room temperature and left to stir for one hour, and the reaction mixture is then concentrated. MTBE (300 mL) is added to the residue, and the mixture is stirred at room temperature for 1 h. The solids are filtered off and washed with MTBE (350 mL) and dried in a vacuum drying cabinet. Yield: 56.4 g (131 mmol, 82%), 96% by NMR.

##STR00209##

[0129] An initial charge under an inert atmosphere in a closed 1 L flask is formed by 3-amino-1-chloro-2-naphthalenecarboxylic acid (11.59 g. 52.3 mmol) [CAS-1823470-44-5], S1a (56.4 g, 131 mmol), K.sub.2CO.sub.3, (16.00 g, 115.9 mmol) and NMP (350 mL). Subsequently, Pd(OAc).sub.2 (350 mg, 1.66 mmol) is added and the reaction mixture is stirred at 145 C. for 17 h.

[0130] After cooling, the reaction is worked up by extraction with ethyl acetate and water. The combined organic phases are washed 3 with water (200 mL each time) and 2 with sat. NaCl solution (100 mL each time) and dried over Na.sub.2SO.sub.4, and the solvent was removed by rotary evaporation on a rotary evaporator. The crude product is purified further by column chromatography. Yield: 3.8 g (13 mmol, 25%), 95% purity by .sup.1H NMR.

##STR00210##

[0131] Compound S2b can be prepared analogously to the procedure described for synthon S2a proceeding from 1-amino-3-chloronaphthalene-2-carboxylic acid and S1a. Yield: 21%

##STR00211##

[0132] An initial charge under an inert atmosphere was formed by 2-bromo-1-chloro-3-nitrobenzene (23.6 g, 100 mmol) [CAS-19128-48-4], B-[2-(1-naphthyl]phenyl]boronic acid (24.8 g, 100 mmol) [CAS-500904-93-8] and sodium carbonate (21.2 g, 200 mmol) in toluene (700 mL) and water (150 mL). Subsequently, tetrakis(triphenylphosphine)palladium(0) (2.32 g, 2.00 mmol) is added and the reaction mixture is stirred under reflux for 16 h. After cooling, the reaction mixture is filtered with suction through a frit packed with toluene and Celite and then worked up by extraction with toluene and water. The organic phase is washed with water (200 mL) and sat. NaCl solution (100 mL) 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: 21.6 g (60 mmol, 60%), 96% purity by .sup.1H NMR.

##STR00212##

[0133] Compound S3b can be prepared analogously to the procedure described for synthon S3a. Rather than B-[2-(1-naphthyl]phenyl]boronic acid, B-[2-(2-naphthyl)phenyl]boronic acid is used. Yield: 55%

##STR00213##

[0134] Compound S3c can be prepared analogously to the procedure described for synthon S3a proceeding from 2-bromo-3-chloro-6-methoxynitrobenzene [1698810-56-8] and B-[2-(1-naphthyl]phenyl]boronic acid. Yield: 46%

##STR00214##

[0135] An initial charge under an inert atmosphere is formed by S3a (21.6 g, 60 mmol) and potassium carbonate (41.5 g, 300 mmol) in dimethylacetamide (400 mL). Subsequently, palladium acetate (674 mg, 3.00 mmol) and 1,3-bis(2,6-diisopropylphenyl)-3H-imidazol-1-ium chloride (2.55 g, 6.00 mmol) [CAS-250285-32-6] are added and the reaction mixture is stirred at 145 C. for 24 h. After cooling, the DMAc is largely removed by rotary evaporation, and the mixture is worked up by extraction with toluene (600 mL) and water. The aqueous phase is extracted 2 with toluene (250 mL each time). Subsequently, the combined organic phases are washed 2 with water (300 mL each time) and sat. NaCl solution (150 mL) and dried over Na.sub.2SO.sub.4, and the filtrate is concentrated by rotary evaporation. 400 mL of n-heptane is added to the crude product and the mixture is stirred at room temperature for 30 min. Subsequently, the solids are filtered off with suction, washed with n-heptane and dried in a vacuum drying cabinet. Yield: 10.1 g (31.2 mmol, 52%), 95% purity by .sup.1H NMR.

##STR00215##

[0136] Compound S4b can be prepared analogously to the procedure described for synthon S4a proceeding from S3b. Yield: 32%

##STR00216##

[0137] Compound S4c can be prepared analogously to the procedure described for synthon S4a proceeding from S3c. Yield: 49%

##STR00217##

[0138] S4a (14.4 g, 44.4 mmol) in 150 mL of ethanol is hydrogenated over 1 g of palladium/charcoal at hydrogen pressure 3 bar over the course of 36 h. The reaction mixture is filtered 2 through a Celite bed. The filtrate is concentrated by rotary evaporation, and the solids obtained are recrystallized from toluene.

[0139] Yield: 10.7 g (36.6 mmol, 82%), 97% purity by .sup.1H NMR.

##STR00218##

[0140] Compound S5b can be prepared analogously to the procedure described for synthon S5a proceeding from S4b. Yield: 87%

##STR00219##

[0141] Compound S5c can be prepared analogously to the procedure described for synthon S5a proceeding from S4c. Yield: 62%

##STR00220##

[0142] An initial charge in a flask is formed by S2a (3.8 g, 13.0 mmol), pivalic acid (2.66 g, 26.0 mmol), Cu(OAc).sub.2 [CAS-142-71-2] (485 mg, 2.67 mmol), [Cp*IrCl.sub.2].sub.2 [CAS-12354-84-6] (426 mg, 0.53 mmol) and NMP (100 mL). Air is passed through the reaction mixture with a needle, and the reaction is stirred at 120 C. for 50 min. After cooling, the NMP is distilled off and the residue is purified further via column chromatography. Yield: 3.1 g (10.5 mmol, 81%), 98% purity by .sup.1H NMR.

##STR00221##

[0143] Analogously to S6a, compound S6b can be prepared proceeding from S5a. Yield: 72%

##STR00222##

[0144] Analogously to S6a, compound S6c can be prepared proceeding from S5b. Yield: 76%

##STR00223##

[0145] Analogously to S6a, compound S6d can be prepared proceeding from S2b. Yield: 44%

##STR00224##

[0146] Analogously to S6a, compound S6e can be prepared proceeding from S5c. Yield 36%

##STR00225##

[0147] An initial charge under an inert atmosphere is formed by DMSO (100 mL), K.sub.3PO.sub.4 (106.15 g, 500 mmol), pyridine-2-carboxylic acid (3.06 g, 24.87 mmol) and CuI (2.37 g, 12.44 mmol). Subsequently, 3-chloro-5-methoxyphenol (45.57 g, 300 mmol) [65262-96-6] and 3-bromo-1-chloronaphthalene (60.38 g, 250 mmol) [325956-47-6] are gradually added successively, and the reaction mixture is heated at 85 C. for 16 h.

[0148] After cooling, the reaction mixture is worked up by extraction with aqueous ammonia solution and methyl tert-butyl ether. The organic phase is washed 5 times with water and twice with sat. NaCl solution, the combined 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: 64.64 g (202 mmol), 81% purity, 95% by .sup.1H NMR.

[0149] 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-00001 Reactant 1 Reactant 2 Product Yield [00226] [00227] [00228] 76% 779198-52-6 325956-47-6 7b [00229] [00230] [00231] 63% 51671-06-8 7c [00232] [00233] [00234] 85% 7d [00235] [00236] [00237] 70% 7e [00238] [00239] [00240] 74% 7f

##STR00241##

[0150] An initial charge of S7a (159.6 g, 500 mmol) in THE (750 mL) under an inert atmosphere is cooled down to 75 C. Subsequently, n-butyllithium (2.5 mol/L in hexane, 400 mL, 1.00 mmol) is slowly added dropwise in such a way that the internal temperature does not exceed 65 C. The mixture is left to stir at 75 C. for a further 4 h, and then bromine (28.0 mL, 546.5 mmol) is added dropwise 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 sat. Na.sub.2SO.sub.3 solution (250 mL). The mixture is worked up by extraction with toluene and water, the combined organic phases are washed 3 times with water and once with sat. NaCl solution and dried over Na.sub.2SO.sub.4, and the solvent is removed on a rotary evaporator. The crude product is extracted by stirring 3 times with 2-propanol under reflux. The product is converted further as an isomer mixture. Yield: 133.8 g (370 mmol, 74%), purity 95% by .sup.1H NMR.

[0151] The following compounds can be prepared analogously: Purification can be effected not only by extractive stirring but also by distillation, or 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 Product Yield [00242] [00243] 70% + [00244] 8b [00245] [00246] 68% + [00247] 8c [00248] [00249] 86% 8d [00250] [00251] 71% + [00252] 8e [00253] [00254] 79% 8f

[0152] S9a:

##STR00255##

[0153] An initial charge of S8d (139.0 mmol), B-(6-methoxy-2-naphthyl)boronic acid (31.21 g, 154.5 mmol) [156641-984] and K.sub.2CO.sub.3 (38.84 g, 281.0 mmol) in THF (720 mL) and water (180 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 16 h. The mixture is worked up by extraction with toluene and water, the combined organic phases are washed with water and sat. 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 ethyl acetate. Yield: 35.8 g (100 mmol, 72%), 97% by .sup.1H NMR.

[0154] 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-00003 Reactant 1 Reactant 2 Product Yield [00256] [00257] [00258] 56% 8d 219834-95-4 S9b [00259] [00260] [00261] 65% + 98-80-6 + [00262] [00263] 8a S9c [00264] [00265] [00266] 51% + 98-80-6 + [00267] [00268] 8b S9d [00269] [00270] [00271] 78% + 98-80-6 + [00272] [00273] 8c S9e [00274] [00275] [00276] 48% + 98-80-6 + [00277] [00278] 8e S9f [00279] [00280] [00281] 55% 8f 219834-95-4 S9g [00282] [00283] [00284] 52% CAS-2136632-67-0 219834-95-4 S9h [00285] [00286] [00287] 58% 219834-95-4 S9i

[0155] S10a:

##STR00288##

[0156] To an initial charge of S9b (35.08 g, 100 mmol) and K.sub.2CO.sub.3 (41.37 g, 299.3 mmol) under an inert atmosphere is added DMAc (500 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 155 C. for 16 h. After cooling, the mixture is poured into ethanol/water (1:1, 800 mL) and stirred for a further 30 min. The precipitated solids are filtered off with suction and washed 5 times with water and 3 times with ethanol. The crude product is extracted by stirring with 2-propanol under reflux. Yield: 26.4 g (82 mmol, 82%), 97% by 1H NMR.

[0157] 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-00004 Reactant 1 Product Yield [00289] [00290] 73% S9a S10b [00291] [00292] 78% + S10c [00293] S9c [00294] [00295] 81% + S10d [00296] S9d [00297] [00298] 85% + S10e [00299] S9e [00300] [00301] 68% + S10f [00302] S9f [00303] [00304] 65% S9g S10g [00305] [00306] 38% S9h S10h [00307] [00308] 49% S9i S10i

[0158] S11a:

##STR00309##

[0159] An initial charge of S10a (32.21 g, 100 mmol) in dichloromethane (650 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 (200 mL). The solvent is drawn off on a rotary evaporator. Subsequently, each of 3 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 as such in the next stage. Yield 19.4 g (63 mmol, 63%).

[0160] 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-00005 Reactant 1 Product Yield [00310] [00311] 70% S10b S11b [00312] [00313] 72% S10c S11c [00314] [00315] 75% S10d S11d [00316] [00317] 66% S10e S11e [00318] [00319] 62% S10f S11f [00320] [00321] 56% S10g S11g [00322] [00323] 55% S10h S11h [00324] [00325] 49% S10i S11i [00326] [00327] 51% S14a S11j

##STR00328##

[0161] S12a

[0162] An initial charge of S11a (13.95 g, 45.3 mmol) and triethylamine (18.8 mL, 135.9 mmol) in dichloromethane (650 mL) is cooled to 0 C. in an ice bath. Subsequently, trifluoromethanesulfonic anhydride (9.9 mL, 58.9 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 400 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 14.95 g (34.0 mmol, 75%)

[0163] 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 1 Product Yield [00329] [00330] 70% S11b S12b [00331] [00332] 72% S11c S12c [00333] [00334] 75% S11d S12d [00335] [00336] 66% S11e S12e [00337] [00338] 62% S11f S12f [00339] [00340] 56% S11g S12g [00341] [00342] 47% S11h S12h [00343] [00344] 43% S11i S12i [00345] [00346] 31% S11j S12j

[0164] S13a

##STR00347##

[0165] An initial charge of S12b (13.28 g, 30.2 mmol), bis(pinacolato)diboron (9.40 g, 36.3 mmol) and KOAc (8.90 g, 90.68 mmol) in 1,4-dioxane (250 ml) is inertized for 30 min. Then Pd(dppf)Cl.sub.2 (740 mg, 0.91 mmol) is added, and the mixture 20 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-methylpyrrolidone, etc.

TABLE-US-00007 Reactant 1 Product Yield [00348] [00349] 48% 12a S13b [00350] [00351] 77% S12c S13c [00352] [00353] 80% S12d S13d [00354] [00355] 64% S12e S13e [00356] [00357] 70% S12f S13f [00358] [00359] 50% S12g S13g [00360] [00361] 47% S12i S13i [00362] [00363] 33% S12j S13j

[0166] S14:

##STR00364##

[0167] An initial charge is formed by S6e (32.1 g, 100 mmol), bromobenzene (17.3 g, 110 mmol) and sodium tert-butoxide (20.18 g, 210 mmol) in toluene (800 mL). Subsequently, XPhos Pd G3 [CAS-1445085-55-1](3.40 g, 4.6 mmol) is added and the reaction solution is heated to boiling for 24 h. The reaction solution is left to cool to room temperature. The reaction mixture is worked up by extraction with toluene and water. 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 recrystallized from n-butyl acetate. Yield: 18.0 g (87 mmol, 87%), purity 98% by .sup.1H NMR.

[0168] Preparation of the Compounds of the Invention

[0169] Synthesis of P1a:

##STR00365##

[0170] An initial charge is formed by S6a (8.30 g, 28.5 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (8.40 g, 31.3 mmol) [CAS-3842-55-5] and sodium tert-butoxide (3.00 g, 31.3 mmol) in toluene (250 mL). Subsequently, XPhos Pd G3 [CAS-1445085-55-1] (2.10 g, 2.8 mmol) is added and the reaction solution is heated to boiling for 72 h. The reaction solution is cooled down to room temperature and the solvent is removed by rotary evaporator. The crude product is purified via column chromatography (n-heptane/ethyl acetate), followed by recrystallization 4 times from n-butyl acetate and sublimation under high vacuum. Yield: 7.9 g (15.1 mmol, 53%); purity: >99.9% by HPLC.

[0171] The following compounds can be prepared analogously: 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-methylpyrrolidone, etc.

TABLE-US-00008 Reactant 1 Reactant 2 Product Yield [00366] [00367] [00368] 46% CAS-3842-55-5 S6b P1b [00369] [00370] [00371] 48% CAS-1300115-09-6 S6a P1c [00372] [00373] [00374] 53% CAS-1300115-09-6 S6b P1d [00375] [00376] [00377] 45% CAS-1472062-95-5 S6a P1e [00378] [00379] [00380] 41% CAS-1472062-95-5 S6b P1f [00381] [00382] [00383] 60% CAS-1621467-30-8 S6a P1g [00384] [00385] [00386] 58% CAS-1621467-30-8 S6b P1h [00387] [00388] [00389] 44% CAS-2142681-84-1 S6a P1i [00390] [00391] [00392] 38% CAS-2142681-84-1 S6b P1j [00393] [00394] [00395] 55% CAS-2074632-09-8 S6a P1k [00396] [00397] [00398] 46% CAS-2074632-09-8 S6b P1l [00399] [00400] [00401] 58% CAS-2172944-02-2 S6a P1m [00402] [00403] [00404] 59% CAS-2172944-02-2 S6b P1n [00405] [00406] [00407] 51% CAS-1472062-94-4 S6a P1o [00408] [00409] [00410] 47% CAS-1472062-94-4 S6b P1p [00411] [00412] [00413] 49% CAS-2260688-83-1 S6a P1q [00414] [00415] [00416] 50% CAS-2260688-83-1 S6b P1r [00417] [00418] [00419] 42% CAS-2915-16-4 S6a P1s [00420] [00421] [00422] 48% CAS-2915-16-4 S6b P1t [00423] [00424] [00425] 34% CAS-6484-25-9 S6a P1u [00426] [00427] [00428] 31% CAS-6484-25-9 S6b P1v [00429] [00430] [00431] 50% CAS-1472062-94-4 S6c P1w [00432] [00433] [00434] 15% CAS-1472062-94-4 S6d P1x [00435] [00436] [00437] 40% CAS-1205748-61-3 S6b P1y [00438] [00439] [00440] 35% CAS-1205748-61-3 S6a P1z [00441] [00442] [00443] 42% CAS-1205748-61-3 S6c P1za [00444] [00445] [00446] 21% CAS-1205748-61-3 S6d P1zb

[0172] P1a:

##STR00447##

[0173] An initial charge is formed by S6a (17.92 g, 61.5 mmol), 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine [CAS-864377-31-1] (25.2 g, 65.0 mmol) and sodium tert-butoxide (13.4 g, 139.1 mmol) in o-xylene (550 mL). Subsequently, XPhos Pd G3 (1.70 g, 2.3 mmol) is added and the reaction solution is heated to boiling for 24 h. The reaction solution is left to cool to room temperature, and the precipitated solids are filtered off with suction and washed 3 with ethanol (150 mL each time). The crude product is subjected to basic hot extraction three times with toluene over aluminum oxide, then recrystallized 2 from 1,4-dioxane and finally sublimed under high vacuum. Yield: 18.0 g (30.1 mmol, 49%), purity: >99.9% by HPLC.

[0174] The following compounds can be prepared analogously: The catalyst system used may also be Pd.sub.2(dba).sub.3 or Pd(OAc).sub.2 together with X-Phos or S-Phos. 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 [00448] [00449] [00450] 57% CAS-864377-31-1 S6b P2b [00451] [00452] [00453] 53% CAS-1907704-74-8 S6a P2c [00454] [00455] [00456] 53% CAS-1907704-74-8 S6b P2d [00457] [00458] [00459] 56% CAS-1613700-80-3 S6a P2e [00460] [00461] [00462] 43% CAS-1613700-80-3 S6b P2f [00463] [00464] [00465] 58% CAS-864377-22-0 S6a P2g [00466] [00467] [00468] 58% CAS-864377-22-0 S6b P2h [00469] [00470] [00471] 66% CAS-1646861-13-3 S6a P2i [00472] [00473] [00474] 61% CAS-1646861-13-3 S6b P2j [00475] [00476] [00477] 40% CAS-1800220-86-7 S6a P2k [00478] [00479] [00480] 35% CAS-1800220-86-7 S6b P2l [00481] [00482] [00483] 46% CAS-2379260-79-2 S6a P2l [00484] [00485] [00486] 50% CAS-2379260-79-2 S6b P2m [00487] [00488] [00489] 59% CAS-2377798-39-3 S6a P2n [00490] [00491] [00492] 36% CAS-2377798-39-3 S6b P2o [00493] [00494] [00495] 40% CAS-1869142-07-3 S6a P2p [00496] [00497] [00498] 41% CAS-1869142-07-3 S6b P2q [00499] [00500] [00501] 40% CAS-1800220-86-7 S6c P2r [00502] [00503] [00504] 17% CAS-1800220-86-7 S6d P2s [00505] [00506] [00507] 34% CAS-2102445-25-8 S6b P2t [00508] [00509] [00510] 38% CAS-2408705-82-6 S6a P2u [00511] [00512] [00513] 36% CAS-2375066-17-2 S6d P2v [00514] [00515] [00516] 37% CAS-2399473-96-0 S6c P2w [00517] [00518] [00519] 44% CAS-12822310-63-3 S6b P2x [00520] [00521] [00522] 48% CAS-185112-61-2 S6b P2y [00523] [00524] [00525] 61% S6a P2z [00526] [00527] [00528] 58% CAS-26608-06-0 S6d P2za [00529] [00530] [00531] 34% CAS-2399464-48-1 S6c P2zb [00532] [00533] [00534] 30% CAS-2183475-67-2 S6b P2zc [00535] [00536] [00537] 38% CAS-2183475-67-2 S6a P2zd [00538] [00539] [00540] 56% CAS-160892-07-9 S6b P2ze [00541] [00542] [00543] 51% CAS-160892-07-9 S6a P2zf

[0175] P3a:

##STR00544##

[0176] To an initial charge of S6a (17.48 g, 60.0 mmol) in DMSO (400 mL) is added sodium tert-butoxide (6.34 g, 66.0 mmol), and the mixture is stirred at room temperature for 30 min. Subsequently, 2-chloro-4-d5-phenylquinazoline (16.25 g, 66.0 mmol) [CAS-1614244-83-5] is added and the reaction is stirred at room temperature for 24 h. Subsequently, the solvent is removed under reduced pressure and the residue is extracted by stirring with 1500 mL hot ethanol. The crude product is subjected to basic hot extraction three times with o-xylene over aluminum oxide, then recrystallized 2 from DMF and finally sublimed under high vacuum. Yield: 16.52 g (33.0 mmol, 55%); purity: >99.9% by HPLC.

[0177] The following compounds can be prepared analogously: 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 [00545] [00546] [00547] 46% CAS-1614244-83-5 S6b P3b [00548] [00549] [00550] 50% CAS-1709578-41-5 S6a P3c [00551] [00552] [00553] 54% CAS-1709578-41-5 S6b P3d [00554] [00555] [00556] 55% CAS-1262866-93-2 S6a P3e [00557] [00558] [00559] 48% CAS-1262866-93-2 S6b P3f [00560] [00561] [00562] 34% CAS-2075660-93-2 S6a P3g [00563] [00564] [00565] 41% CAS-2075660-93-2 S6b P3h [00566] [00567] [00568] 57% CAS-666854-39-3 S6a P3i [00569] [00570] [00571] 50% CAS-666854-39-3 S6b P3j [00572] [00573] [00574] 43% CAS-29874-83-7 S6c P3k [00575] [00576] [00577] 24% CAS-29874-83-7 S6d P3l

[0178] P4a:

##STR00578##

[0179] To an initial charge of S6a (17.48 g, 60.0 mmol) and 2-chloro-3-phenylquinoxaline (20.0 g, 60.0 mmol) [CAS-7065-92-1] in DMF (350 mL) is added potassium phosphate (38.20 g, 180.0 mmol), and the mixture is stirred under reflux for 24 h. After cooling, the solvent is removed under reduced pressure, and the residue obtained is suspended in 250 mL of ethanol and 250 mL of water. The solids are filtered off and washed with ethanol (5150 mL). The crude product is subjected to basic hot extraction twice with toluene and twice with n-butyl acetate over aluminium oxide, and then sublimed under high vacuum. Yield: 13.96 g (28.2 mmol, 47%), purity: >99.9% by HPLC.

[0180] The following compounds can be prepared analogously: 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-methyl pyrrolidone, etc.

TABLE-US-00011 Reactant 1 Reactant 2 Product Yield [00579] [00580] [00581] 50% CAS-7065-92-1 S6b P4b [00582] [00583] [00584] 51% CAS-2305856-66-8 S6a P4c [00585] [00586] [00587] 45% CAS-2305856-66-8 S6b P4d [00588] [00589] [00590] 50% CAS-.2376527-28-3 S6a P4e [00591] [00592] [00593] 50% CAS-.2376527-28-3 S6b P4f [00594] [00595] [00596] 32% CAS-955938-18-8 S6a P4g [00597] [00598] [00599] 30% CAS-955938-18-8 S6b P4h [00600] [00601] [00602] 38% CAS-2176462-89-6 S6a P4i [00603] [00604] [00605] 40% CAS-2176462-89-6 S6b P4j [00606] [00607] [00608] 34% CAS-2245928-02-1 S6a P4k [00609] [00610] [00611] 40% CAS-2245928-02-1 S6b P4l [00612] [00613] [00614] 44% CAS-2376527-27-2 S6a P4m [00615] [00616] [00617] 32% CAS-2376527-27-2 S6b P4n [00618] [00619] [00620] 36% CAS-7065-92-1 S6c P4o

[0181] P5a:

##STR00621##

[0182] An initial charge of S13a (33.3 mmol) of 2-[1,1-biphenyl]-4-yl-4-(3-bromophenyl)-6-phenyl-1,3,5-triazine (35.0 mmol) [CAS-1955546-91-4] and K.sub.3PO.sub.4 (14.14 g, 66.6 mmol) in toluene/dioxane/water (200 mL/200 mL/100 mL) is inertized for 30 min. Subsequently, triphenylphosphine (175 mg, 0.67 mmol) and Pd.sub.2(dba).sub.3 (305 mg, 0.33 mmol) are added successively, and the mixture is stirred under reflux for 16 h. The mixture is worked up by extraction with toluene and water. 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 subjected to hot extraction three times with toluene/heptane 1:1, then recrystallized twice from n-butyl acetate and finally sublimed under high vacuum. Yield: 10.6 g (15.7 mmol, 47%), purity: >99.9% by HPLC The following compounds can be prepared analogously: The catalyst system used may also be S-Phos or X-Phos or P(o-tol).sub.3 with Pd.sub.2(dba).sub.3 or Pd(OAc).sub.2. 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-methyl pyrrolidone, etc.

TABLE-US-00012 Reactant 1 Reactant 2 Product Yield [00622] [00623] [00624] 50% CAS-955938-18-8 S13c P5b [00625] [00626] [00627] 54% CAS-1800220-86-7 S13c P5c [00628] [00629] [00630] 48% CAS-2142681-84- S13d P5d [00631] [00632] [00633] 56% CAS-2260688-83-1 S13e P5e [00634] [00635] [00636] 36% CAS-6484-25-9 S13f P5f [00637] [00638] [00639] 25% CAS-1646861-13-3 S13g P5g [00640] [00641] [00642] 27% S12h CAS-1373359-67-1 P5h [00643] [00644] [00645] 36% CAS-1428551-28-3 S12i P5i [00646] [00647] [00648] 25% CAS-1800220-86-7 S12i P5j [00649] [00650] [00651] 18% CAS-2176462-89-6 S13j P5k [00652] [00653] [00654] 36% CAS-1449401-87-9 S13j P5l [00655] [00656] [00657] 37% CAS-1428551-28-3 S13j P5m [00658] [00659] [00660] 49% CAS-160892-07-9 S13j P5n [00661] [00662] [00663] 45% CAS-955959-84-9 S12i P5o [00664] [00665] [00666] 60% CAS-160892-07-9 S13c P5p [00667] [00668] [00669] 48% CAS-1257220-44-2 S13c P5q [00670] [00671] [00672] 32% CAS-1614244-83-5 S13b P5r

[0183] Production of the OLEDs

[0184] Pretreatment for Examples V1 to E5h: 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.

[0185] 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 table 1. The materials required for production of the OLEDs are shown in table 3. The data of the OLEDs are listed in table 2.

[0186] All materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the emission layer always consists of at least one matrix material (host material) and an emitting dopant (emitter) which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as P1a:IC2:TER1 (57%:40%:3%) mean here that the material P1a is present in the layer in a proportion by volume of 57%, IC2 in a proportion by volume of 40% and TER1 in a proportion by volume of 3%. Analogously, the electron transport layer may also consist of a mixture of two materials.

[0187] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the external quantum efficiency (EQE, measured in %) as a function of the luminance, calculated from current-voltage-luminance characteristics assuming Lambertian radiation characteristics, and the lifetime are determined. 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 U1000 in table 3 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.sub.0. A figure of L1=95% in table 3 means that the lifetime reported in the LT column corresponds to the time after which the luminance falls to 95% of its starting value.

[0188] Use of Mixtures of the Invention in the Emission Layer of Phosphorescent OLEDs

[0189] The inventive materials are used in examples E1a-E1n, E2a-E2j, E3a-E3f, E4a-E4e and E5a-E5h as matrix material in the emission layer of red-phosphorescing OLEDs. By comparison with the prior art (V1 to V5), it is possible to achieve a distinct improvement in lifetime with otherwise comparable parameters.

TABLE-US-00013 TABLE 1 Structure of the OLEDs HIL HTL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thicknes thickness thickness V1 SpMA1:PD1 SpMA1 SpMA2 SdT1:IC2: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 E1a SpMA1:PD1 SpMA1 SpMA2 P1a:IC2: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 E1b SpMA1:PD1 SpMA1 SpMA2 P1h:IC2: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 E1c SpMA1:PD1 SpMA1 SpMA2 P1o:IC2: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 E1d SpMA1:PD1 SpMA1 SpMA2 P1za:IC2: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 E1e SpMA1:PD1 SpMA1 SpMA2 P2c:IC2: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 E1f SpMA1:PD1 SpMA1 SpMA2 P2l:IC2: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 E1g SpMA1:PD1 SpMA1 SpMA2 P2r:IC2: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 E1h SpMA1:PD1 SpMA1 SpMA2 P2u:IC2: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 E1i SpMA1:PD1 SpMA1 SpMA2 P2zc:IC2: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 E1j SpMA1:PD1 SpMA1 SpMA2 P3a:IC2: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 E1k SpMA1:PD1 SpMA1 SpMA2 P3j:IC2: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 E1l SpMA1:PD1 SpMA1 SpMA2 P4b:IC2: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 E1m SpMA1:PD1 SpMA1 SpMA2 P4c:IC2: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 E1n SpMA1:PD1 SpMA1 SpMA2 P5c:IC2: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 V2 SpMA1:PD1 SpMA1 SpMA2 SdT2:IC1: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 E2a SpMA1:PD1 SpMA1 SpMA2 P1s:IC1: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 E2b SpMA1:PD1 SpMA1 SpMA2 P1v:IC1: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 E2c SpMA1:PD1 SpMA1 SpMA2 P1x:IC1: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 E2d SpMA1:PD1 SpMA1 SpMA2 P2g:IC1: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 E2e SpMA1:PD1 SpMA1 SpMA2 P2j:IC1: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 E2f SpMA1:PD1 SpMA1 SpMA2 P3f:IC1: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 E2g SpMA1:PD1 SpMA1 SpMA2 P4l:IC1: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 E2h SpMA1:PD1 SpMA1 SpMA2 P4m:IC1: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 E2i SpMA1:PD1 SpMA1 SpMA2 P4o:IC1: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 E2j SpMA1:PD1 SpMA1 SpMA2 P5f:IC1: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 V3 SpMA1:PD1 SpMA1 SpMA2 SdT3:IC3: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 E3a SpMA1:PD1 SpMA1 SpMA2 P3b:IC3: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 E3b SpMA1:PD1 SpMA1 SpMA2 P3g:IC3: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 E3c SpMA1:PD1 SpMA1 SpMA2 P4a:IC3: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 E3d SpMA1:PD1 SpMA1 SpMA2 P4d:IC3: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 E3e SpMA1:PD1 SpMA1 SpMA2 P2s:IC3: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 E3f SpMA1:PD1 SpMA1 SpMA2 P2v:IC3: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 V4 SpMA1:PD1 SpMA1 SpMA2 IC4:SdT4:TER1 ST2 ST2:LiQ LiQ (95%:5%) 110 nm 10 nm (47%:50%:3%) 10 nm (50%:50%) 1 nm 20 nm 35 nm 30 nm E4a SpMA1:PD1 SpMA1 SpMA2 IC4:P2y:TER1 ST2 ST2:LiQ LiQ (95%:5%) 110 nm 10 nm (47%:50%:3%) 10 nm (50%:50%) 1 nm 20 nm 35 nm 30 nm E4b SpMA1:PD1 SpMA1 SpMA2 IC4:P5h: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 E4c SpMA1:PD1 SpMA1 SpMA2 IC4:P5i: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 E4d SpMA1:PD1 SpMA1 SpMA2 IC4:P5l:TER1 ST2 ST2:LiQ LiQ (95%:5%) 110 nm 10 nm (47%:50%:3%) 10 nm (50%:50%) 1 nm 20 nm 35 nm 30 nm E4e SpMA1:PD1 SpMA1 SpMA2 IC4:P5q:TER1 ST2 ST2:LiQ LiQ (95%:5%) 110 nm 10 nm (47%:50%:3%) 10 nm (50%:50%) 1 nm 20 nm 35 nm 30 nm V5 SpMA1:PD1 SpMA1 SpMA2 SdT5:IC2: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 P5a:IC2: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 P5c:IC2: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 P5d:IC2: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 P5b:IC2: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 P5e:IC2: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 E5f SpMA1:PD1 SpMA1 SpMA2 P5f:IC2: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 E5g SpMA1:PD1 SpMA1 SpMA2 P5g:IC2: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 E5h SpMA1:PD1 SpMA1 SpMA2 P5p:IC2: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 2 Data of the OLEDs U1000 EQE 1000 CIE x/y at j.sub.0 L1 LT Ex. (V) (%) 1000 cd/m.sup.2 (mA/cm.sup.2) (%) (h) V1 3.4 25.3 0.66/0.33 60 95 34 E1a 3.3 25.9 0.67/0.33 60 95 95 E1b 3.2 25.2 0.66/0.33 60 95 82 E1c 3.3 25.6 0.67/0.33 60 95 111 E1d 3.4 25.0 0.66/0.33 60 95 64 E1e 3.3 24.7 0.66/0.33 60 95 82 E1f 3.2 25.6 0.66/0.33 60 95 147 E1g 3.4 24.4 0.67/0.33 60 95 122 E1h 3.3 26.0 0.66/0.33 60 95 126 E1i 3.2 26.2 0.66/0.33 60 95 154 E1j 3.7 25.2 0.66/0.33 60 95 225 E1k 3.7 24.6 0.66/0.33 60 95 185 E1l 3.4 25.7 0.67/0.33 60 95 132 E1m 3.3 24.3 0.67/0.33 60 95 110 E1n 3.2 26.2 0.67/0.33 60 95 59 V2 3.4 25.9 0.66/0.33 60 95 19 E2a 3.3 25.6 0.66/0.33 60 95 53 E2b 3.4 25.2 0.66/0.33 60 95 40 E2c 3.2 25.8 0.66/0.33 60 95 62 E2d 3.4 24.7 0.67/0.33 60 95 34 E2e 3.6 23.9 0.67/0.33 60 95 78 E2f 3.8 25.0 0.66/0.33 60 95 236 E2g 3.3 26.0 0.66/0.33 60 95 117 E2h 3.4 25.7 0.66/0.33 60 95 103 E2i 3.6 24.5 0.67/0.33 60 95 90 E2 3.9 24.8 0.67/0.33 60 95 33 V3 3.8 24.9 0.66/0.33 60 95 67 E3a 3.8 25.4 0.67/0.33 60 95 201 E3b 3.7 24.5 0.66/0.33 60 95 132 E3c 3.4 25.8 0.66/0.33 60 95 115 E3d 3.4 24.7 0.67/0.33 60 95 102 E3e 3.6 26.0 0.66/0.33 60 95 167 E3f 3.3 26.0 0.66/0.33 60 95 126 V4 3.9 24.2 0.66/0.33 60 95 36 E4a 3.7 24.4 0.66/0.33 60 95 52 E4b 3.4 25.0 0.67/0.33 60 95 82 E4c 3.5 25.2 0.66/0.33 60 95 91 E4d 3.4 24.7 0.66/0.33 60 95 65 E4e 3.8 24.0 0.66/0.33 60 95 57 V5 3.7 24.1 0.66/0.33 60 95 12 E5a 3.4 25.0 0.66/0.33 60 95 34 E5b 3.5 25.1 0.67/0.33 60 95 62 E5c 3.6 24.7 0.67/0.33 60 95 45 E5d 3.3 24.4 0.66/0.33 60 95 84 E5e 3.5 24.0 0.66/0.33 60 95 39 E5f 3.7 24.3 0.66/0.33 60 95 49 E5g 3.8 23.9 0.66/0.33 60 95 146 E5h 3.9 24.1 0.67/0.33 60 95 32

TABLE-US-00015 TABLE 3 Structural formulae of the materials of the OLEDs used, if not already described before: [00673] PD1 (CAS 1224447-88-4) [00674] SpMA1 [00675] SpMA2 [00676] ST2 [00677] LiQ [00678] TER1 [00679] IC1 [00680] IC2 [00681] IC3 [00682] IC4 [00683] SdT1 [00684] SdT2 [00685] SdT3 [00686] SdT4 [00687] SdT5