Materials for organic electroluminescent devices

Abstract

The present invention relates to compounds suitable for use in electronic devices, and to electronic devices, especially organic electroluminescent devices, comprising these compounds.

Claims

1. A compound of formula (1) ##STR00518## where the symbols and indices used are as follows: X is the same or different at each instance and is CR or N; Y is NR′, C(R″).sub.2, C═O, BR′, O or S; R, R″ are the same or different at each instance and are H, D, F, Cl, Br, I, N(R.sup.1).sub.2, NAr.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 and 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, C═O, 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; in addition, two R″ radicals together may also form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system; R′ 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; 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, Cl, Br, I, N(R.sup.2).sub.2, 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 in each case be substituted by one or more R.sup.2 radicals and where one or more nonadjacent CH.sub.2 groups may be replaced by Si(R.sub.2).sup.2, C═O, NR.sup.2, O, S or CONR.sup.2, 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 a ring system; R.sup.2 is the same or different at each instance and is H, D, F 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; with the proviso that the compound of the formula (1) contains at least one substituent R′ and/or that the compound of the formula (1) contains at least one substituent R selected from the group consisting of NAr.sub.2 and an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; where the following compounds are excluded from the invention: ##STR00519## ##STR00520## ##STR00521##

2. The compound as claimed in claim 1, characterized in that Y is NR′, O or S.

3. The compound as claimed in claim 1, characterized in that the compound contains not more than two nitrogen atoms per ring.

4. The compound as claimed in claim 1, wherein the compound is of one of the formulae (2a) to (2k) ##STR00522## ##STR00523## where the symbols used have the definitions given in claim 1.

5. The compound as claimed in claim 1, wherein the compound is of one of the formulae (2a′) and (2a″) ##STR00524## where R and R′ have the definitions given in claim 1 and at least one R group in formula (2a″) is selected from the group consisting of NAr.sub.2 and an aromatic or heteroaromatic ring system.

6. The compound as claimed in claim 1, wherein the compound is of formula (3) ##STR00525## where the symbols used have the definitions given in claim 1.

7. The compound as claimed in claim 1, wherein the compound is of formula (5) or formula (6) ##STR00526## where the symbols used have the definitions given in claim 1.

8. The compound as claimed in claim 1, wherein the compound is of one of the formulae (5′), (5″), (6′) and (6″) ##STR00527## where R and R′ have the definitions given in claim 1 and the R group in the formulae (5″) and (6″) is selected from the group consisting of NAr.sub.2 and an aromatic or heteroaromatic ring system.

9. The compound as claimed in claim 1, characterized in that R or R′ or Ar′, when they are aromatic or heteroaromatic ring systems, are selected from phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, phenanthrene, triphenylene or a combination of two or three of these groups, each of which may be substituted by one or more R.sup.1 radicals.

10. A formulation comprising at least one compound as claimed in claim 1 and at least one further compound, where the further compound is one or more solvents and/or a further organic or inorganic compound.

11. An electronic device comprising at least one compound as claimed in claim 1.

12. An organic electroluminescent device, characterized in that the compound as claimed in claim 1, is used as matrix material for phosphorescent emitters and/or in an electron transport layer and/or in a hole blocker layer.

Description

EXAMPLES

(1) The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The solvents and reagents can be purchased from ALDRICH or ABCR. The numbers given for the reactants that are not commercially available are the corresponding CAS numbers. Further literature: thesis: “Entwicklung neuer Synthesewege zu Pyridoacridinen” by Stephan Raeder (2012), University of Munich.

a) 4-Methyl-2-oxo-1,2-dihydroquinoline-3-carbonitrile

(2) ##STR00263##

(3) To 10.0 g (73.9 mmol) of 2-aminoacetophenone are added 10.0 g (88.4 mmol) of ethyl cyanoacetate. The mixture is heated under reflux at 200° C. in an oil bath for 1 h. Subsequently, the mixture is cooled down and 50 ml of ethanol are added. A light-colored precipitate forms, which is filtered off. In order to increase the yield, another 5 g of ethyl cyanoacetate can be added to the supernatant and it can be heated to 200° C. for a further 1.5 h. The residue is purified by suspending it in dichloromethane and then in petroleum benzene, separating it off as white crystals and drying. Yield: 5.4 g (29 mmol), 40% of theory.

(4) The following compounds are prepared in an analogous manner:

(5) TABLE-US-00003 Reactant 1 Reactant 2 Product Yield 1a 37% 2a 34%

b) 2-Chloro-4-methylquinoline-3-carbonitrile

(6) ##STR00270##

(7) 5 g (27 mmol) of 4-methyl-2-oxo-1,2-dihydroquinoline-3-carbonitrile are heated under reflux with 50 ml of phosphoryl chloride for 3 h. Subsequently, the phosphoryl chloride is drawn off under reduced pressure, ammonium chloride solution is added and the residue is filtered off. The residue is washed with water and recrystallized from ethanol. Yield: 5.5 g (27 mmol), 90% of theory.

(8) The following compounds are prepared in an analogous manner:

(9) TABLE-US-00004 Reactant 1 Product Yield 1b 89% 2b 88%

c) 4-Methylquinoline-3-carbonitrile

(10) ##STR00275##

(11) To 15 g (74 mmol) of 2-chloro-4-methylquinoline-3-carbonitrile are added 8 g of sodium acetate and the mixture is suspended in about 800 ml of methanol. To this are added about 200 mg of palladium-charcoal (10%), and the mixture is hydrogenated under H.sub.2 atmosphere at room temperature and standard pressure for 24 h. After the catalyst has been filtered off, a yellow-green solution is obtained, which, after removal of the methanol by rotary evaporation, forms a yellow residue. Purification is effected by means of flash chromatography on silica gel (eluent: dichloromethane:ethyl acetate=5:1). Yield: 12 g (71 mmol), 92% of theory.

(12) The following compounds are prepared in an analogous manner:

(13) TABLE-US-00005 Reactant 1 Product Yield 1c 90% 2c 85%

d) 4-Bromobenzo[c][2,7]naphthyridine

(14) ##STR00280##

(15) 25 g (150 mmol) of 4-methylquinoline-3-carbonitrile are dissolved in 500 ml of DMF, and 50 g (290 mmol) of Bredereck's reagent are added. The mixture is converted in a microwave reactor at 150 W and max. 165° C. for 15 min.

(16) The solvent is distilled off on a rotary evaporator and the residue is dissolved in 600 ml of hydrogen bromide in glacial acetic acid (40%) and 400 ml of glacial acetic acid. The reaction mixture is heated to 60° C. for 1 h, then transferred into 500 ml of water, neutralized with potassium carbonate and extracted with dichloromethane (4×150 ml). The organic phases are combined and dried over MgSO.sub.4, and the solvent is distilled off on a rotary evaporator. The residue is purified by means of flash column chromatography (dichloromethane:methanol=97:3). Yield: 36 g (136 mmol), 95% of theory.

(17) The following compounds are prepared in an analogous manner:

(18) TABLE-US-00006 Reactant 1 Product Yield 1d 92% 2d 90%

e) Ethyl 4-bromobenzo[c][2,7]naphthyridine-5-carboxylate

(19) ##STR00285##

(20) 12 g (45 mmol) of ethyl 4-bromo-5,6-dihydrobenzo[c][2,7]naphthyridine-5-carboxylate are dissolved in 400 ml of dichloromethane, and 39 g (450 mmol) of manganese(IV) oxide. The mixture was converted in a microwave reactor at 150 W at max. 7.0 bar and 100° C. for 10 min (ramp time: 6 min). After being cooled down, the reaction mixture is filtered and washed with methanol, and the solvent is distilled off on a rotary evaporator. Yield: 14 g (42 mmol), 98% of theory.

(21) The following compounds are prepared in an analogous manner:

(22) TABLE-US-00007 Reactant 1 Product Yield 1e 93% 2e 90%

f) Ethyl 4-phenylbenzo[c][2,7]naphthyridine-5-carboxylate

(23) ##STR00290##

(24) 60 g (180 mmol) of ethyl 4-bromobenzo[c][2,7]naphthyridine-5-carboxylate and 4 g (18 mmol) of palladium(II) acetate are suspended in 400 ml of THF. To this are added a solution of 33 g (270 mmol) of benzeneboronic acid and 450 ml (540 mmol) of 1 M potassium carbonate solution in 400 ml of THF. The mixture is heated under reflux under a nitrogen atmosphere for 40 h, then transferred into 200 ml of water and extracted with dichloromethane (4×200 ml). The combined organic phases are dried over MgSO.sub.4, and the solvent is distilled off on a rotary evaporator. The residue is purified by means of flash column chromatography (dichloromethane:ethyl acetate=3:1). Yield: 35 g (106 mmol), 60% of theory.

(25) The following compounds are prepared in an analogous manner:

(26) TABLE-US-00008 Reactant 1 Product Yield 1f 57% 2f 53%

g) 1,8-Diazabenzo[fg]naphthacen-9-one

(27) ##STR00295##

(28) 20 g (60 mmol) of ethyl 4-phenylbenzo[c][2,7]naphthyridine-5-carboxylate are dissolved in 100 ml of trifluoromethanesulfonic acid and converted with the aid of a microwave (reaction conditions: 150 W, reaction time 15 min, ramp time: 1 min, maximum pressure 7.0 bar, max. 85° C.). Subsequently, the mixture is admixed with 200 ml of ice-water, neutralized with K.sub.2CO.sub.3 and extracted with dichloromethane (3×250 ml). The combined organic phases are dried over MgSO.sub.4 and concentrated under reduced pressure. The residue is purified by means of flash column chromatography (dichloromethane:ethyl acetate=3:1). Yield: 7 g (24 mmol), 42% of theory.

(29) The following compounds are prepared in an analogous manner:

(30) TABLE-US-00009 Reactant 1 Product Yield 1g 41% 2g 37%

h) 11-Methyl-5-oxa-6-azanaphthacen-12-one

(31) ##STR00300##

(32) 52.6 g (211 mmol) of ethyl 2-chloro-4-methylquinoline-3-carboxylate are dissolved together with 54 g (317 mmol) of sodium phenoxide in 100 ml of dimethylformamide and reacted at 155° C. for 6 h. Thereafter, the solvent is removed on a rotary evaporator, 10 times the amount of polyphosphoric acid is added to the residue and the mixture is heated to 130° C. for 5 h. The mixture is poured onto ice and neutralized with 6 N NaOH. The neutralized solution is extracted with ethyl acetate (4×500 ml). The combined organic phases are dried over MgSO.sub.4, and the solvent is distilled off on a rotary evaporator. The residue is purified by means of flash column chromatography (dichloromethane:ethyl acetate=3:1). Yield: 13.8 g (52 mmol), 25% of theory.

(33) The following compounds are prepared in an analogous manner:

(34) TABLE-US-00010 Reactant 1 Reactant 2 Product Yield 1h 01 02 03 26% 2h 04 05 06 25%

j) 9-Oxa-1,8-diazabenzo[fg]naphthacene

(35) ##STR00307##

(36) 15.7 g (60 mmol) of 11-methyl-5-oxa-6-azanaphthacen-12-one are dissolved together with 22 g (150 mmol) of diethyl acetal in 10 ml of DMF and reacted in a laboratory microwave at 150° C. and 200 W for 3 h. Thereafter, the solvent is removed on a rotary evaporator, 10 times the amount of NH.sub.4OAc is added to the residue and the mixture is heated to 114° C. for 2 h. The mixture is poured onto ice and extracted with dichloromethane (4×50 ml). The combined organic phases are dried over MgSO.sub.4, and the solvent is distilled off on a rotary evaporator. The residue is purified by means of flash column chromatography (dichloromethane:ethyl acetate=3:1). Yield: 7.8 g (27 mmol), 50% of theory.

(37) The following compounds are prepared in an analogous manner:

(38) TABLE-US-00011 Reactant 1 Product Yield 1j 08 09 52% 2j 0 46% 3j 48%

l) 4-Methyl-2-phenylaminoquinoline-3-carbonitrile

(39) ##STR00314##

(40) 38 g (190 mmol) of 2-chloro-4-methyl-3-quinolinecarbonitrile are dissolved together with 27 g (285 mmol) of aniline in 100 ml of ethylene glycol and heated to 140° C. for 6 h. Subsequently, the mixture is transferred to 50 ml of water and extracted with dichloromethane (3×50 ml). The combined organic phases are dried over MgSO.sub.4, and the solvent is distilled off on a rotary evaporator. The residue is purified by means of flash column chromatography (dichloromethane:methanol=3:1). Yield: 39 g (152 mmol), 80% of theory.

(41) The following compounds are prepared in an analogous manner:

(42) TABLE-US-00012 Reactant 1 Reactant 2 Product Yield 1i 76% 2i 0 78%

k) 4-((E)-2-Dimethylaminovinyl)-2-phenylaminoquinoline-3-carbonitrile

(43) ##STR00321##

(44) 46 g (185 mmol) of 4-methyl-2-phenylaminoquinoline-3-carbonitrile together with 99.6 g (835 mmol) of d($!C258AAEC-1A15-4881-9D65-2CF1E685CC9A!$)imethoxymethyldimethylamine in 400 ml of N($!2F08A8C9-A65C-45E5-BE32-BC64E08B605A!$),N-dimethylformamide (400 ml) are heated to 100° C. for 12 h. After cooling, 1000 ml of ice-water are added. The solids are filtered off with suction and washed with a little heptane. Yield: 50 g (160 mmol), 89% of theory.

(45) The following compounds are prepared in an analogous manner:

(46) TABLE-US-00013 Reactant 1 Product Yield 1k 80% 2k 77% 3k 63% 4k 64% 5k 0 63% 6k 60%

l) 9H-1,8,9-Triazabenzo[fg]naphthacene

(47) ##STR00334##

(48) 27.3 g (87 mmol) of 4-((E)-2-dimethylaminovinyl)-2-phenylaminoquinoline-3-carbonitrile are suspended in 60 ml of conc. H.sub.2SO.sub.4 under protective gas and heated to 70° C. for 4 h. After cooling, the mixture is added to ice-water, the pH is adjusted to 9 with Na.sub.2CO.sub.3 solution, and the mixture is extracted with ethyl acetate. After concentration, the product is purified by chromatography (methanol:dichloromethane 1:2). Yield: 50 g (160 mmol), 89% of theory.

(49) The following compounds are prepared in an analogous manner:

(50) TABLE-US-00014 Reactant 1 Product Yield 1l 84% 2l 86%

m) 1,8,11,13-Tetraazabenzo[fg]naphthacen-9-one

(51) ##STR00339##

(52) 24.7 g (75 mmol) of 11-((E)-2-dimethylaminovinyl)-1,3,6-triazanaphthacene-5,12-dione together with 28.9 g (375 mmol) of ammonium acetate in 400 ml ethanol are heated under reflux for 3 h. The solids are filtered off with suction and washed with a little heptane. Yield: 19.1 g (67 mmol), 90% of theory.

(53) The following compounds are prepared in an analogous manner:

(54) TABLE-US-00015 Reactant 1 Product Yield 1m 0 86% 2m 83% 3m 84%

n) Spiro Synthesis

(55) ##STR00346##

(56) A 1 l four-neck flask is initially charged with 23 g (99 mmol) of 2-bromobiphenyl in 100 ml of THF and cooled to −78° C. By means of a dropping funnel, 41.0 ml (103 mmol) of n-BuLi (2.5 M in n-hexane) are added dropwise at this temperature and the mixture is stirred for 1 h. Subsequently, 13 g (49 mmol) of 1,8,11,13-tetraazabenzo[fg]naphthacen-9-one, dissolved in 300 ml of THF, are added by means of a dropping funnel and the reaction is warmed to room temperature within 3 h. This is followed by hydrolysis with 500 ml of water and removal of the organic solvents on a rotary evaporator. The solid that precipitates out is filtered, suspended in 400 ml of glacial acetic acid and, after addition of 150 ml of concentrated hydrochloric acid, stirred at 100° C. for 2 h. After cooling to room temperature, 400 ml of water are added, and the precipitated solids are filtered off and washed with 200 ml of water, 200 ml of ethanol and lastly with 200 ml of n-heptane. The solids are subjected to hot extraction and recrystallization with n-heptane/toluene over alumina. Further purification is effected by means of recrystallization from toluene/heptane and zone sublimation (310° C., 10.sup.−5 bar). Yield: 15.9 g (37 mmol), 83% of theory

(57) The following compounds are prepared in an analogous manner:

(58) TABLE-US-00016 Reactant 1 Product Yield 1n 82% 2n 0 79% 3n 81% 4n 86% 5n 65%

o) 9-Phenyl-9H-1,8,9-triazabenzo[fg]naphthacene

(59) ##STR00357##

(60) A degassed solution of 23 g (147 mmol) of bromobenzene and 39 g (147 mmol) of 9H-1,8,9-triazabenzo[fg]naphthacene in 600 ml of toluene is saturated with N.sub.2 for 1 h. Added to the solution thereafter are first 2.09 ml (8.6 mmol) of P(tBu).sub.3, then 1.38 g (6.1 mmol) of palladium(II) acetate, and then 17.7 g (185 mmol) of NaOtBu are added in the solid state. The reaction mixture is heated under reflux for 1 h. After cooling to room temperature, 500 ml of water are added cautiously. The aqueous phase is washed with 3×50 ml of toluene, dried over MgSO.sub.4, and the solvent is removed under reduced pressure. Thereafter, the crude product is purified by chromatography using silica gel with heptane/ethyl acetate (20/1). The residue is recrystallized from toluene and finally sublimed under high vacuum (p=5×10.sup.−6 mbar). The yield is 40 g (115 mmol), corresponding to 80% of theory.

(61) The following compounds are prepared in an analogous manner:

(62) TABLE-US-00017 Reactant 1 Reactant 2 Product Yield 1o 0 83% 2o 81% 3o 77% 4o 72% 5o 0 63% 6o 52% 7o 81% 8o 0 84% 9o 87% 10o 80% 11o 0 78% 12o 77% 13o 79% 14o 60% 15o 00 01 02 61% 16o 03 04 05 68% 17o 06 07 08 65% 18o 09 0 62%

p) 9-(4,6-Diphenylpyridin-2-yl)-9H-1,8,9-triazabenzo[fg]naphthacene

(63) ##STR00412##

(64) 16 g (60 mmol) of 9H-1,8,9-triazabenzo[fg]naphthacene are dissolved in 300 ml of dimethylformamide under protective gas atmosphere, and 3 g of NaH, 60% in mineral oil, (75 mmol) are added. After 1 h at room temperature, a solution of 19 g (62 mmol) of 4-bromo-2,6-diphenylpyrimidine in 150 ml of dimethylformamide is added dropwise. The reaction mixture is stirred at room temperature for 12 h. After this time, the reaction mixture is poured onto ice and extracted three times with dichloromethane. The combined organic phases are dried over Na.sub.2SO.sub.4 and concentrated. The residue is recrystallized from toluene and finally fractionally sublimed twice (p about 10.sup.−6 mbar, T=330-360° C.). Yield: 23 g, 80% of theory; purity: 99.9% by HPLC.

(65) The following compounds are prepared in an analogous manner:

(66) TABLE-US-00018 Reactant 1 Reactant 2 Product Yield 1p 76% 2p 77% 3p 0 82% 4p 67% 5p 87% 6p 0 88% 7p 74% 8p 75% 9p 76% 10p 0 81% 11p 82% 12p 84% 13p 0 86% 14p 80%

q) 5-Bromo-9-thia-1,8-diazabenzo[fg]naphthacene

(67) ##STR00455##

(68) 10.6 g (37.3 mmol) of 9-thia-1,8-diazabenzo[fg]naphthacene are initially charged in 80 ml of DMF. Subsequently, 13.3 g (74.6 mmol) of NBS are added in portions and the reaction mixture is stirred at 40° C. for 4 h. Subsequently, 15 ml of water are added to the mixture and extraction is effected with CH.sub.2Cl.sub.2. The organic phase is dried over MgSO.sub.4 and the solvents are removed under reduced pressure. The product is subjected to extractive stirring with hot hexane and filtered off with suction. Yield: 11.4 g (31 mmol), 70% of theory, purity by .sup.1H NMR about 97%.

(69) The following compounds are prepared in an analogous manner:

(70) TABLE-US-00019 Reactant Product Yield 1q 71% 2q 68% 3q 0 66% 4q 67%

r) 5-[3-Eth-(Z)-ylidene-1-phenyl-2-prop-2-en-(E)-ylidene-2,3-dihydro-1H-indol-5-yl]-9-thin-1,8-diazabenzo[fg]naphthacene

(71) ##STR00464##

(72) 24 g (66 mmol) of 5-bromo-9-thia-1,8-diazabenzo[fg]naphthacene, 17 g (664 mmol) of 2-N-phenylcarbazole-3-boronic acid and 13.7 g (100 mmol) of sodium tetraborate are dissolved in 100 ml of THF and 60 ml of water and degassed. 0.91 g (1.3 mmol) of bis(triphenylphosphine)palladium(II) chloride and 1 g (20 mmol) of hydrazinium hydroxide are added. The reaction mixture is then stirred under a protective gas atmosphere at 70° 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). Yield: 29 g (55 mmol), 84% of theory.

(73) The following compounds are prepared in an analogous manner:

(74) TABLE-US-00020 Reactant 1 Reactant 2 Product Yield 1r 80% 2r 0 78% 3r 76% 4r 81% 5r 76% 6r 0 79% 7r 69% 8r 66%

(75) Production of the OLEDs

(76) Examples I1 to I21 which follow (see table 1) present the use of the materials of the invention in OLEDs.

(77) Pretreatment for Examples I1-I21:

(78) Glass plaques 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 plaques form the substrates to which the OLEDs are applied.

(79) 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 2.

(80) 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 IC1:IC2:TER1 (50%:45%:5%) mean here that the material IC1 is present in the layer in a proportion by volume of 50%, IC2 in a proportion by volume of 45% and TER1 in a proportion by volume of 5%. Analogously, the electron transport layer may also consist of a mixture of two materials.

(81) The OLEDs are characterized in a standard manner. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y color coordinates are calculated therefrom.

(82) Use of Materials of the Invention in OLEDs

(83) The materials of the invention can be used in the emission layer in red-phosphorescing OLEDs. The inventive compounds IV1 to IV21 are used in Examples I1 to I21 as matrix material in the emission layer. The color coordinates of the electroluminescence spectra of the OLEDs are CIEx=0.67 and CIEy=0.33. The materials are thus suitable for use in the emission layer of red OLEDs.

(84) In addition, the materials of the invention can be used successfully in the hole blocker layer (HBL) or electron blocker layer (EBL). This is shown in experiments 19 and 121. Here too, the color coordinates of the spectrum of each of the OLEDs are CIEx=0.67 and CIEy=0.33.

(85) TABLE-US-00021 TABLE 1 Structure of the OLEDs HIL HTL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness I1 HATCN SpMA1 SpMA2 IC1:IV1:TER1 — ST1:LiQ (50%:50%) — 5 nm 125 nm 10 nm (50%:45%:5%) 40 nm 35 nm I2 HATCN SpMA1 SpMA2 IC1:IV2:TER1 — ST1:LiQ (50%:50%) — 5 nm 125 nm 10 nm (50%:45%:5%) 40 nm 35 nm I3 HATCN SpMA1 SpMA2 IC1:IV3:TER1 — ST1:LiQ (50%:50%) — 5 nm 125 nm 10 nm (50%:45%:5%) 40 nm 35 nm I4 HATCN SpMA1 SpMA2 IC1:IV4:TER1 — ST1:LiQ (50%:50%) — 5 nm 125 nm 10 nm (50%:45%:5%) 40 nm 35 nm I5 HATCN SpMA1 SpMA2 IC1:IV5:TER1 — ST1:LiQ (50%:50%) — 5 nm 125 nm 10 nm (50%:45%:5%) 40 nm 35 nm I6 HATCN SpMA1 SpMA2 IV6:TER1 — ST1:LiQ (50%:50%) — 5 nm 125 nm 10 nm (95%:5%) 40 nm 35 nm I7 HATCN SpMA1 SpMA2 IC1:IV7:TER1 — ST1:LiQ (50%:50%) — 5 nm 125 nm 10 nm (50%:45%:5%) 40 nm 35 nm I8 HATCN SpMA1 SpMA2 IC1:IV8:TER1 — ST1:LiQ (50%:50%) — 5 nm 125 nm 10 nm (50%:45%:5%) 40 nm 35 nm I9 HATCN SpMA1 SpMA2 IV9:TER1 IV9 ST1:LiQ (50%:50%) — 5 nm 125 nm 10 nm (95%:5%) 40 nm 5 nm 30 nm I10 HATCN SpMA1 SpMA2 IV10:TER1 — ST1:LiQ (50%:50%) — 5 nm 125 nm 10 nm (95%:5%) 40 nm 35 nm I11 HATCN SpMA1 SpMA2 IC1:IV11:TER1 — ST1:LiQ (50%:50%) — 5 nm 125 nm 10 nm (50%:45%:5%) 40 nm 35 nm I12 HATCN SpMA1 SpMA2 IV12:TER1 — ST1:LiQ (50%:50%) — 5 nm 125 nm 10 nm (95%:5%) 40 nm 35 nm I13 HATCN SpMA1 SpMA2 IV13:TER1 — ST1:LiQ (50%:50%) — 5 nm 125 nm 10 nm (95%:5%) 40 nm 35 nm I14 HATCN SpMA1 SpMA2 IC2:IV14:TER1 — ST1:LiQ (50%:50%) — 5 nm 125 nm 10 nm (50%:45%:5%) 40 nm 35 nm I15 HATCN SpMA1 SpMA2 IV15:TER1 — ST1:LiQ (50%:50%) — 5 nm 125 nm 10 nm (95%:5%) 40 nm 35 nm I16 HATCN SpMA1 SpMA2 IV16:TER1 — ST1:LiQ (50%:50%) — 5 nm 125 nm 10 nm (95%:5%) 40 nm 35 nm I17 HATCN SpMA1 SpMA2 IV17:TER1 — ST1:LiQ (50%:50%) — 5 nm 125 nm 10 nm (95%:5%) 40 nm 35 nm I18 HATCN SpMA1 SpMA2 IV18:TER1 — ST1:LiQ (50%:50%) — 5 nm 125 nm 10 nm (95%:5%) 40 nm 35 nm I19 HATCN SpMA1 SpMA2 IC2:IV19:TER1 — ST1:LiQ (50%:50%) — 5 nm 125 nm 10 nm (50%:45%:5%) 40 nm 35 nm I20 HATCN SpMA1 SpMA2 IV20:TER1 — ST1:LiQ (50%:50%) — 5 nm 125 nm 10 nm (95%:5%) 40 nm 35 nm I21 HATCN SpMA1 EG21 IC1:IV21:TER1 — ST1:LiQ (50%:50%) — 5 nm 125 nm 10 nm (50%:45%:5%) 40 nm 35 nm

(86) TABLE-US-00022 TABLE 2 Structural formulae of the materials for the OLEDs 0 HATCN SpMA1 SpMA2 ST1 TER1 LiQ IC1 IC2 IV1 IV2 00 IV3 IV4 01 02 IV5 IV6 03 04 IV7 IV8 05 06 IV9 IV10 07 08 IV11 IV12 09 0 IV13 IV14 IV15 IV16 IV17 IV18 IV19 IV20 IV21