Metal complexes

Abstract

The present invention relates to metal complexes and to electronic devices, in particular organic electroluminescent devices, comprising these metal complexes.

Claims

1. A compound of formula (1):
M(L).sub.n(L′).sub.m  (1) comprising a moiety M(L).sub.n of formula (2) or formula (3): ##STR00272## wherein M is a transition metal selected from the group consisting of chromium, molybdenum, tungsten, rhenium, osmium, rhodium, iridium, nickel, platinum, copper, silver, and gold; X is selected on each occurrence, identically or differently, from the group consisting of CR and N; Y is selected on each occurrence, identically or differently, from the group consisting of C(R.sup.1).sub.2, Si(R.sup.1).sub.2, PR.sup.1, P(═O)R.sup.1, and BR.sup.1; Z is selected on each occurrence, identically or differently, from the group consisting of NR.sup.1 and C(R.sup.1).sub.2, or —Y-Z— is selected on each occurrence, identically or differently, from the group consisting of —Si(R.sup.1).sub.2—O—, —P(═O)R.sup.1—O—, and —BR.sup.1—O—; D is on each occurrence, identically or differently, C or N, with the proviso that at least one D is N; E is on each occurrence, identically or differently, C or N, with the proviso that at least one of E or D in the five-membered ring is N; R and R.sup.1 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, OH, COOH, C(═O)N(R.sup.2).sub.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, alkoxy, or thioalkoxy group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 C atoms, each of which is optionally substituted by one or more radicals R.sup.2, wherein one or more non-adjacent CH.sub.2 groups are optionally replaced by R.sup.2C═CR.sup.2, C≡C, Si(R.sup.2).sub.2, C═O, NR.sup.2, O, S, or CONR.sup.2, and wherein one or more H atoms are optionally replaced by D, F, Cl, Br, I, or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, or a diarylamino group, diheteroarylamino group, or arylheteroarylamino group having 10 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.2; and wherein two adjacent radicals R or two adjacent radicals R.sup.1optionally define a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another; and wherein a radical R and a radical R.sup.1optionally define a mono- or polycyclic, aliphatic or heteroaromatic ring system with one another; R.sup.2 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R.sup.3).sub.2, CN, NO.sub.2, Si(R.sup.3).sub.3, B(OR.sup.3).sub.2, C(═O)R.sup.3, P(═O)(R.sup.3).sub.2, S(═O)R.sup.3, S(═O).sub.2R.sup.3, OSO.sub.2R.sup.3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, each of which is optionally substituted by one or more radicals R.sup.3, wherein one or more non-adjacent CH.sub.2 groups are optionally replaced by R.sup.3C═CR.sup.3, C≡C, Si(R.sup.3).sub.2, C═O, NR.sup.3, O, S, or CONR.sup.3, and wherein one or more H atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms optionally substituted by one or more radicals R.sup.3, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.3, an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.3, or a diarylamino group, diheteroarylamino group, or arylheteroarylamino group having 10 to 40 aromatic ring atoms optionally be substituted by one or more radicals R.sup.3; and wherein two or more adjacent radicals R.sup.2 with one another or a radical R.sup.2 and a radical R or a radical R.sup.1 optionally define a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system; R.sup.3 is on each occurrence, identically or differently, H, D, F, or an aliphatic, aromatic, and/or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, wherein one or more H atoms is optionally replaced by F; and wherein two or more substituents R.sup.3 optionally define a mono- or polycyclic, aliphatic ring system with one another; L′ is, identically or differently on each occurrence, any desired co-ligand; n is 1, 2, or 3; m is 0, 1, 2, 3, or 4; wherein a plurality of ligands L with one another or a ligand L with a ligand L′ are optionally linked via a single bond or a divalent or trivalent bridge to form a tridentate, tetradentate, pentadentate, or hexadentate ligand system, wherein L′ is not a separate co-ligand, but instead a coordinating group; and wherein a substituent R is optionally additionally coordinated to M.

2. The compound of claim 1, wherein M is selected from the group consisting of molybdenum, tungsten, rhenium, osmium, iridium, copper, platinum, and gold.

3. The compound of claim 1, wherein the moiety of formula (2) is selected from the group consisting of moieties of formulae (2a), (2b), and (2c) and the moiety of formula (3) is selected from the group consisting of moieties of formulae (3a), (3b), and (3c): ##STR00273## ##STR00274##

4. The compound of claim 1, wherein the group —Y—Z— is, identically or differently on each occurrence, —C(R.sup.1).sub.2—NR.sup.1—, —Si(R.sup.1).sub.2—NR.sup.1—, —Si(R.sup.1).sub.2—O—, or —C(R.sup.1).sub.2—C(R.sup.1).sub.2—.

5. The compound of claim 1, wherein R.sup.1 is selected, identically or differently on each occurrence, from the group consisting of F, CN, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, each of which is optionally substituted by one or more radicals R.sup.2, wherein one or more non-adjacent CH.sub.2 groups are optionally replaced by R.sup.2C═CR.sup.2, and wherein one or more H atoms are optionally replaced by F, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms optionally substituted by one or more radicals R.sup.2, or a diarylamino group, diheteroarylamino group, or arylheteroarylamino group having 10 to 30 aromatic ring atoms optionally substituted by one or more radicals R.sup.2; and wherein two adjacent radicals R.sup.1 optionally define a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system with one another; and wherein a radical R and a radical R.sup.1 optionally define a mono- or polycyclic, aliphatic or heteroaromatic ring system with one another.

6. The compound of claim 1, wherein 0, 1, or 2 groups X in the ligand L is N.

7. The compound of claim 1, wherein the moiety of formula (2) is selected from the group consisting of moieties of formulae (2-A) to (2-G) and the moiety of formula (3) is selected from the group consisting of moieties of formulae (3-A) to (3-H): ##STR00275## ##STR00276## ##STR00277## ##STR00278##

8. The compound of claim 1, wherein E is N and either the D in the five-membered ring or the D in the six-membered ring is N, while the other D is C, or E is C and both D are N.

9. The compound of claim 1, wherein, if one or more X is N, a group R which is not H or D is bonded as a substituent adjacent to this nitrogen atom.

10. The compound of claim 9, wherein, if one or more X is N, a group selected from the group consisting of CF.sub.3, OCF.sub.3, alkyl or alkoxy groups having 1 to 10 C atoms, aromatic or heteroaromatic ring systems or aralkyl or heteroaralkyl groups, wherein these groups are each optionally substituted by one or more radicals R.sup.2, is bonded as a substituent adjacent to this nitrogen atom.

11. The compound of claim 10, wherein the alkyl or alkoxy groups are branched or cyclic alkyl or alkoxy groups having 3 to 10 C atoms.

12. The compound of claim 1, wherein two adjacent X are CR and the respective radicals R, together with the C atoms, define a ring of formula (4) or formula (5), ##STR00279## wherein the dashed bonds indicate the linking of the two carbon atoms in the ligand; A.sup.1 and A.sup.3 are, identically or differently on each occurrence, C(R.sup.4).sub.2, O, S, NR.sup.4, or C(═O); A.sup.2 is C(R.sup.2).sub.2, O, S, NR.sup.4, or C(═O); G is an alkylene group having 1, 2 or 3 C atoms optionally substituted by one or more radicals R.sup.3, or is —CR.sup.3═CR.sup.3— or an ortho-linked arylene or heteroarylene group having 5 to 14 aromatic ring atoms optionally substituted by one or more radicals R.sup.3; R.sup.4 is, identically or differently on each occurrence, F, a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, each of which is optionally substituted by one or more radicals R.sup.3, wherein one or more non-adjacent CH.sub.2 groups are optionally replaced by R.sup.3C═CR.sup.3, C≡C, Si(R.sup.3).sub.2, C═O, NR.sup.3, O, S, or CONR.sup.3 and wherein one or more H atoms are optionally replaced by D or F, an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms optionally substituted by one or more radicals R.sup.3, an aryloxy or heteroaryloxy group having 5 to 24 aromatic ring atoms optionally substituted by one or more radicals R.sup.3, or an aralkyl or heteroaralkyl group having 5 to 24 aromatic ring atoms optionally substituted by one or more radicals R.sup.3; and wherein two radicals R.sup.4 which are bonded to the same carbon atom optionally define an aliphatic or aromatic ring system with one another here to form a spiro system; and wherein R.sup.4 optionally defines an aliphatic ring system with an adjacent radical R, R.sup.1 or R.sup.2; with the proviso that no two heteroatoms in A.sup.1-A.sup.2-A.sup.3 are bonded directly to one another.

13. The compound of claim 1, wherein the compound is selected from the group consisting of the structures of formulae (12) to (23): ##STR00280## ##STR00281## ##STR00282## wherein V is a single bond or a bridging unit containing 1 to 80 atoms from the third, fourth, fifth and/or sixth main group (group 13, 14, 15 or 16 in accordance with IUPAC) or a 3- to 6-membered homo- or heterocycle which covalently bonds the part-ligands L to one another or L to L′.

14. The compound of claim 1, wherein the ligands L′ are selected from the group consisting of carbon monoxide, nitrogen monoxide, alkyl cyanides, aryl cyanides, alkyl isocyanides, aryl isocyanides, amines, phosphines, phosphites, arsines, stibines, nitrogen-containing heterocycles, carbenes, hydride, deuteride, F.sup.−,Cl.sup.−, Br.sup.−, I.sup.−, alkylacetylides, arylacetylides, cyanide, cyanate, isocyanate, thiocyanate, isothiocyanate, aliphatic alcoholates, aromatic alcoholates, aliphatic thioalcoholates, aromatic thioalcoholates, amides, carboxylates, aryl groups, O.sup.2−, S.sup.2−, carbides, nitrenes, N.sup.3−, diamines, imines, diimines, heterocycles containing two nitrogen atoms, diphos-phines, 1,3-diketonates derived from 1,3-diketones, 3-ketonates derived from 3-keto-esters, carboxylates derived from aminocarboxylic acids, salicyliminates derived from salicylimines, dialcoholates derived from dialcohols, dithiolates derived from dithiols, bis(pyrazolyl boraten), bis(imidazolyl) boraten, 3-(2-pyridyl)diazoles, 3-(2-pyridyl)triazoles, bidentate monoanionic, neutral ligands, and dianionic ligands.

15. The compound of claim 14, wherein the ligands L′ are monoanionic ligands, which, with M, define a cyclometallated five-membered ring or six-membered ring having at least one metal-carbon bond.

16. A process for preparing a compound of claim 1 comprising reacting a free ligand L and optionally L′ with a metal alkoxide of formula (75), a metal ketoketonate of formula (76), a metal halides of formula (77), a dimeric metal complex of formula (78), or a metal complex of formula (79): ##STR00283## wherein Hal is F, Cl, Br, or I; L″ is an alcohol or a nitrile; and (anion) is a non-coordinating anion.

17. An oligomer, polymer, or dendrimer comprising one or more compounds of claim 1, wherein one or more bonds are present from the compound to the polymer, oligomer, or dendrimer.

18. A formulation comprising the oligomer, polymer, or dendrimer of claim 17 and at least one further compound.

19. The formulation of claim 18, wherein the at least one further compound is a solvent and/or a further organic or inorganic compound.

20. An electronic device comprising in at least one layer at least one oligomer, polymer, or dendrimer of claim 17.

21. The electronic device of claim 20, wherein the device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, and organic laser diodes.

22. A formulation comprising the compound of claim 1 and at least one further compound.

23. The formulation of claim 22, wherein the at least one further compound is a solvent and/or a further organic or inorganic compound.

24. An electronic device comprising in at least one layer at least one compound of claim 1.

25. The electronic device of claim 24, wherein the device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, and organic laser diodes.

Description

EXAMPLES

(1) The following syntheses are carried out, unless indicated otherwise, in dried solvents under a protective-gas atmosphere. The metal complexes are additionally handled with exclusion of light or under yellow light. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The respective numbers in square brackets or the numbers indicated for individual compounds relate to the CAS numbers of the compounds known from the literature.

(2) A: Synthesis of the Synthones S:

Example S1

1,1,3,3-Tetramethylindane-5,6-diamine, [83721-95-3], S1

(3) ##STR00125##
Variant A
A: 5,6-Dibromo-1,1,3,3-tetramethylindane, S1a

(4) ##STR00126##

(5) 1.3 g of anhydrous iron(III) chloride and then, dropwise with exclusion of light, a mixture of 64.0 ml (1.25 mol) of bromine and 300 ml of dichloro-methane are added to a solution of 87.2 g (500 mmol) of 1,1,3,3-tetramethylindane [4834-33-7] in 2000 ml of dichloromethane at such a rate that the temperature does not exceed 25° C., if necessary with countercooling using a cold-water bath. The reaction mixture is stirred at room temperature for a further 16 h, 500 ml of saturated sodium sulfite solution are then added slowly, the aqueous phase is separated off, the organic phase is washed three times with 1000 ml of water each time, dried over sodium sulfate, filtered through a short silica-gel column, and the solvent is then stripped off. Finally, the solid is recrystallised once from a little (about 100 ml) ethanol. Yield: 121.2 g (365 mmol), 73%; purity: about 95% according to .sup.1H-NMR.

(6) B: 1,1,3,3-Tetramethylindane-5,6-diamine, S1

(7) 9.34 g (15 mmol) of rac-BINAP and then 3.36 g (15 mmol) of palladium(II) acetate are added to a mixture of 121.2 g (365 mmol) of 5,6-dibromo-1,1,3,3-tetramethylindane, 153.2 ml (913 mmol) of benzhydrylidenamine [1013-88-3], 96.1 g (1.0 mol) of sodium tert-butoxide and 1000 ml of toluene, and the mixture is subsequently heated under reflux for 16 h. After cooling, 500 ml of water are added, the organic phase is separated off, washed twice with 500 ml of saturated sodium chloride solution each time, the toluene is removed in a rotary evaporator, the residue is taken up in 500 ml of THF, 200 ml of 2 N hydrochloric acid are added, and the reaction mixture is heated under reflux for 16 h. The solvent is removed in vacuo, the residue is taken up in 1000 ml of ethyl acetate, the organic phase is washed with sodium hydrogencarbonate solution until pH=7 has been reached, the organic phase is dried over magnesium sulfate, the desiccant is filtered off, 500 g of silica gel are added to the filtrate, and the solvent is removed in vacuo. The loaded silica gel is placed on a silica-gel column (1500 g, slurried in n-heptane: ethyl acetate, 95:5 vv), firstly the benzophenone is eluted with n-heptane: ethyl acetate (95:5 vv), the eluent is then switched to ethyl acetate, and the product is eluted. Yield: 56.8 g (278 mmol), 76%; purity: about 95% according to .sup.1H-NMR.

(8) Variant B

(9) A: 5,6-Dinitro-1,1,3,3-tetramethylindane, S1b

(10) ##STR00127##

(11) 350 ml of 100% by weight nitric acid are slowly added dropwise to a vigorously stirred mixture, cooled to 0° C., of 87.2 g (500 mmol) of 1,1,3,3-tetramethylindane [4834-33-7] and 350 ml of 95% by weight sulfuric acid at such a rate that the temperature does not exceed +5° C. The reaction mixture is subsequently allowed to warm slowly to room temperature over the course of 2-3 h and is then poured into a vigorously stirred mixture of 6 kg of ice and 2 kg of water. The mixture is adjusted to pH=8-9 by addition of 40% by weight NaOH, extracted three times with 1000 ml of ethyl acetate each time, the combined organic phases are washed twice with 1000 ml of water each time, dried over magnesium sulfate, the ethyl acetate is then removed virtually completely in vacuo until crystallisation commences, and the crystallisation is completed by addition of 500 ml of heptane. The beige crystals obtained in this way are filtered off with suction and dried in vacuo. Yield: 121.6 g (460 mmol), 92%; purity: about 94% according to .sup.1H-NMR, remainder about 4% of 4,6-dinitro-1,1,3,3-tetramethylindane. About 3% of 4,5-dinitro-1,1,3,3-tetramethylindane can be isolated from the mother liquor.

(12) B: 1,1,3,3-Tetramethylindane-5,6-diamine, S1

(13) 126.9 g (480 mmol) of 5,6-dinitro-1,1,3,3-tetramethylindane, S16b, are hydrogenated in 1200 ml of ethanol on 10 g of palladium/charcoal at room temperature at a hydrogen pressure of 3 bar for 24 h. The reaction mixture is filtered through a Celite bed twice, the brown solid obtained after removal of the ethanol is distilled in a bulb tube (T about 160° C., p about 10.sup.−4 mbar). Yield: 90.3 g (442 mmol), 92%; purity: about 95% according to .sup.1H-NMR.

(14) 1,1,3,3-Tetramethylindane-5,6-diamine dihydrochloride, S16×2HCl, can be obtained from S16 by dissolution in dichloromethane and introduction of gaseous HCl to saturation and subsequent removal of the dichloromethane.

(15) The following compounds are prepared analogously:

(16) TABLE-US-00002 Variant Yield Step Ex. Starting material Product A + B S2 A 63% B 78% S3 0 B 80% S4 B 76% S5 B 71%

Example S6

2-(5,5,7,7-Tetramethyl-1,5,6,7-tetrahydroindeno[5,6-d]-imidazol-2-yl]phenylamine, S6

(17) ##STR00136##

(18) Preparation analogous to Pandey, Rampal et al., Tetrahedron Letters, 53(28), 3550, 2012.

(19) A solution of 20.4 g (100 mmol) of 1,1,3,3-tetramethylindane-5,6-diamine, S1 and 13.7 g (100 mmol) of 2-aminobenzoic acid [118-92-3] in 400 ml of methanol is heated at room temperature for 30 min. and then under reflux for 6 h, during which 200 ml of methanol are gradually distilled off. After slow cooling, the mixture is stirred at room temperature for a further 12 h, the crystals are filtered off with suction, washed with a little methanol and dried in vacuo. Yield: 25.0 g (82 mmol) 82%. Purity: 97% according to .sup.1H-NMR.

(20) 2-(2-Hydroxyphenyl)benzimidazoles are obtained analogously to M. Al Messmary et al., Int. Arch. Appl. Science and Tech. 1(1), 84, 2011 in accordance with the above procedure, with methanol being replaced by glacial acetic acid.

(21) The following compounds are prepared analogously:

(22) TABLE-US-00003 Ex. Diamine Carboxylic acid Product Yield S7 79% S8 0 77% S9 80% S10 73% S11 0 57% S12 54%
B: Synthesis of the Ligands L:

Example L1

6,6-Dimethyl-5,6-dihydrobenzo[4,5]imidazo[1,2-c]-quinazoline

(23) ##STR00155##

(24) 13.5 ml (110 mmol) of 2,2-dimethoxypropane and then 6.6 ml (110 mmol) of glacial acetic acid are added to a solution of 20.9 g (100 mmol) of 2-(2-aminophenyl)benzimidazole [5805-39-0] in 100 ml of acetone, and the mixture is stirred at room temperature for 16 h. The precipitated solid is filtered off with suction, washed once with 20 ml of acetone and dried in vacuo. Yield: 19.5 g (78 mmol) 78%. Purity: 99% according to .sup.1H-NMR. The ligands obtained in this way are freed from boiling components and non-volatile secondary components by bulb-tube distillation or fractional sublimation (p approx. 10.sup.−4-10.sup.−5 mbar, T approx. 160-240° C.). Compounds containing aliphatic radicals having more than 6 C atoms or those containing aralkyl groups having more than 9 C atoms are typically purified by chromatography and then dried in vacuo in order to remove low-boiling components. Purity according to .sup.1H-NMR typically >99.5%.

(25) The following compounds are prepared analogously:

(26) TABLE-US-00004 Ex. Amine Alcohol Ketal Solvent Product Yield L2  34% L3  0 75% L4  68% L5  69% L6  0 73% L7  46% L8  64% L9  55% L10 0 49%

Example L11

5,6,6-Trimethyl-5,6-dihydrobenzo[4,5]imidazo[1,2-c]-quinazoline

(27) ##STR00183##

(28) A mixture of 24.9 g (100 mmol) of 6,6-dimethyl-5,6-dihydrobenzo[4,5]-imidazo[1,2-c]quinazoline, L1 and 11.5 g (120 mmol) of sodium tert-butoxide in 300 ml of THF is stirred at 60° C. for 30 min. After cooling to room temperature, 7.5 ml (120 mmol) of methyl iodide in 50 ml of THF are added dropwise, the mixture is then stirred at 60° C. for a further 4 h, the THF is removed in vacuo, the residue is taken up in 500 ml of ethyl acetate, the organic phase is washed twice with 300 ml of water each time, once with saturated sodium chloride solution, dried over magnesium sulfate, and the solvent is then removed in vacuo. Yield: 17.9 g (68 mmol) 68%. Purity: 99% according to .sup.1H-NMR.

(29) The ligands obtained in this way are freed from low-boiling components and non-volatile secondary components by bulb-tube distillation or fractional sublimation (p approx. 10.sup.−4-10 .sup.−5 mbar, T approx. 160-240° C.). Compounds containing aliphatic radicals having more than 6 C atoms, or those containing aralkyl groups having more than 9 C atoms, are typically purified by chromatography and then dried in vacuo in order to remove low-boiling components. Purity according to .sup.1H-NMR typically >99.5%.

(30) The following compounds are prepared analogously:

(31) TABLE-US-00005 Alkylating Ex. Amine agent Product Yield L12 H.sub.3C—I 73% L13 H.sub.3C—I 70% L14 n-Bu—I 48% L15 0 H.sub.3C—I 67% L16 H.sub.3C—I 70% L17 H.sub.3C—I 36%

Example L18

6,6-Dimethyl-5-phenyl-5,6-dihydrobenzo[4,5]imidazo-[1,2-c]quinazoline

(32) ##STR00196##

(33) A mixture of 24.9 g (100 mmol) of 6,6-dimethyl-5,6-dihydrobenzo[4,5]-imidazo[1,2-c]quinazoline, L1, 11.2 ml (120 mmol) of fluorobenzene [462-06-6] and 11.5 g (120 mmol) of sodium tert-butoxide in dimethyl-acetamide is stirred at 160° C. for 30 h. After cooling to room temperature, 500 ml of ethyl acetate are added, the organic phase is washed five times with 300 ml of water each time, once with saturated sodium chloride solution, dried over magnesium sulfate, and the solvent is then removed in vacuo. The oily residue is distilled twice in a bulb tube (p approx. 10.sup.−4-10.sup.−5 mbar, T approx. 200-220° C.). Yield: 15.3 g (47 mmol) 47%. Purity: 99.5% according to .sup.1H-NMR.

(34) The following compounds can be prepared analogously.

(35) TABLE-US-00006 Fluoroaromatic Ex. Amine compound Product Yield L19 43% L20 00 01 02 45%

Example L21

6,6-Dimethyl-5-oxa-6a,11-diaza-6-silabenzo[a]fluorene

(36) ##STR00203##

(37) A mixture of 12.8 ml (105 mmol) of dichlorodimethylsilane [75-78-5] and 50 ml of THF is added dropwise to a solution of 21.0 g (100 mmol) of 2-(2-hydroxyphenyl)benzimidazole [2963-66-8] in a mixture of 300 ml of THF and 30.5 ml (220 mmol) of triethylamine, and the mixture is stirred at room temperature for 16 h. The THF is removed in vacuo, the residue is taken up in 200 ml of cyclohexane, the triethylammonium chloride is filtered off with suction, and the cyclohexane is removed in vacuo. The oily residue is distilled twice in a bulb tube (p approx. 10.sup.−4-10.sup.−5 mbar, T approx. 200-220° C.). Yield: 13.6 g (51 mmol) 51%. Purity: 99.5% according to .sup.1H-NMR.

(38) The following compounds are prepared analogously:

(39) TABLE-US-00007 Ex. Imidazole Electrophile Product Yield L22 04 05 06 54% L23 07 08 09 47% L24 0 50% L25 39% L26 44% L27 0 40% L28 30% L29 27%

Example L30

5,5,6,6-Tetramethyl-5,6-dihydrobenzo[4,5]imidazo-[2,1a]isoquinoline

(40) ##STR00228##

(41) A mixture of 19.4 g (100 mmol) of 2-phenylbenzimidazole [716-79-0], 11.0 g (110 mmol) of 2,2,3,3-tetramethyloxirane [5076-20-0], 0.5 ml of boron trifluoride etherate and 50 ml of triethylene glycol dimethyl ether is heated at 180° C. in an autoclave for 12 h. After cooling, 300 ml of ethyl acetate are added to the reaction mixture, the mixture is washed five times with 200 ml of water each time, once with 200 ml of sat. sodium chloride solution, and the org. phase is dried over magnesium sulfate. The org. phase is freed from solvent, 300 ml of glacial acetic acid, 30 ml of acetic anhydride and 10 ml of conc. sulfuric acid are added, and the mixture is then stirred at 80° C. for 4 h. The acetic acid is removed in vacuo, the residue is taken up in 500 ml of dichloromethane, carefully rendered alkaline using 10% by weight NaOH solution with ice-cooling, the org. phase is separated off, washed once with 200 ml of water, once with 200 ml of sat. sodium chloride solution and dried over magnesium sulfate. The residue remaining after removal of the solvent is chromatographed on silica gel (ethyl acetate: MeOH 9:1) and then distilled twice in a bulb tube (p approx. 10.sup.−4-10.sup.−5 mbar, T approx. 200-210° C.). Yield: 8.6 g (31 mmol) 31%. Purity: 99.5% according to .sup.1H-NMR.

(42) C: Synthesis of the Metal Complexes

(43) 1) Homoleptic Tris-facial Iridium Complexes:

(44) Variant A: Trisacetylacetonatoiridium(III) as Iridium Starting Material

(45) A mixture of 10 mmol of trisacetylacetonatoiridium(III) [15635-87-7] and 60 mmol of the ligand L and a glass-clad magnetic stirrer bar are melted into a thick-walled 50 ml glass ampoule in vacuo (10.sup.−5 mbar). The ampoule is heated at the temperature indicated for the time indicated, during which the molten mixture is stirred with the aid of a magnetic stirrer. In order to prevent sublimation of the ligands onto relatively cold parts of the ampoule, the entire ampoule must have the temperature indicated. Alternatively, the synthesis can be carried out in a stirred autoclave with glass insert. After cooling (NOTE: the ampoules are usually under pressure!), the ampoule is opened, the sinter cake is stirred for 3 h with 100 g of glass beads (diameter 3 mm) in 100 ml of a suspension medium (the suspension medium is selected so that the ligand is readily soluble, but the metal complex has low solubility therein, typical suspension media are methanol, ethanol, dichloromethane, acetone, THF, ethyl acetate, toluene, etc.) and mechanically digested in the process. The fine suspension is decanted off from the glass beads, the solid is filtered off with suction, rinsed with 50 ml of the suspension medium and dried in vacuo. The dry solid is placed on a 3-5 cm deep aluminium oxide bed (aluminium oxide, basic, activity grade 1) in a continuous hot extractor and then extracted with an extractant (initially introduced amount about 500 ml, the extractant is selected so that the complex is readily soluble therein at elevated temperature and has low solubility therein when cold, particularly suitable extractants are hydrocarbons, such as toluene, xylenes, mesitylene, naphthalene, o-dichloro-benzene, halogenated aliphatic hydrocarbons are generally unsuitable since they may halogenate or decompose the complexes). When the extraction is complete, the extractant is evaporated to about 100 ml in vacuo. Metal complexes which have excessively good solubility in the extractant are brought to crystallisation by dropwise addition of 200 ml of methanol. The solid of the suspensions obtained in this way is filtered off with suction, washed once with about 50 ml of methanol and dried. After drying, the purity of the metal complex is determined by means of NMR and/or HPLC. If the purity is below 99.5%, the hot extraction step is repeated, omitting the aluminium oxide bed from the 2nd extraction. When a purity of 99.5-99.9% has been reached, the metal complex is heated or sublimed. The heating is carried out in a high vacuum (p about 10.sup.−6 mbar) in the temperature range from about 200-300° C. The sublimation is carried out in a high vacuum (p about 10.sup.−6 mbar) in the temperature range from about 300-400° C., with the sublimation preferably being carried out in the form of a fractional sublimation. If ligands in point group C1 are employed in the form of a racemic mixture, the derived fac-metal complexes are produced in the form of a diastereomer mixture. The enantiomer pair Λ,Δ in point group C3 generally has significantly lower solubility in the extractant than that in point group C1, which is consequently enriched in the mother liquor. Separation of the diastereomers by this method is frequently possible. In addition, the diastereomers can also be separated by chromatography. If ligands in point group C1 are employed in enantiomerically pure form, the enantiomer pair Λ,Δ in point group C3 is formed.

(46) Variant B: Tris-(2,2,6,6-tetramethyl-3,5-heptanedionato)iridium(III) as Iridium Starting Material

(47) Procedure analogous to variant A, using 10 mmol of tris(2,2,6,6-tetra-methyl-3,5-heptanedionato)iridium [99581-86-9] instead of 10 mmol of tris-acetylacetonatoiridium(III) [15635-87-7]. The use of this starting material is advantageous since the purity of the crude products obtained is frequently better than in the case of variant A. In addition, the build-up of pressure in the ampoule is frequently not as pronounced.

(48) TABLE-US-00008 Variant Reaction temp./ reaction time Ligand Ir complex Suspension medium Ex. L Diastereomer Extractant Yield Ir(L2).sub.3 L2 A 230° C./60 h DCM Mesitylene 24% Ir(L9).sub.3 L9 0 A 230° C./60 h DCM Mesitylene 21% Ir(L12).sub.3 L12 B 240° C./80 h DCM Mesitylene 25% Ir(L15).sub.3 L15 B 240° C./80 h Acetone Mesitylene 23% Ir(L16).sub.3 L16 B 250° C./80 h Acetone Mesitylene 21% Ir(L20).sub.3 L20 B 250° C./80 h Acetone Mesitylene 22% Ir(L24).sub.3 L24 B 250° C./100 h Acetone Mesitylene 18% Ir(L27).sub.3 L27 B 230° C./100 h THF Mesitylene 21% Ir(L28).sub.3 L28 A 260° C./30 h THF Toluene 15% Ir(L29).sub.3 L29 A 260° C./30 h THF Toluene 13% Ir(L30).sub.3 L30 A 255° C./60 h EtOH Toluene 24%
2) Heteroleptic Iridium Complexes:
Variant A:
Step 1:

(49) A mixture of 10 mmol of sodium bisacetylacetonatodichloroiridate(III) [770720-50-8] and 24 mmol of ligand L and a glass-clad magnetic stirrer bar are melted into a thick-walled 50 ml glass ampoule in vacuo (10.sup.−5 mbar). The ampoule is heated at the temperature indicated for the time indicated, during which the molten mixture is stirred with the aid of a magnetic stirrer. After cooling—NOTE: the ampoules are usually under pressure!—the ampoule is opened, the sinter cake is stirred for 3 h with 100 g of glass beads (diameter 3 mm) in 100 ml of the suspension medium indicated (the suspension medium is selected so that the ligand is readily soluble, but the chloro dimer of the formula [Ir(L).sub.2Cl].sub.2 has low solubility therein, typical suspension media are dichloromethane, acetone, ethyl acetate, toluene, etc.) and mechanically digested at the same time. The fine suspension is decanted off from the glass beads, the solid (Ir(L).sub.2Cl].sub.2 which still contains about 2 eq. of NaCl, referred to below as the crude chloro dimer) is filtered off with suction and dried in vacuo.

(50) Step 2:

(51) The crude chloro dimer of the formula [Ir(L).sub.2Cl].sub.2 obtained in this way is suspended in a mixture of 75 ml of 2-ethoxyethanol and 25 ml of water, 13 mmol of the co-ligand CL or the co-ligand compound CL and 15 mmol of sodium carbonate are added. After 20 h under reflux, a further 75 ml of water are added dropwise, after cooling the solid is filtered off with suction, washed three times with 50 ml of water each time and three times with 50 ml of methanol each time and dried in vacuo. The dry solid is placed on an aluminium oxide bed (aluminium oxide, basic activity grade 1) with a depth of 3-5 cm in a continuous hot extractor and then extracted with the extraction medium indicated (initially introduced amount about 500 ml, the extractant is selected so that the complex is readily soluble therein at elevated temperature and has low solubility therein when cold, particularly suitable extractants are hydrocarbons, such as toluene, xylenes, mesitylene, naphthalene, o-dichlorobenzene; halogenated aliphatic hydrocarbons are generally unsuitable since they may halogenate or decompose the complexes). When the extraction is complete, the extraction medium is evaporated to about 100 ml in vacuo. Metal complexes which have excessively good solubility in the extraction medium are brought to crystallisation by dropwise addition of 200 ml of methanol. The solid of the suspensions obtained in this way is filtered off with suction, washed once with about 50 ml of methanol and dried. After drying, the purity of the metal complex is determined by means of NMR and/or HPLC. If the purity is below 99.5%, the hot-extraction step is repeated, if a purity of 99.5-99.9% has been reached, the metal complex is heated or sublimed. Besides the hot extraction method for purification, the purification can also be carried out by chromatography on silica gel or aluminium oxide. The heating is carried out in the temperature range from about 200-300° C. in a high vacuum (p about 10.sup.−6 mbar). The sublimation is carried out in the temperature range from about 300-400° C. in a high vacuum (p about 10.sup.−6 mbar), where the sublimation is preferably carried out in the form of a fractional sublimation.

(52) TABLE-US-00009 Ir complex Step 1: reaction temp./ reaction time/ Co- suspension medium Ligand ligand Step 2: Ex. L CL extractant Yield Ir(L10).sub.2(CL1) L10 0 27% Ir(L11).sub.2(CL2) L11 24% Ir(L17).sub.2(CL3) L17 20% Ir(L18).sub.2(CL4) L18 23%
Variant B:
Step 1:

(53) See variant A, step 1.

(54) Step 2:

(55) The crude chloro dimer of the formula [Ir(L).sub.2Cl].sub.2 obtained in this way is suspended in 1000 ml of dichloromethane and 150 ml of ethanol, 20 mmol of silver(I) trifluoromethanesulfonate are added to the suspension, and the mixture is stirred at room temperature for 24 h. The precipitated solid (AgCl) is filtered off with suction via a short Celite bed, and the filtrate is evaporated to dryness in vacuo. The solid obtained in this way is taken up in 100 ml of ethylene glycol, 20 mmol of co-ligand CL are added, and the mixture is then stirred at 130° C. for 30 h. After cooling, the solid is filtered off with suction, washed twice with 50 ml of ethanol each time and dried in vacuo. Hot extraction and sublimation as in variant A.

(56) TABLE-US-00010 Ir complex Step 1: reaction temp./ reaction time/ Co- suspension medium Ligand ligand Step 2: Ex. L CL extractant Yield Ir(L13).sub.2(CL5) L13 26% Ir(L14).sub.2(CL5) L14 CL5 0 29% Ir(L19).sub.2(CL6) L19 24% Ir(L21).sub.2(CL6) L21 CL6 24% Ir(L23).sub.2(CL6) L23 CL6 22% Ir(L26).sub.2(CL6) L26 CL6 17%
Heteroleptic Platinum Complexes:

(57) A mixture of 10 mmol of platinum(II) chloride and 12 mmol of ligand L and a glass-clad magnetic stirre bar are melted into a thick-walled 50 ml glass ampoule in vacuo (10.sup.−5 mbar). The ampoule is heated at the temperature indicated for the time indicated, during which the molten mixture is stirred with the aid of a magnetic stirrer. After cooling—NOTE: the ampoules are usually under pressure!—the ampoule is opened, the sinter cake is stirred for 3 h with 100 g of glass beads (diameter 3 mm) in 100 ml of the suspension medium indicated (the suspension medium is selected so that the ligand is readily soluble, but the chloro dimer of the formula [Ir(L).sub.2Cl].sub.2 has low solubility therein, typical suspension media are dichloromethane, acetone, ethyl acetate, toluene, etc.) and mechanically digested at the same time. The fine suspension is decanted off from the glass beads, the solid is filtered off with suction and dried in vacuo. The crude chloro dimer of the formula [Pt(L)Cl].sub.2 obtained in this way is suspended in a mixture of 60 ml of 2-ethoxyethanol and 20 ml of water, and 20 mmol of co-ligand CL or co-ligand compound CL and 20 mmol of sodium carbonate are added. After 20 h under reflux, a further 100 ml of water are added dropwise, after cooling the solid is filtered off with suction, washed three times with 50 ml of water each time and three times with 50 ml of methanol each time and dried in vacuo. The solid obtained in this way is placed on a Celite bed with a depth of 3-5 cm in a hot extractor and then extracted with the extraction medium indicated (initially introduced amount about 500 ml). When the extraction is complete, the extraction medium is evaporated to about 100 ml in vacuo. Metal complexes which have excessively good solubility in the extraction medium are brought to crystallisation by dropwise addition of 200 ml of methanol. The solid of the suspensions obtained in this way is filtered off with suction, washed once with about 50 ml of methanol and dried. After drying, the purity of the metal complex is determined by means of NMR and/or HPLC. If the purity is below 99.5%, the hot-extraction step is repeated, if a purity of 99.5-99.9% has been reached, the metal complex is heated or sublimed. The heating is carried out in the temperature range from about 200-300° C. in a high vacuum (p about 10.sup.−6 mbar). The sublimation is carried out in the temperature range from about 250-350° C. in a high vacuum (p about 10.sup.−6 mbar), where the sublimation is preferably carried out in the form of a fractional sublimation.

(58) TABLE-US-00011 Co- Ligand ligand Ex. L CL Pt complex Yield Pt(L22)(CL7) L22 21% Pt(L25)(CL2) L25 23%
Production of the OLEDs
1) Vacuum-Processed Devices:

(59) OLEDs according to the invention and OLEDs in accordance with the prior art are produced by a general process in accordance with WO 2004/058911, which is adapted to the circumstances described here (layer-thickness variation, materials used).

(60) The results for various OLEDs are presented in the following examples. Glass plates with structured ITO (indium tin oxide) form the substrates to which the OLEDs are applied. The OLEDs have in principle the following layer structure: substrate/hole-transport layer 1 (HTL1) consisting of HTM doped with 3% of NDP-9 (commercially available from Novaled), 20 nm/hole-transport layer 2 (HTL2)/electron-blocking layer (EBL)/emission layer (EML)/optional hole-blocking layer (HBL)/electron-transport layer (ETL)/optional electron-injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm

(61) Firstly, vacuum-processed OLEDs are described. For this purpose, all materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer here always consists of at least one matrix material (host material) and an emitting dopant (emitter), which is admixed with the matrix material or matrix materials in a certain proportion by volume by co-evaporation. An expression such as M3:M2:Ir(L1).sub.3 (55%:35%:10%) here means that material M3 is present in the layer in a proportion by volume of 55%, M2 is present in the layer in a proportion of 35% and Ir(L1).sub.3 is present in the layer in a proportion of 10%. Analogously, the electron-transport layer may also consist of a mixture of two materials. The precise structure of the OLEDs is shown in Table 1. The materials used for the production of the OLEDs are shown in Table 6.

(62) The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A) and the voltage (measured at 1000 cd/m.sup.2 in V) are determined from current/voltage/luminance characteristic lines (IUL characteristic lines). For selected experiments, the lifetime is determined. The lifetime is defined as the time after which the luminous density has dropped to a certain proportion from a certain initial luminous density. The expression LT50 means that the lifetime given is the time at which the luminous density has dropped to 50% of the initial luminous density, i.e. from, for example, 1000 cd/m.sup.2 to 500 cd/m.sup.2. Depending on the emission colour, different initial luminances were selected. The values for the lifetime can be converted to a figure for other initial luminous densities with the aid of conversion formulae known to the person skilled in the art. The lifetime for an initial luminous density of 1000 cd/m.sup.2 is a usual figure here.

(63) Use of Compounds According to the Invention as Emitter Materials in Phosphorescent OLEDs

(64) The compounds according to the invention can be employed, inter alia, as phosphorescent emitter materials in the emission layer in OLEDs. The results for the OLEDs are summarised in Table 2.

(65) TABLE-US-00012 TABLE 1 Structure of the OLEDs HTL2 EBL EML HBL ETL Ex. Thickness Thickness Thickness Thickness Thickness D-Ir(L2).sub.3 HTM EBM M1:M4:lr(L2).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L9).sub.3 HTM EBM M1:M3:lr(L9).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L12).sub.3 HTM EBM M1:M4:lr(L12).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L15).sub.3 HTM EBM M1:M4:lr(L15).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L16).sub.3 HTM EBM M1:M3:lr(L16).sub.3 HBM ETM1:ETM2 180 nm 20 nm (55%:40%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L24).sub.3 HTM EBM M1:M4:lr(L24).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L27).sub.3 HTM EBM M1:M4:lr(L27).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L10).sub.2(CL1) HTM EBM M1:M3:lr(L10).sub.2(CL1) HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L11).sub.2(CL2) HTM EBM M1:M4:lr(L11).sub.2(CL2) HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L18).sub.2(CL4) HTM EBM M1:M4:lr(L18).sub.2(CL4) HBM ETM1:ETM2 180 nm 20 nm (75%:20%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L13).sub.2(CL5) HTM EBM M1:M4:lr(L230).sub.3 HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L19).sub.2(CL6) HTM EBM M1:M4:lr(L19).sub.2(CL6) HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L21).sub.2(CL6) HTM EBM M1:M4:lr(L21).sub.2(CL6) HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L23).sub.2(CL6) HTM EBM M1:M4:lr(L23).sub.2(CL6) HBM ETM1:ETM2 180 nm 20 nm (65%:30%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Ir(L26).sub.2(CL6) HTM EBM M1:M4:lr(L26).sub.2(CL6) HBM ETM1:ETM2 180 nm 20 nm (75%:20%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Pt(L22)(CL7) HTM EBM M1:M4:Pt(L22)(CL7) HBM ETM1:ETM2 180 nm 20 nm (75%:20%:5%) 10 nm (50%:50%) 25 nm 20 nm D-Pt(L25)(CL2) HTM EBM M1:M4:Pt(L25)(CL2) HBM ETM1:ETM2 180 nm 20 nm (75%:20%:5%) 10 nm (50%:50%) 25 nm 20 nm

(66) TABLE-US-00013 TABLE 2 Results of the vacuum-processed OLEDs EQE (%) 1000 cd/ Voltage (V) CIE x/y LT50 (h) Ex. m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 D-Ir(L2).sub.3 9.4 4.6 0.16/0.24 — D-Ir(L9).sub.3 14.3 4.1 0.15/0.36 600 D-Ir(L12).sub.3 9.9 4.5 0.16/0.24 250 D-Ir(L15).sub.3 16.4 4.3 0.15/0.38 700 D-Ir(L16).sub.3 16.0 4.2 0.15/0.38 — D-Ir(L24).sub.3 15.5 4.1 0.15/0.30 — D-Ir(L27).sub.3 9.7 4.3 0.15/0.35 — D-Ir(L10).sub.2(CL1) 15.5 4.1 0.15/0.27 — D-Ir(L11).sub.2(CL2) 14.1 4.2 0.15/0.34 500 D-Ir(L18).sub.2(CL4) 9.9 4.6 0.17/0.31 — D-Ir(L13).sub.2(CL5) 13.8 4.3 0.15/0.33 — D-Ir(L19).sub.2(CL6) 12.9 4.4 0.16/0.26 — D-Ir(L21).sub.2(CL6) 10.5 4.3 0.16/0.34 — D-Ir(L23).sub.2(CL6) 15.5 4.3 0.16/0.35 600 D-Ir(L26).sub.2(CL6) 4.4 4.9 0.15/0.22 — D-Pt(L22)(CL7) 6.7 4.8 0.15/0.25 — D-Pt(L25)(CL2) 8.7 4.4 0.15/0.35 —
2) Solution-Processed Devices:
A: From Soluble Functional Materials

(67) The complexes according to the invention can also be processed from solution, where they result in OLEDs which are significantly simpler as far as the process is concerned, compared with the vacuum-processed OLEDs, with nevertheless good properties. The production of components of this type is based on the production of polymeric light-emitting diodes (PLEDs), which has already been described many times in the literature (for example in WO 2004/037887).

(68) The structure is composed of substrate/ITO/PEDOT (80 nm)/interlayer (80 nm)/emission layer (80 nm)/cathode. To this end, use is made of substrates from Technoprint (soda-lime glass), to which the ITO structure (indium tin oxide, a transparent, conductive anode) is applied. The substrates are cleaned with DI water and a detergent (Deconex 15 PF) in a clean room and then activated by a UV/ozone plasma treatment. An 80 nm layer of PEDOT (PEDOT is a polythiophene derivative (Baytron P VAI 4083sp.) from H. C. Starck, Goslar, which is supplied as an aqueous dispersion) is then applied as buffer layer by spin coating, likewise in the clean room. The spin rate required depends on the degree of dilution and the specific spin coater geometry (typically for 80 nm: 4500 rpm). In order to remove residual water from the layer, the substrates are dried by heating on a hotplate at 180° C. for 10 minutes. The interlayer used serves for hole injection, in this case HIL-012 from Merck is used. The interlayer may alternatively also be replaced by one or more layers, which merely have to satisfy the condition of not being detached again by the subsequent processing step of EML deposition from solution. In order to produce the emission layer, the emitters according to the invention are dissolved in toluene together with the matrix materials. The typical solids content of such solutions is between 16 and 25 g/l if, as here, the typical layer thickness of 80 nm for a device is to be achieved by means of spin coating. The solution-processed devices comprise an emission layer comprising (polystyrene):M5:M6:Ir(L).sub.3 (25%:25%:40%:10%). The emission layer is applied by spin coating in an inert-gas atmosphere, in the present case argon, and dried by heating at 130° C. for 30 min. Finally, a cathode is applied by vapour deposition from barium (5 nm) and then aluminium (100 nm) (high-purity metals from Aldrich, particularly barium 99.99% (Order No. 474711); vapour-deposition equipment from Lesker, inter alia, typical vapour-deposition pressure 5×10.sup.−6 mbar). Optionally, firstly a hole-blocking layer and then an electron-transport layer and only then the cathode (for example Al or LiF/Al) can be applied by vacuum vapour deposition. In order to protect the device against air and atmospheric moisture, the device is finally encapsulated and then characterised. The OLED examples given have not yet been optimised, Table 3 summarises the data obtained.

(69) TABLE-US-00014 TABLE 3 Resuts with solution-processed materials EQE (%) CIE x/y 1000 cd/ Voltage (V) 1000 cd/ Ex. Complex m.sup.2 1000 cd/m.sup.2 m.sup.2 D-Ir(L20).sub.3 Ir(L20).sub.3 12.6 4.7 0.16/0.36 D-Ir(L28).sub.3 Ir(L28).sub.3 9.6 4.5 0.15/0.32 D-Ir(L30).sub.3 Ir(L30).sub.3 13.8 4.8 0.16/0.33 D-Ir(L17).sub.2(CL3) Ir(L17).sub.2(CL3) 8.7 5.0 0.17/0.35 D-Ir(L14).sub.2(CL5) Ir(L14).sub.2(CL5) 9.3 4.9 0.16/0.27
3) White-Emitting OLEDs

(70) A white-emitting OLED having the following layer structure is produced in accordance with the general processes from 1):

(71) TABLE-US-00015 TABLE 4 Structure of the white OLEDs EML EML EML HTL2 Red Blue Green HBL ETL Ex. Thickness Thickness Thickness Thickness Thickness Thickness D-W1 HTM EBM:Ir-R M1:M3:Ir(L9).sub.3 M3:Ir-G M3 ETM1:ETM2 230 nm (97%:3%) (45%:50%:5%) (90%:10%) 10 nm (50%:50%) 9 nm 8 nm 7 nm 30 nm

(72) TABLE-US-00016 TABLE 5 Device results CIE x/y LT50 EQE (%) Voltage (V) 1000 cd/m.sup.2 (h) Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 CRI 1000 cd/m.sup.2 D-W1 13.0 6.6 0.45/0.4380 1500

(73) TABLE-US-00017 TABLE 6 Structural formulae of the materials used 0 HTM EBM M1 M2 M3 M4 = HBM M5 M6 Ir-R Ir-G 0 ETM1 ETM2