Electroluminescent bridged metal complexes for use in electronic devices

Abstract

The present invention relates to metal complexes and to electronic devices, especially organic electroluminescent devices, comprising these metal complexes. The metal complex is, for example, represented by a compound formula (1) M(L).sub.n(L′).sub.m, containing a substructure M(L).sub.n of the formula (2), and where M is iridium or platinum. ##STR00001##

Claims

1. A compound of formula (1):
M(L).sub.n(L′).sub.m  (1) comprising a substructure M(L).sub.n of formula (2): ##STR00202## wherein M is iridium or platinum; CyC is a structure of formula (CyC-1): ##STR00203## wherein CyC-1 binds to CyN at the position identified by # and coordinates to M at the position identified by * and the bicyclic group containing Y and Z is bonded at the position identified by o; CyN is a structure of formula (CyN): ##STR00204## wherein the CyN binds to CyC at the position identified by # and coordinates to M at the position identified by * and the bicyclic group containing Y and Z is bonded at the position identified by o; X is the same or different in each instance and is CR or N, with the proviso that not more than two X in CyC and not more than two X in CyN are N; Y is the same or different in each instance and is CR.sub.2; Z is the same or different in each instance and is CR.sub.2; R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, 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′, 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, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, each of which is optionally substituted by one or more R.sup.1 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1C═CR.sup.1, R.sup.1C═N, Si(R.sup.1).sub.2, C═O, NR.sup.1, O, S, or CONR.sup.1 and wherein one or more hydrogen atoms are optionally replaced by D, F, Cl, Br, I, or CN, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals, an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals, or a diarylamino group, diheteroarylamino group, or arylheteroarylamino group having 10 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two adjacent R radicals together optionally define a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system; R.sup.1 is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.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 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, each of which is optionally substituted by one or more R.sup.2 radicals, wherein one or more nonadjacent CH.sub.2 groups is optionally replaced by R.sup.2C═CR.sup.2, R.sup.2C═N, Si(R.sup.2).sub.2, C═O, NR.sup.2, O, S, or CONR.sup.2 and wherein one or more hydrogen atoms is optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.2 radicals, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals, an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals, or a diarylamino group, diheteroarylamino group, or arylheteroarylamino group having 10 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; and wherein two or more adjacent R.sup.1 radicals together optionally define a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system; R.sup.2 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic organic radical having 1 to 20 carbon atoms, wherein one or more hydrogen atoms are optionally replaced by F; and wherein two or more R.sup.2 substituents together optionally define a mono- or polycyclic ring system; L′ is the same or different in each instance and is a ligand; y is in each instance 3; z is in each instance 3; n is 1, 2, or 3; m is 0, 1, 2, 3, or 4; and wherein two or more ligands L are optionally joined together or L is optionally joined to L′ by a single bond or a bivalent or trivalent bridge so as to form a tridentate, tetradentate, pentadentate, or hexadentate ligand system; and R optionally is coordinated to M.

2. The compound of claim 1, wherein CyN is selected from the group consisting of structures of formulae (CyN-1) through (CyN-4): ##STR00205##

3. The compound of claim 1, wherein CyC is selected from the group consisting of structures of formulae (CyC-1a) through (CyC-1k) and CyN is selected from the group consisting of structures of formulae (CyN-1a) through (CyN-1c) and (CyN-2a) ##STR00206## ##STR00207## ##STR00208## wherein R and R.sup.1 do not form an aromatic or heteroaromatic ring system with one another and W is the same or different in each instance and is NR.sup.1, O, or S.

4. The compound of claim 1, wherein the structure of formula (2) is a structure of formula (2a): ##STR00209##

5. The compound of claim 1, wherein R, which, when X is CR, is bonded to the corresponding carbon atom, is the same or different in each instance and is selected from the group consisting of H, D, F, Br, I, N(R.sup.1).sub.2, CN, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(═O)R.sup.1, a straight-chain alkyl group having 1 to 10 carbon atoms, an alkenyl having 2 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, each of which is optionally substituted by one or more R.sup.1 radicals, and wherein one or more hydrogen atoms are optionally replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals; and wherein two R radicals together or an R radical together with an R.sup.1 radical optionally define a ring system and wherein R, which, when Y and/or Z is CR.sub.2, is bonded to the corresponding carbon atom, is the same or different in each instance and is selected from the group consisting of H, D, F, a straight-chain alkyl group having 1 to 10 carbon atoms and is optionally substituted by one or more R.sup.1 radicals, a branched or cyclic alkyl group having 3 to 10 carbon atoms and is optionally substituted by one or more R.sup.1 radicals, or an aromatic or heteroaromatic ring system having 6 to 13 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals; and wherein two or more R radicals together optionally define a ring system.

6. The compound of claim 1, wherein L′ is a bidentate monoanionic ligand.

7. The compound of claim 6, wherein L′ is selected from the group consisting of 1,3-diketonates derived from 1,3-diketones, 3-ketonates derived from 3-keto esters, carboxylates derived from aminocarboxylic acids, and ligands which have, with M, a cyclometallated five-membered ring or six-membered ring having at least one metal-carbon bond.

8. A process for preparing a compound of claim 1 comprising reacting a free ligands L and optionally L′ with a metal alkoxide of formula (58), a metal ketoketonate of formula (59), a metal halide of formula (60), a dimeric metal complex of formula (61), a metal complex of formula (62), or a metal compound bearing both alkoxide and/or halide and/or hydroxyl radicals and ketoketonate radicals: ##STR00210## wherein Hal is F, Cl, Br or I; L″ is an alcohol or a nitrile; and (Anion) is a non-coordinating anion.

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

10. A formulation comprising a compound of claim 1 and at least one further compound.

11. A formulation comprising an oligomer, polymer or dendrimer of claim 9 and at least one further compound.

12. A compound of formula (63′) ##STR00211## wherein X is the same or different in each instance and is CR or N, with the proviso that not more than two X are N; Y is the same or different in each instance and is CR.sub.2; Z is the same or different in each instance and is CR.sub.2; y is in each instance 3; and z is in each instance 3; R is the same or different in each instance and is H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, 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, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, each of which is optionally substituted by one or more R.sup.1 radicals, wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by R.sup.1C═CR.sup.1, R.sup.1C═N, Si(R.sup.1).sub.2, C═O, NR.sup.1, O, S, or CONR.sup.1 and wherein one or more hydrogen atoms are optionally replaced by D, F, Cl, Br, I, or CN, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals, an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals, or a diarylamino group, diheteroarylamino group, or arylheteroarylamino group having 10 to 40 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals; and wherein two adjacent R radicals together optionally define a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system; 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, 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 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, each of which may be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.2C═CR.sup.2, R.sup.2C═N, Si(R.sup.2).sub.2, C═O, NR.sup.2, O, S or CONR.sup.2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or an aralkyl or heteroaralkyl group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group which has 10 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals; at the same time, two or more adjacent R.sup.1 radicals together may form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system; R.sup.2 is the same or different at each instance and is H, D, F or an aliphatic, aromatic and/or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F; at the same time, two or more R.sup.2 substituents together may also form a mono- or polycyclic ring system.

13. An electronic device comprising a compound of claim 1.

14. The electronic device of claim 13, wherein the electronic device is an organic electroluminescent device comprising one or more emitting layers, wherein the compound is present in the one or more emitting layers as an emitting compound.

15. An electronic device comprising an oligomer, polymer, or dendrimer of claim 9.

16. The electronic device of claim 15, wherein the electronic device is an organic electroluminescent device comprising one or more emitting layers, wherein the oligomer, polymer, or dendrimer is present in the one or more emitting layers as an emitting compound.

Description

EXAMPLES

(1) The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. 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 figures in square brackets or the numbers quoted for individual compounds relate to the CAS numbers of the compounds known from the literature.

(2) A: Synthesis of the Synthons S and ligands L:

Example S1 and L1

(3) ##STR00045##

(4) Analogous to G. Abbiati et al., J. Org. Chem., 2003, 68, 18, 6959.

(5) 73.1 g (500 mmol) of 1-tetralone [529-34-0], 44.1 g (800 mmol) of propargylamine [2450-71-7] and 2.9 g (10 mmol) of sodium dichloroaurate(I) [21534-24-7] in 1000 ml of abs. ethanol are stirred in an autoclave at 130° C. for 12 h. After cooling, the EtOH is removed under reduced pressure, and the residue is taken up in 300 ml of dichloromethane and filtered through a silica gel bed. After the filtrate has been concentrated, the residue is distilled under reduced pressure (p about 0.05 mbar, T about 185° C.). Yield: 58.9 g (325 mmol), 65%; purity: about 98% by .sup.1H NMR.

(6) The following compounds can be prepared in an analogous manner, it being possible to purify the crude products by distillation, Kugelrohr distillation, recrystallization or chromatography:

(7) TABLE-US-00005 Ex. Reactant Product Yield L2 28% S2 63% S3 0 58% S4 60% S5 71% S6 66% S7 78% S8 0 56% S9 63% S10 70% S11 73% S12 53% S13 0 55% L3 31% L4 27%

Example S14

(8) ##STR00076##

(9) Analogous to L. Ren et al., Green Chemistry, 2015, 17, 2369.

(10) To a mixture of 2.0 g (10 mmol) of S12, 6.9 g (50 mmol) of tert-butyl hydroperoxide [75-91-2] (65% by weight in water) and 50 ml of tert-butanol are added, at 25° C., 35 mg (0.1 mmol) of manganese(II) trifluoromethanesulphonate [55120-76-8], and the mixture is stirred for 30 h. 45 ml of the solvent are removed under reduced pressure, 200 ml of water are added to the residue, and the mixture is extracted three times with 200 ml each time of dichloromethane. The combined extracts are washed five times with 200 ml each time of water and twice with 100 ml each time of saturated sodium chloride solution, and dried over magnesium sulphate. The oil remaining after the solvent has been removed is used without further purification. Yield: 1.7 g (7.9 mmol), 79%; purity: about 95% by .sup.1H NMR.

(11) In an analogous manner, it is possible to prepare S15 from S13. Yield 76%.

Example S16

(12) ##STR00077##

(13) To a mixture of 45.3 g (250 mmol) of S1, 250 ml of glacial acetic acid and 250 ml of acetic anhydride are added in portions, with good stirring, 10 portions each of 11.2 g (375 mmol) of sodium dichromate dihydrate every 30 min, and then the mixture is stirred at room temperature for 1 day and at 35° C. for 3 days. Then the yellow suspension is stirred cautiously (exothermic!) into 5 kg of ice and stirred for a further 30 min., and the yellow solids are filtered off with suction, washed five times with 300 ml each time of water and dried by suction. The crude product is dissolved in 500 ml of dichloromethane and filtered through a silica gel bed. The dichloromethane is removed under reduced pressure and the solids are extracted by stirring once with 200 ml of hot methanol. Yield: 29.9 g (143 mmol), 57%; purity: about 99% by .sup.1H NMR.

(14) In an analogous manner, it is possible to prepare the following compounds:

(15) TABLE-US-00006 Ex. Reactant Product Yield S17 63% S18 0 18% S19 21% S20 64% S21 60% S22 78% S23 0 71% S24 34% S25 48% S26 55%

Example S27

(16) ##STR00098##

(17) A sodium methoxide solution is prepared from 23.0 g (1 mol) of sodium and 2000 ml of methanol. To the latter are added, while stirring, 87.1 g (500 mmol) of dimethyl 1,3-acetonedicarboxylate [1830-54-2] and the mixture is stirred for a further 10 min. Then 41.8 g (200 mmol) of S16 are added in solid form. After stirring under reflux for 16 h, the methanol is removed under reduced pressure. To the residue are cautiously added 1000 ml of glacial acetic acid (caution: foaming!), and to the brown solution are added 60 ml of water and 180 ml of conc. hydrochloric acid. The reaction mixture is heated under reflux for 16 h, then allowed to cool, poured onto 5 kg of ice and neutralized while cooling by addition of solid sodium hydroxide solution. The precipitated solids are filtered off with suction, washed three times with 300 ml each time of water and dried under reduced pressure. The crude product is stirred in 2000 ml of dichloromethane at 40° C. for 1 h and then filtered while still warm through a Celite bed in order to remove insoluble fractions. After the dichloromethane has been removed under reduced pressure, the residue is dissolved in 100 ml of dioxane at boiling and then 500 ml of methanol are added dropwise starting from 80° C. After cooling and stirring at room temperature for a further 12 h, the solids are filtered off with suction, washed with a little methanol and dried under reduced pressure. Yield: 29.5 g (102 mmol), 51%; purity: about 90% by .sup.1H NMR. The product thus obtained is converted further without purification.

(18) In an analogous manner, it is possible to prepare the following compounds:

(19) TABLE-US-00007 Ex. Reactant Product Yield S28 00 50% S29 01 02 53% S30 03 04 48% S31 05 06 57% S32 07 08 55% S33 09 0 21% S34 59% S35 54% S36 63% S37 60% S38 0 55% S39 11%

Example L5

(20) ##STR00123##

(21) A mixture of 28.9 g (100 mmol) of S27, 50.1 g (1 mol) of hydrazine hydrate, 67.3 g (1.2 mol) of potassium hydroxide and 400 ml of ethylene glycol is heated under reflux for 4 h. Then the temperature is increased gradually and the water formed and excess hydrazine hydrate are distilled off on a water separator. After 16 h under reflux, the reaction mixture is allowed to cool, poured into 2 l of water and extracted three times with 500 ml each time of dichloromethane. The dichloromethane phase is washed five times with 300 ml each time of water and twice with 300 ml each time of saturated sodium chloride solution, and dried over magnesium sulphate. After the dichloromethane has been removed under reduced pressure, the oily residue is chromatographed on silica gel with dichloromethane (Rf about 0.6). For further purification, the pale yellow oil thus obtained can be subjected to Kugelrohr distillation or recrystallized from methanol. Yield: 12.0 g (46 mmol), 46%; purity: about 99% by .sup.1H NMR.

(22) In an analogous manner, it is possible to prepare the following compounds:

(23) TABLE-US-00008 Ex. Reactant Product Yield L6 51% L7 48% L8 43% L9 0 55% L10 21% L11 62% L12 58% L13 61% L14 0 59% L15 50% L16 63% L17 31%

(24) C: Synthesis of the Metal Complexes:

(25) 1) Tris-Facial Homoleptic Ir Complexes

Example Ir(L5).SUB.3

(26) ##STR00148##

(27) Variant A:

(28) A mixture of 9.2 g (35 mmol) of ligand L5, 4.90 g (10 mmol) of trisacetylacetonatoiridium(III) [15635-87-7] and 100 g of hydroquinone [123-31-9] is initially charged in a 500 ml two-neck round-bottomed flask with a glass-sheathed magnetic core. The flask is provided with a water separator (for media of lower density than water) and an air condenser with argon blanketing. The flask is placed in a metal heating bath. The apparatus is purged with argon from the top via the argon blanketing system for 15 min, allowing the argon to flow out of the side neck of the two-neck flask. Through the side neck of the two-neck flask, a glass-sheathed Pt-100 thermocouple is introduced into the flask and the end is positioned just above the magnetic stirrer core. Then the apparatus is thermally insulated with several loose windings of domestic aluminium foil, the insulation being run up to the middle of the riser tube of the water separator. Then the apparatus is heated rapidly with a heated laboratory stirrer system to 260° C., measured with the Pt-100 thermal sensor which dips into the molten stirred reaction mixture. Over the next 1.5 h, the reaction mixture is kept at 260° C., in the course of which a small amount of condensate is distilled off and collects in the water separator. After cooling to 100° C., 500 ml of methanol are cautiously added to the melt cake, and boiled until a yellow suspension has formed. The yellow suspension thus obtained is filtered through a double-ended frit (P3), and the yellow solids are washed three times with 100 ml of methanol and then dried under reduced pressure. Crude yield: quantitative. The yellow product is purified further by continuous hot extraction five times with toluene (amount initially charged in each case about 150 ml, extraction thimble: standard Soxhlet thimbles made from cellulose from Whatman) with careful exclusion of air and light. Finally, the product is subjected to fractional sublimation under high vacuum (p about 10.sup.−5 mbar, T 340° C.). Yield: 7.6 g (7.8 mmol), 78%. Purity: >99.9% by HPLC.

(29) Variant B:

(30) Procedure analogous to Example Ir(L5).sub.3, Variant A, except that 300 ml of ethylene glycol [107-21-1] are used rather than 100 g of hydroquinone and the mixture is stirred under reflux for 48 h. After cooling to 70° C., the mixture is diluted with 300 ml of ethanol, and the solids are filtered off with suction (P3), washed three times with 100 ml each time of ethanol and dried under reduced pressure. Further purification is effected as described in Variant A. Yield: 4.4 g (4.5 mmol), 45%. Purity: >99.9% by HPLC.

(31) Variant C:

(32) Sodium [cis,trans-dichloro(bisacetylacetonato]iridate(III) as Iridium Reactant

(33) A mixture of 10 mmol of sodium [cis,trans-dichloro(bisacetylacetonato]iridate(III) [876296-21-8] and 40 mmol of the ligand in 100 ml of ethylene glycol (or else alternatively propylene glycol or diethylene glycol) is heated under gentle reflux under a gentle argon stream for the time specified. After cooling to 60° C., the mixture is diluted while stirring with a mixture of 50 ml of ethanol and 50 ml of 2 N hydrochloric acid and stirred for a further 1 h, and the precipitated solids are filtered off with suction, washed three times with 30 ml each time of ethanol and then dried under reduced pressure. Purification as described under A. Yield: 5.9 g (6.1 mmol), 61%. Purity: >99.9% by HPLC.

(34) The purification of the complexes obtained according to Variant A, B and C can, as well as purification by repeated hot extraction, also be effected by recrystallization or by chromatography.

(35) If chiral ligands are used, the fac metal complexes derived are obtained as a diastereomer mixture. The enantiomers Λ,Δ of the C3 point group generally have much lower solubility in the extractant than the enantiomers of the C1 point group, which consequently accumulate in the mother liquor. Separation of the C3 from the C1 diastereomers in this way is frequently possible. In addition, the diastereomers can also be separated by chromatography. If ligands of the C1 point group are used in enantiomerically pure form, a Λ,Δ diastereomer pair of the C3 point group is the result. The diastereomers can be separated by crystallization or chromatography and hence be obtained as enantiomerically pure compounds.

(36) In an analogous manner, it is possible to prepare the following compounds:

(37) TABLE-US-00009 Variant Reaction time* Reaction temperature* Product Ligand Extractant* Yield Ir(L1).sub.3 (comp.) L1 42% Ir(L2).sub.3 L2 A 26% (comp.) 2 h ethyl acetate Ir(L3).sub.3 L3 0 56% Ir(L4).sub.3 L4 A 58% diastereomer mixture Ir(L6).sub.3 L6 A 76% 3 h Ir(L7).sub.3 L7 A 78% Ir(L8).sub.3 L8 A 75% Ir(L9).sub.3 L9 A 81% C, 60 h 69% 10/3 L10 A 58% B 46% Ir(11).sub.3 L11 A 80% 2 h mesitylene Ir(L12).sub.3 L12 A 76% Ir(L13).sub.3 L13 A 81% Ir(L14).sub.3 L14 66% Ir(L15).sub.3 L15 A 63 3 h 270° C. *if different from the conditions described

(38) 2) Iridium Complexes of the [Ir(L).sub.2Cl]2 Type

(39) Variant A:

(40) A mixture of 22 mmol of the ligand, 10 mmol of iridium(III) chloride hydrate [876296-21-8], 75 ml of 2-ethoxyethanol and 25 ml of water is heated under reflux with good stirring for 16-24 h. If the ligand dissolves incompletely in the solvent mixture if at all under reflux, 1,4-dioxane is added until a solution has formed. After cooling, the precipitated solids are filtered off with suction, washed twice with ethanol/water (1:1, v/v) and then dried under reduced pressure. The chloro dimer of the formula [Ir(L).sub.2Cl].sub.2 thus obtained is converted further without purification.

(41) Variant B:

(42) A mixture of 10 mmol of sodium bisacetylacetonatodichloroiridate(III) [876296-21-8] and 22 mmol of the ligand L and a glass-ensheathed magnetic stirrer bar are sealed by melting under reduced pressure (10.sup.−5 mbar) into a thick-wall 100 ml glass ampoule. Hydroquinone may be added as a melting aid and reaction medium. The ampoule is heated at the temperature specified for the time specified, in the course of which the molten mixture is stirred with the aid of a magnetic stirrer. After cooling (CAUTION: the ampoules are usually under pressure!), the ampoule is opened, the sinter cake is stirred with 100 g of glass beads (diameter 3 mm) in 100 ml of the suspension medium specified (the suspension medium is chosen such that the ligand has good solubility but the chloro dimer of the formula [Ir(L).sub.2Cl].sub.2 has sparing solubility therein; typical suspension media are methanol, ethanol, dichloromethane, acetone, ethyl acetate, toluene, etc.) for 3 h and mechanically digested in the process. The fine suspension is decanted off from the glass beads, and the [(Ir(L).sub.2 Cl].sub.2 solids, which still contain about 2 eq of NaCl, referred to hereinafter as the crude chloro dimer, are filtered off with suction and dried under reduced pressure. The crude chloro dimer of the formula [Ir(L).sub.2Cl].sub.2 thus obtained is converted further without purification.

(43) TABLE-US-00010 Ir complex Variant Temp./time Ligand Melting aid Ex. L Suspension medium Yield [Ir(L5).sub.2Cl].sub.2 L5 76% [Ir(L5).sub.2Cl].sub.2 L5 [Ir(L5).sub.2Cl].sub.2 81% B 230° C./12 h hydroquinone [Ir(L7).sub.2Cl].sub.2 L7 [Ir(L7).sub.2Cl].sub.2 84% B 230° C./12 h [Ir(L9).sub.2Cl].sub.2 L9 [Ir(L9).sub.2Cl].sub.2 93% B 230° C./12 h [Ir(L12).sub.2Cl].sub.2 L12 [Ir(L12).sub.2Cl].sub.2 90% B 230° C./12 h hydroquinone [Ir(L14).sub.2Cl].sub.2 L14 [Ir(L14).sub.2Cl].sub.2 76% B 240° C./12 h [Ir(L16).sub.2Cl].sub.2 L16 [Ir(L16).sub.2Cl].sub.2 92% B 230° C./12 h [Ir(L17).sub.2Cl].sub.2 L17 [Ir(L17).sub.2Cl].sub.2 89% B 230° C./12 h

(44) 3) Iridium Complexed of the [Ir(L).sub.2(HOME).sub.2]OTf Type

(45) To a suspension of 5 mmol of the chloro dimer [Ir(L).sub.2Cl].sub.2 in 150 ml of dichloromethane are added 5 ml of methanol and then 10 mmol of silver(I) trifluoromethanesulphonate [2923-28-6], and the mixture is stirred at room temperature for 18 h. The precipitated silver(I) chloride is filtered off with suction through a Celite bed, the filtrate is concentrated to dryness, the yellow residue is taken up in 30 ml of toluene or cyclohexane, and the solids are filtered off, washed with n-heptane and dried under reduced pressure. The product of the formula [Ir(L).sub.2(HOMe).sub.2]OTf thus obtained is converted further without purification.

(46) TABLE-US-00011 Ex. [Ir(L).sub.2Cl].sub.2 [Ir(L).sub.2(HOMe).sub.2]OTf Yield [Ir(L5).sub.2(HOMe).sub.2]OTf Ir[(L5)Cl].sub.2 81% [Ir(L7).sub.2(HOMe).sub.2]OTf [Ir(L7).sub.2Cl].sub.2 [Ir(L7).sub.2(HOMe).sub.2]OTf 85% [Ir(L9).sub.2(HOMe).sub.2]OTf [Ir(L9).sub.2Cl].sub.2 [Ir(L9).sub.2(HOMe).sub.2]OTf 79% [Ir(L12).sub.2(HOMe).sub.2]OTf [Ir(L12).sub.2Cl].sub.2 [Ir(L12).sub.2(HOMe).sub.2]OTf 74% [Ir(L14).sub.2(HOMe).sub.2]OTf [Ir(L14).sub.2Cl].sub.2 [Ir(L14).sub.2(HOMe).sub.2]OTf 83% [Ir(L16).sub.2(HOMe).sub.2]OTf [Ir(L16).sub.2Cl].sub.2 [Ir(L16).sub.2(HOMe).sub.2]OTf 91% [Ir(L17).sub.2(HOMe).sub.2]OTf [Ir(L17).sub.2Cl].sub.2 [Ir(L17).sub.2(HOMe).sub.2]OTf 88%

(47) 4) Heteroleptic Tris-Facial Iridium Complexes:

(48) A mixture of 10 mmol of the ligand L or L′, 10 mmol of bis(methanol)bis[2-(2-pyridinyl-κN]phenyl-κC]iridium(III) trifluoromethanesulphonate [1215692-14-0] or inventive iridium complexes of the [Ir(L).sub.2(HOMe).sub.2]OTf type, 11 mmol of 2,6-dimethylpyridine and 150 ml of ethanol is heated under reflux for 40 h. After cooling, the precipitated solids are filtered off with suction, washed three times with 30 ml each time of ethanol and dried under reduced pressure. The crude product thus obtained is chromatographed on silica gel (solvents or mixtures thereof, for example ethyl acetate, DCM, THF, toluene, n-heptane, cyclohexane), and fractionally sublimed as described in 1) Variant A.

(49) TABLE-US-00012 [Ir(L).sub.2(HOMe).sub.2]OTf Ligand Ir complex Ex. L Diastereomer Yield Ir200 (comp.) 1215692-14-0 L1 27% Ir201 1215692-14-0 L3 39% Ir202 1215692-14-0 L5 44% Ir203 [Ir(L5).sub.2(HOMe).sub.2]OTf 1008-89-5 48% Ir204 [Ir(L5).sub.2(HOMe).sub.2]OTf 26274-35-1 45% Ir205 [Ir(L5).sub.2(HOMe).sub.2]OTf 156021-09-8 50% Ir206 [Ir(L5).sub.2(HOMe).sub.2]OTf 1609373-99-0 0 54% Ir207 [Ir(L5).sub.2(HOMe).sub.2]OTf 1609374-17-5 51% Ir208 [Ir(L12).sub.2(HOMe).sub.2]OTf 1609374-06-2 46% Ir209 [Ir(L14).sub.2(HOMe).sub.2]OTf 1609374/−23 48% Ir210 [Ir(L5).sub.2(HOMe).sub.2]OTf L7 50% Ir211 [Ir(L5).sub.2(HOMe).sub.2]OTf L9 50% Ir212 [Ir(L5).sub.2(HOMe).sub.2]OTf L11 44% Ir213 [Ir(L5).sub.2(HOMe).sub.2]OTf L12 47% Ir214 [Ir(L5).sub.2(OMe).sub.2]OTf L14 34% Ir215 [Ir(L14).sub.2(HOMe).sub.2]OTf L5 52% Ir216 [Ir(L14).sub.2(HOMe).sub.2]OTf L13 0 49% Ir217 [Ir(L5).sub.2(HOMe).sub.2]OTf 230-27-3 31% Ir218 [Ir(L14).sub.2(HOMe).sub.2]OTf 1541107/−37 39% Ir219 [Ir(L14).sub.2(HOMe).sub.2]OTf 914306-48-2 40%

(50) 5) Heteroleptic Iridium Complexes Containing Ligands of the Arduengo Carbene Type:

(51) Preparation analogous to A. G. Tennyson et al., Inorg. Chem., 2009, 48, 6924.

(52) A mixture of 22 mmol of the ligand precursor (imidazolium salt), 10 mmol of iridium chloro dimer [Ir(L).sub.2Cl]2, 10 mmol of silver(I) oxide and 300 ml of 1,2-dichloroethane is stirred at 90° C. for 30 h. After cooling, the precipitated solids are filtered off with suction through a Celite bed and washed once with 30 ml of 1,2-dichloroethane, and the filtrate is concentrated to dryness under reduced pressure. The crude product thus obtained is chromatographed on silica gel (solvents or mixtures thereof, for example ethyl acetate, dichloromethane, THF, toluene, n-heptane, cyclohexane), and fractionally sublimed as described in 1) Variant A.

(53) TABLE-US-00013 [Ir(L).sub.2Cl].sub.2 Ex. Ligand L Ir complex Yield Ir300 [Ir(L14).sub.2(HOMe).sub.2]OTf 1610514-63-0 35%

(54) 6) Iridium Complexes of the Ir(L).sub.2L′ Type Containing Non-o-Metallated Ligands L′

(55) A mixture of 25 mmol of the ligand L′, 10 mmol of iridium chloro dimer [Ir(L).sub.2Cl].sub.2, 30 mmol of sodium hydrogencarbonate, 100 ml of 2-ethoxyethanol and 30 ml of water is stirred at 90° C. for 16 h. After cooling, the precipitated solids are filtered off with suction, washed three times with 30 ml each time of ethanol and dried under reduced pressure. The crude product thus obtained is chromatographed on silica gel (solvents or mixtures thereof, for example ethyl acetate, dichloromethane, THF, toluene, n-heptane, cyclohexane) or recrystallized, and fractionally sublimed as described in 1) Variant A.

(56) TABLE-US-00014 [Ir(L).sub.2Cl].sub.2 Ir complex Ex. Ligand L′ Diastereomer Yield Ir400 [Ir(L5).sub.2Cl].sub.2 123/−54 79% Ir401 [Ir(L9).sub.2Cl].sub.2 1118-71-4 71% Ir402 [Ir(L16).sub.2Cl].sub.2 123-54-6 77% Ir403 [Ir(L17).sub.2Cl].sub.2 123-54-6 68% Ir404 [Ir(L16).sub.2Cl].sub.2 1118-71-4 76% Ir405 [Ir(L17).sub.2Cl].sub.2 1118-71-4 0 69% Ir406 [Ir(L5).sub.2Cl].sub.2 1137-68-4 71%

(57) 7) Platinum Complexes of the PtLL′ Type Containing Non-o-Metallated Ligands L′

(58) Preparation analogous to J. Brooks et al., Inorg. Chem. 2002, 41, 3055. A mixture of 20 mmol of the ligand L, 10 mmol of K.sub.2PtCl.sub.4, 75 ml of 2-ethoxyethanol and 25 ml of water is heated under reflux for 16 h. After cooling and addition of 100 ml of water, the precipitated solids are filtered off with suction, washed once with 30 ml of water and dried under reduced pressure. The platinum chloro dimer of the formula [PtLCl].sub.2 thus obtained is suspended in 100 ml of 2-ethoxyethanol, 30 mmol of the ligand L′ and 50 mmol of sodium carbonate are added, and the reaction mixture is stirred at 100° C. for 16 h and then concentrated to dryness under reduced pressure. The crude product thus obtained is chromatographed on silica gel (solvents or mixtures thereof, for example ethyl acetate, dichloromethane, THF, toluene, n-heptane, cyclohexane) or recrystallized, and fractionally sublimed as described in 1) Variant A.

(59) TABLE-US-00015 Ligand L Ex. Ligand L′ Pt complex Yield Pt001 L5 123-54-6 36% Pt002 L16 1118-71-4 44% Pt003 L16 867291-13-2 51%

(60) Comparison of Thermal Stability

(61) For comparison of thermal stability, 50 mg each of the compounds Ir(L1).sub.3 (comparative example according to EP 1400514) and Ir(L5).sub.3, and also Ir200 (comparative example) and Ir202, are sealed by melting in glass ampoules under reduced pressure (p about 10.sup.−5 mbar) and then heated to 350° C. with exclusion of light for 14 days. After the thermal treatment has ended, the samples are examined for changes by means of visual assessment by eye and HPLC-MS. The inventive complexes Ir(L5).sub.3 and Ir202 appear unchanged after the thermal treatment has ended, assessed visually by eye. It is not possible to detect any changes with the aid of HPLC-MS. The complexes Ir(L1).sub.3 and Ir200 (comparative examples) have taken on an orange-brown discolouration. With the aid of HPLC-MS, it is possible to detect decomposition in the order of magnitude of about 0.5% (several species). The mass of the decomposition peaks (M+-2H and M+-4H) suggests that a portion of the dihydrobenzo[h]quinoline ligands has been converted to benzo[h]quinoline ligands by elimination of hydrogen (dehydrogenation). This thermal decomposition is highly problematic for OLED construction, since the complexes formed by dehydrogenation are likewise emissive in the OLED but emit at a much longer wavelength than the starting complexes, such that there can be colour shifts in the OLED components in the course of system operation.

(62) Comparison of Photochemical Stability

(63) 1 mmolar solutions of Ir(L1).sub.3 (comparative example) and Ir(L5).sub.3 in toluene are left to stand in test tubes under air and daylight for 10 h. Thereafter, the samples are examined by means of thin-layer chromatography (silica gel plates, eluent: toluene:DCM 9:1). Ir(L5).sub.3 shows no change compared to the original sample. The chromatogram of Ir(L1).sub.3 (comparative example) shows several secondary components (starting spot and two spots having lower Rf than the sample) that are not observed in the original material. According to NMR studies, the instability of the comparative complex is attributable to the reaction of the CH.sub.2 groups of the dihydrobenzo[h]quinoline ligand with singlet oxygen generated by triplet sensitization, forming oxidation products (hydroperoxides, alcohols, ketones). These oxidation products have an adverse effect on the properties (for example the component lifetime) of OLED components processed from solution under standard laboratory conditions.

(64) Production of the OLEDs

(65) 1) Vacuum-Processed Devices

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

(67) In the examples which follow, the results for various OLEDs are presented. Glass plaques with structured ITO (50 nm, indium tin oxide) form the substrates to which the OLEDs are applied. The OLEDs basically have the following layer structure: substrate/hole transport layer 1 (HTL1) consisting of HTM doped with 3% NDP-9 (commercially available from Novaled), 20 nm/hole transport layer 2 (HTL2)/optional 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 aluminium layer of thickness 100 nm.

(68) First of all, vacuum-processed OLEDs are described. For this purpose, all the materials are applied by thermal vapour 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-evapouration. Details given in such a form as M3:M2:Ir(L1).sub.3 (55%:35%:10%) mean here that the material M3 is present in the layer in a proportion by volume of 55%, M2 in a proportion of 35% and Ir(L1).sub.3 in a proportion of 10%. Analogously, the electron transport layer may also consist of a mixture of two materials. The exact structure of the OLEDs can be found in Table 1. The materials used for production of the OLEDs are shown in Table 3.

(69) The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the power efficiency (measured in cd/A) and the voltage (measured at 1000 cd/m.sup.2 in V) are determined from current-voltage-brightness characteristics (IUL characteristics). For selected experiments, the lifetime is determined. The lifetime is defined as the time after which the luminance has fallen from a particular starting luminance to a certain proportion. The figure LD50 means that the lifetime specified is the time at which the luminance has dropped to 50% of the starting luminance, i.e. from, for example, 1000 cd/m.sup.2 to 500 cd/m.sup.2. According to the emission colour, different starting brightnesses were selected. The values for the lifetime can be converted to a figure for other starting luminances with the aid of conversion formulae known to those skilled in the art. In this context, the lifetime for a starting luminance of 1000 cd/m.sup.2 is a standard figure.

(70) Use of Compounds of the Invention as Emitter Materials in Phosphorescent OLEDs

(71) One use of the compounds of the invention is as phosphorescent emitter materials in the emission layer in OLEDs. The iridium compounds according to Table 4 are used as a comparison according to the prior art. The results for the OLEDs are collated in Table 2.

(72) TABLE-US-00016 TABLE 1 Structure of the OLEDs HTL2 EBL EML HBL ETL Ex. thickness thickness thickness thickness thickness Red OLEDs D-IrR1 HTM — M7:M8:IrR1 ETM1 ETM1:ETM2 comp. 50 nm (60%:35%:5%) 10 nm (50%:50%) 40 nm 40 nm D-Ir402 HTM — M7:M8:Ir402 ETM1 ETM1:ETM2 50 nm (60%:35%:5%) 10 nm (50%:50%) 40 nm 40 nm D-Ir404 HTM — M7:M8:Ir404 ETM1 ETM1:ETM2 50 nm (60%:35%:5%) 10 nm (50%:50%) 40 nm 40 nm Yellow OLEDs D-IrY1 HTM — M7:M8:IrY1 ETM1 ETM1:ETM2 comp. 40 nm (62%:30%:8%) 10 nm (50%:50%) 30 nm 45 nm D-Ir(L11).sub.3 HTM — M7:M8:Ir(L11).sub.3 ETM1 ETM1:ETM2 40 nm (62%:30%:8%) 10 nm (50%:50%) 30 nm 45 nm D-Ir204 HTM — M7:M8:Ir204 ETM1 ETM1:ETM2 40 nm (62%:30%:8%) 10 nm (50%:50%) 30 nm 45 nm D-Ir217 HTM — M7:M8:Ir217 ETM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 45 nm Green OLEDs D-IrG1 HTM — M7:M8:IrG1 ETM1 ETM1:ETM2 comp. 30 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 35 nm D-IrG2 HTM — M7:M8:IrG2 ETM1 ETM1:ETM2 comp. 30 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 35 nm D-Ir(L1).sub.3 HTM — M7:M8:Ir(L1).sub.3 ETM1 ETM1:ETM2 comp. 30 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 35 nm D-Ir(L2).sub.3 HTM — M7:M8:Ir(L2).sub.3 ETM1 ETM1:ETM2 comp. 30 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 35 nm D-Ir200 HTM — M7:M8:Ir200 ETM1 ETM1:ETM2 comp. 30 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 35 nm D-Ir(L5).sub.3 HTM — M7:M8:Ir(L5).sub.3 ETM1 ETM1:ETM2 30 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 35 nm D-Ir(L6).sub.3 HTM — M7:M8:Ir(L6).sub.3 ETM1 ETM1:ETM2 30 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 35 nm D-Ir(L9).sub.3 HTM — M7:M8:Ir(L9).sub.3 ETM1 ETM1:ETM2 30 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 35 nm D-Ir203 HTM — M7:M8:Ir203 ETM1 ETM1:ETM2 30 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 35 nm D-Ir205 HTM — M7:M8:Ir205 ETM1 ETM1:ETM2 30% (60%:30%:10%) 10 nm (50%:50%) 30 nm 35 nm D-Ir206 HTM — M7:M8:Ir206 ETM1 ETM1:ETM2 30 nm (40%:50%:10%) 10 nm (50%:50%) 30 nm 35 nm D-Ir211 HTM — M7:M8:Ir211 ETM1 ETM1:ETM2 30 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 35 nm D-Ir400 HTM — M7:M8:Ir400 ETM1 ETM1:ETM2 30 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 35 nm D-Pt100 HTM — M7:M8:Pt100 ETM1 ETM1:ETM2 30 nm (40%:50%:10%) 10 nm (50%:50%) 30 nm 35 nm Blue OLEDs D-Ir(L14).sub.3 HTM EBM M1:M4:Ir(L14).sub.3 HBM ETM1:ETM2 30 nm 10 nm (60%:35%:5%) 10 nm (50%:50%) 25% 15 nm D-Ir218 HTM EBM M1:M4:Ir218 HBM ETM1:ETM2 30 nm 10 nm 60/5 10% (50%:50%) 25% 15 nm

(73) TABLE-US-00017 TABLE 2 Results for the vacuum-processed OLEDs EQE (%) Voltage (V) CIE x/y LD80 (h) Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 Red OLEDs D-IrR1 16.8 2.8 0.65/0.35 14000 D-Ir402 16.5 3.0 0.63/0.36 18000 D-Ir404 17.2 2.9 0.64/0.36 21000 Yellow OLEDs D-IrY1 22.3 3.0 0.44/0.54 30000 D-Ir(L11).sub.3 19.8 2.9 0.39/0.57 23000 D-Ir204 23.4 2.9 0.46/0.53 43000 D-Ir217 20.9 2.9 0.46/0.53 42000 Green OLEDs D-IrG1 18.0 3.4 0.32/0.64 9000 D-IrG2 18.3 3.3 0.33/0.63 23000 D-Ir(L1).sub.3 19.1 3.3 0.34/0.62 15000 D-Ir(L2).sub.3 18.9 3.4 0.35/0.63 12000 D-Ir200 19.2 3.3 0.34/0.62 11000 D-Ir(L5).sub.3 20.3 3.3 0.32/0.64 29000 D-Ir(L6).sub.3 20.7 3.3 0.32/0.65 35000 D-Ir(L9).sub.3 20.5 3.5 0.33/0.64 27000 D-Ir203 20.0 3.3 0.32/0.64 20000 D-Ir205 20.1 3.2 0.33/0.63 28000 D-Ir206 23.3 3.2 0.32/0.65 29000 D-Ir211 22.2 3.3 0.32/0.64 33000 D-Ir400 23.1 3.5 0.35/0.63 20000 D-Pt100 19.1 3.6 0.31/0.62 — Blue OLEDs D-Ir(L14).sub.3 21.7 4.8 0.16/0.30 1400 D-Ir218 23.5% 4.6 0.16/0.31 1600

(74) 2) Solution-Processed Devices Made from Soluble Functional Materials

(75) The complexes of the invention may also be processed from solution and in that case lead to OLEDs which are much simpler in terms of process technology compared to the vacuum-processed OLEDs, but nevertheless have good properties. The production of such components 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). The structure is composed of substrate/ITO/PEDOT (80 nm)/interlayer (80 nm)/emission layer (80 nm)/cathode. For this purpose, substrates from Technoprint (soda-lime glass) are used, to which the ITO structure (indium tin oxide, a transparent conductive anode) is applied. The substrates are cleaned in a cleanroom with DI water and a detergent (Deconex 15 PF) and then activated by a UV/ozone plasma treatment. Thereafter, likewise in the cleanroom, as a buffer layer, an 80 nm layer of PEDOT (PEDOT is a polythiophene derivative (Baytron P VAI 40835p.) from H. C. Starck, Goslar, which is supplied as an aqueous dispersion) is applied by spin-coating. The required spin rate depends on the degree of dilution and the specific spin-coater geometry (typical value for 80 nm: 4500 rpm). In order to remove residual water from the layer, the substrates are baked 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 fulfil the condition of not being leached off again by the subsequent processing step of EML deposition from solution. For production of the emission layer, the emitters of the invention are dissolved together with the matrix materials in toluene. The typical solids content of such solutions is between 16 and 25 WI when, as here, the layer thickness of 80 nm which is typical of a device is to be achieved by means of spin-coating. The type 1 solution-processed devices contain an emission layer composed of (polystyrene):M5:M6:Ir(L).sub.3 (20%:30%:40%:10%); the type 2 devices contain an emission layer composed of (polystyrene):M5:M6:Ir(L204).sub.3:Ir(L).sub.3 (20%:20%:40%:15%:5%). The emission layer is spun on in an inert gas atmosphere, argon in the present case, and baked at 130° C. for 30 min. Lastly, a cathode composed of barium (5 nm) and then aluminium (100 nm) (high-purity metals from Aldrich, particularly barium 99.99% (cat. no. 474711); vapour deposition systems from Lesker or the like, typical vapour deposition pressure 5×10.sup.−6 mbar) is applied by vapour deposition. It is optionally possible first to apply a hole blocker layer and then an electron transport layer and only then the cathode (e.g. Al or LiF/Al) by vapour deposition under reduced pressure. In order to protect the device from air and air humidity, the device is finally encapsulated and then characterized. The OLED examples cited are yet to be optimized; Table 3 summarizes the data obtained.

(76) Table 3: Results with Materials Processed from Solution

(77) TABLE-US-00018 TABLE 3 Results with materials processed from solution EQE (%) Emitter Efficiency at Voltage (V) CIE x/y Ex. Device 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 Red OLEDs D-Sol001 Ir405 16.3 4.0 0.64/0.36 Type 2 Green OLEDs D-Sol100 Ir207 20.3 5.1 0.59/0.39 Type 1 D-Sol-101 Ir211 20.7 5.3 0.62/0.34 Type 1

(78) TABLE-US-00019 TABLE 4 Structural formulae of the materials used 0 00 01