Metal complexes

Abstract

The invention relates to metal complexes and to electronic devices, in particular organic electroluminescence devices, containing said metal complexes.

Claims

1. A compound of formula (1):
[Ir(L).sub.n(L′).sub.m]  (1) wherein the compound of formula (1) comprises a substructure Ir(L).sub.n of formula (2): ##STR00549## wherein Y is the same or different in each instance and is CR or N, with the proviso that not more than one Y per cycle is N, or two adjacent Y together are a group of formula (3): ##STR00550## wherein the dotted bonds denote the linkage of this group in the ligand; X is the same or different in each instance and is CR or N, with the proviso that not more than two X per ligand are N; R is the same or different in each instance and is H, D, F, Cl, 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, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, a straight-chain alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, or thioalkoxy group having 3 to 40 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, 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, or CN, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.1 radicals, an aryloxy or heteroaryloxy group having 5 to 60 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 or more adjacent R radicals together optionally define a mono- or polycyclic, aliphatic, aromatic and/or benzofused 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, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(═O)R.sup.2, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a straight-chain alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, or thioalkoxy group having 3 to 40 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 are optionally replaced by R.sup.2C═CR.sup.2, Si(R.sup.2).sub.2, C═O, NR.sup.2, O, S, or CONR.sup.2 and wherein one or more hydrogen atoms are optionally replaced by D, F, or CN, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals, an aryloxy or heteroaryloxy group having 5 to 60 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 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 D or F; and wherein two or more R.sup.2 substituents together optionally define a mono- or polycyclic, aliphatic or aromatic ring system; L′ is the same or different in each instance and is a mono- or bidentate ligand; n is 1, 2, or 3; m is 0, 1, 2, 3, or 4; wherein, in the substructure of formula (2), two adjacent Y are CR and the respective R radicals together with the carbon atoms to which they are attached define a ring of formula (4) or formula (5) and/or two adjacent Y are a group of formula (3) and two adjacent X in the group of formula (3) are CR and the respective R radicals together with the carbon atoms to which they are attached define a ring of formula (4) or formula (5): ##STR00551## wherein the dotted bonds denote the linkage of the two carbon atoms in the ligand; A.sup.1 and A.sup.3 are the same or different in each instance and are C(R.sup.3).sub.2, O, S, NR.sup.3, or C(═O); A.sup.2 is C(R.sup.1).sub.2, O, S, NR.sup.3, or C(═O); G is an alkylene group having 1, 2, or 3 carbon atoms and is optionally substituted by one or more R.sup.2 radicals, —CR.sup.2═CR.sup.2—, or an ortho-bonded arylene or heteroarylene group having 5 to 14 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; R.sup.3 is the same or different in each instance and is F, a straight-chain alkyl or alkoxy group having 1 to 10 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 10 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 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 hydrogen atoms are optionally replaced by D or F, an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals, an aryloxy or heteroaryloxy group having 5 to 24 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals, or an aralkyl or heteroaralkyl group having 5 to 24 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; and wherein two R.sup.3 radicals bonded to the same carbon atom together optionally define an aliphatic or aromatic ring system and thus form a spiro system; and wherein R.sup.3 with an adjacent R or R.sup.1 radical optionally defines an aliphatic ring system; with the proviso that no two heteroatoms in A.sup.1-A.sup.2-A.sup.1 are bonded directly to one another and no two C═O groups are bonded directly to one another.

2. The compound of claim 1, wherein n is 3 and m is 0, or n is 2 and m is 1, wherein L′ is a bidentate ligand which coordinates to the iridium via one carbon atom and one nitrogen atom, one carbon atom and one oxygen atom, two oxygen atoms, two nitrogen atoms, or one oxygen atom and one nitrogen atom, or n is 1 and m is 2, where L′ is an ortho-metalated ligand which coordinates to the iridium via one carbon atom and one nitrogen or oxygen atom.

3. The compound of claim 1, wherein the substructure Ir(L).sub.n is selected from the group consisting of structures of formulae (6) through (15): ##STR00552## ##STR00553## wherein Y is the same or different in each instance and is CR or N.

4. The compound of claim 1, wherein a total of 0, 1, or 2 of Y and, if present, X in L are N.

5. The compound of claim 1, wherein the substructure Ir(L).sub.nis selected from the group consisting of structures of formulae (6-1) through (6-7), (7-1) through (7-6), (8-1) through (8-5), (9-1) through (9-5), (10-1) through (10-5), (11-1) through (11-6), (12-1) through (12-4), (13-1) through (13-3), (14-1) through (14-4), and (15-1) through (15-3): ##STR00554## ##STR00555## ##STR00556## ##STR00557## ##STR00558## ##STR00559## ##STR00560## ##STR00561## ##STR00562## ##STR00563## ##STR00564## ##STR00565##

6. The compound of claim 1, wherein one or more of Y and/or X are N and a substituent R bonded adjacent to N is selected from the group consisting of CF.sub.3, OCF.sub.3, alkyl or alkoxy groups having 1 to 10 carbon atoms, a dialkylamino group having 2 to 10 carbon atoms, aromatic or heteroaromatic ring systems optionally substituted by one or more substituents R.sup.1, or aralkyl or heteroaralkyl groups optionally substituted by one or more substituents R.sup.1, or wherein the substituent R bonded adjacent to N is incorporated in a structure of formula (4) or (5).

7. The compound of claim 1, wherein the substructure Ir(L).sub.n is selected from the group consisting of substructures of formulae (6a) through (15h): ##STR00566## ##STR00567## ##STR00568## ##STR00569## ##STR00570## ##STR00571## ##STR00572## ##STR00573## ##STR00574## ##STR00575## ##STR00576## ##STR00577## ##STR00578## ##STR00579## wherein * in each case denotes the position at which the two adjacent Y or X are CR and the respective R radicals together with the carbon atoms to which they are attached define a ring of formula (4) or formula (5).

8. The compound of claim 1, wherein the structure of formula (4) is selected from the group consisting of formulae (4-A), (4-B), (4-C), (4-D), and (4-E): ##STR00580## wherein A.sup.1, A.sup.2 and A.sup.3 are the same or different in each instance and are O or NR.sup.3, and wherein the structure of formula (5) is selected from the group consisting of formulae (5-A), (5-B), and (5-C): ##STR00581##

9. The compound of claim 1, wherein R.sup.3 is the same or different in each instance and is F, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein one or more nonadjacent CH.sub.2 groups or optionally replaced by R.sup.2C═CR.sup.2 and one or more hydrogen atoms are optionally replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 14 aromatic ring atoms and is optionally substituted by one or more R.sup.2 radicals; and wherein two R.sup.3 radicals bonded to the same carbon atom together optionally define an aliphatic or aromatic ring system and thus form a spiro system; and wherein R.sup.3 optionally defines an aliphatic ring system with an adjacent R or R.sup.1 radical.

10. A process for preparing the compound of claim 1 comprising reacting the ligand with an iridium alkoxide of formula (44), an iridium ketoketonate of formula (45), an iridium halide of formula (46), or a dimeric iridium complex of formula (47) or (48): ##STR00582## wherein Hal is F, Cl, Br, or I, or reacting the ligand L with an iridium complex of formula [Ir(L′).sub.2(HOMe).sub.2]A or [Ir(L′).sub.2(NCMe).sub.2]A or reacting the ligand L′ with an iridium complex of formula [Ir(L).sub.2(HOMe).sub.2]A or [Ir(L).sub.2(NCMe).sub.2]A, wherein A is a non-coordinating anion, or reacting the ligand with an iridium compound having both alkoxide and/or halide and/or hydroxyl radicals and ketoketonate radicals.

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

12. The formulation of claim 11, wherein the at least one further compound is a solvent.

13. An electronic device comprising at least one compound of claim 1.

14. The electronic device of claim 13, wherein the electronic 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.

15. The electronic device of claim 14, wherein the electronic device is an organic electroluminescent device, wherein the compound is used as an emitting compound in one or more emitting layers comprising a matrix material.

16. The electronic device of claim 15, wherein the matrix material comprises ketones, phosphine oxides, sulfoxides, sulfones, triarylamines, carbazoles, indolocarbazoles, indenocarbazoles, azacarbazoles, bipolar matrix materials, azaboroles, boronic esters, diazasiloles, diazaphospholes, triazines, zinc complexes, beryllium complexes, dibenzofurans, and/or bridged carbazole derivatives.

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 VWR, Sigma-ALDRICH or ABCR. The numbers for the compounds known from the literature, some of which are also stated in square brackets, are the CAS numbers of the compounds.

2,3-Substituted Benzo[h]Quinolines—Synthesis Methods

(2) General Method:

(3) An aromatic o-aminocarbaldehyde (400 mmol) is dissolved in 1.1 of dry 1,4-dioxane at 60° C. and the entire apparatus is carefully purged with inert gas. A (bi)cyclic α-methylene ketone (600 mmol, 1.5 eq) and potassium tert-butoxide (400 mmol, 1 eq) are added and the reaction mixture is heated to 90° C. until the reactant has been entirely depleted. After cooling, the reaction is diluted with water and extracted with ethyl acetate. The organic phases are combined, washed with water and saturated NaCl solution and freed of the solvent under reduced pressure. The residue is taken up in 1 of dichloromethane and filtered through silica gel. For further removal of secondary components, recrystallization is effected from methanol and column chromatography purification is effected using silica gel with ethyl acetate/heptane.

(4) Example: Ligand 1 (L1)

(5) ##STR00077##

(6) 1-aminonaphthalene-2-carbaldehyde (407 mmol, 69.7 g), norcamphor (611 mmol, 67.3 g, 1.5 eq) and, as base, potassium tert-butoxide (407 mmol, 45.7 g) are converted by the general method. For removal of secondary components, recrystallization is effected from methanol and column chromatography purification is effected using silica gel with ethyl acetate/heptane (1:5). 63.7 g (259 mmol, 64%) of a colorless solid are obtained.

(7) The reactants reacted with one another by the general method may be the o-aminocarbaldehydes and (bi)cyclic α-methylene ketones specified in the following tables:

(8) TABLE-US-00001 ο-Amino- (Bi)cyclic α-methylene Ex. carbaldehyde ketone Ligand Yield L1 0 64% L2 53% L3 33% L4 40% L5 0 11% L6  9% L7 43% L8 00 01 53% L9 02 03 04 30% L10 05 06 07 36% L11 08 09 0 24% L12 29% L13 30% L14 32% L15 0 30% L16 26% L17 39% L18 0 36% L19 23% L20 38% L21 0 31% L22 22% L23 24% L24 27% L25 0 32% L26 37% L27 29% L28 0 58% L29 48% L30 37% L31 0 32% L32 34% L33 35% L34 36% L35 0 31% L36 71%

3,4-substituted benzo[h]quinolines

(9) Reaction Scheme:

(10) ##STR00186##
Synthesis Methods
General Method for Step 1: Conversion of an α-methylene Ketone to a Bromoalkenecarbaldehyde

(11) A mixture of DMF (25 mL) and chloroform (80 mL) is cooled to 0° C. and inertized. 5.8 mL (60 mmol) of PBr.sub.3 in 10 mL of chloroform are slowly added dropwise and the reaction mixture is stirred at room temperature for 2 h. The suspension is heated to reflux and the ketone (50 mmol) in 15 mL of chloroform is slowly added dropwise. The reaction is boiled under reflux for a further 12 h, cooled down and added gradually to a 1 M NaOH solution. The mixture is extracted repeatedly with diethyl ether and dried over sodium sulfate, and the solvent is removed under reduced pressure.

(12) Example for S2:

(13) ##STR00187##

(14) A mixture of DMF (25 mL) and chloroform (80 mL) is cooled to 0° C. and inertized. 5.8 mL (60 mmol) of PBr.sub.3 in 10 mL of chloroform are slowly added dropwise and the reaction mixture is stirred at room temperature for 2 h. The suspension is heated to reflux and the (+)-camphor (50 mmol, 7.6 g) in 15 mL of chloroform is slowly added dropwise. The mixture is boiled under reflux for a further 12 h, cooled down and added gradually to a 1 M NaOH solution. The mixture is extracted repeatedly with diethyl ether and dried over sodium sulfate, and the solvent is removed under reduced pressure. The oil obtained is purified further by means of a vacuum distillation. A pale yellow oil is obtained in a yield of 24% (2.92 g, 12 mmol). The following (bi)cyclic α-methylene ketones can be converted to bromoalkenecarbaldehydes by the general method in the yield reported:

(15) TABLE-US-00002 Bromoalkene- Ex. Methylene ketone carbaldehyde Yield S1 27% S2 0 24% S3 15% S4  8% S5 21% S6 14% S7 00 01 44% S8 02 03 13% S9 04 05 10% S10 06 07 22% S11 08 09 15% S12 0 12% S13 16% S14 15% S15 17%
General Method for Step 2: N-acetylation of an o-aminobromonaphthalene

(16) A 1-amino-2-bromoaromatic (100 mmol) is added in portions and with good stirring to an initial charge of acetic anhydride (2.1 mL, 20 mmol) cooled to 0° C. The ice bath is removed and the reaction mixture is heated to reflux for 30 minutes. After cooling, the acetic acid and the excess acetic anhydride are distilled off under reduced pressure. The residue is dissolved in dichloromethane or ethyl acetate and filtered through a silica gel column, such that the 1-(N-acetylamino)-2-bromoaromatic is obtained in 80%-95% yield.

(17) Example for S100:

(18) ##STR00218##

(19) 8.5 mL of acetic anhydride (90 mmol, 2 eq) are initially charged and cooled to 0° C. 10 g (45 mmol) of 2-bromoaminonaphthalene are added in small portions. The reaction mixture is allowed to warm up gradually to room temperature, then heated under reflux for 1 h. The mixture is cooled and the acetic acid or the excess acetic anhydride is distilled off under reduced pressure. The residue is dissolved in ethyl acetate and filtered through a silica gel column. 10.5 g (88%, 39.8 mmol) of a white solid are obtained.

(20) The following N-acetylbromoaromatics can be obtained by the general method in the yield reported:

(21) TABLE-US-00003 Amino-2- N-Acetylamino-2- Ex. bromoaromatic bromoaromatic Yield S100 0 88% S101 85% S102 92% S103 89% S104 95% S105 0 80%
General Method for Step 3: Coupling of the Bromoalkenecarbaldehyde with 1-(N-Acetylamino)-2-bromonaphthalene and Subsequent Cyclization

(22) A mixture of bromoalkenecarbaldehyde (5 mmol), the 1-(N-acetylamino)-2-bromoaromatic (5 mmol) from step 2, copper powder (2.6 g, 41 mmol) and Pd(PPh.sub.3).sub.4 (577 mg, 0.5 mmol) is dissolved in 15 mL of dry DMSO and carefully inertized. The reaction mixture is heated to 85° C. for 12 h, then anhydrous K.sub.2CO.sub.3 is added and the mixture is heated for a further 6 h. The reaction mixture is cooled down and diluted with 100 mL of ethyl acetate. The mixture is filtered, and the filtrate is washed with water, dried over sodium sulfate and freed of the solvent under reduced pressure. The residue is purified by column chromatography and a colorless powder is obtained in 35%-65% yield.

(23) Example for L501

(24) ##STR00231##

(25) A mixture of bromoalkenecarbaldehyde (S2, 1.22 g, 5 mmol), the 1-(N-acetylamino)-2-bromonaphthalene (S100, 1.32 g, 5 mmol), copper powder (2.6 g, 41 mmol) and Pd(PPh.sub.3).sub.4 (577 mg, 0.5 mmol) is dissolved in 15 mL of dry DMSO and carefully inertized. The reaction mixture is heated to 85° C. for 12 h, then anhydrous K.sub.2CO.sub.3 is added and the mixture is heated for a further 6 h. The reaction mixture is cooled down and diluted with 100 mL of ethyl acetate. The mixture is filtered, and the filtrate is washed with water, dried over sodium sulfate and freed of the solvent under reduced pressure. The residue is purified by column chromatography (silica gel, eluent: heptane/EA 3:1), and a colorless powder is obtained in 65% yield (1.13 g, 3.2 mmol).

(26) The synthons S1-S15 can be used to prepare the following ligands by the general method:

(27) TABLE-US-00004 Methyl- Reac- ene tant Ex. ketone 2 Ligand Yield L500 S1 S100 59% L501 S2 S100 65% L502 S3 S100 66% L503 S4 S100 49% L504 S5 S100 68% L505 S6 S100 68% L506 S7 S100 62% L507 S8 S100 60% L508 S9 S100 0 37% L509 S10 S100 62% L510 S11 S100 61% L511 S12 S100 37% L512 S13 S100 38% L513 S14 S100 43% L514 S15 S100 47% L515 S1 S101 52% L516 S2 S101 58% L517 S3 S101 37% L518 S4 S101 0 48% L519 S5 S101 71% L520 S6 S101 54% L521 S7 S101 67% L522 S8 S101 51% L523 S9 S101 53% L524 S10 S101 41% L525 S11 S101 51% L526 S12 S101 56% L527 S13 S101 61% L528 S14 S101 0 41% L529 S15 S101 59% L530 S1 S102 65% L531 S2 S102 45% L532 S3 S102 47% L533 S4 S102 56% L534 S5 S102 68% L535 S6 S102 72% L536 S7 S102 55% L537 S8 S102 56% L538 S9 S102 0 57% L539 S10 S102 44% L540 S11 S102 36% L541 S12 S102 42% L542 S13 S102 53% L543 S14 S102 67% L544 S15 S102 67% L545 S1 S103 35% L546 S2 S103 63% L547 S3 S103 68% L548 S4 S103 0 64% L549 S5 S103 38% L550 S6 S103 36% L551 S7 S103 56% L552 S8 S103 43% L553 S9 S103 60% L554 S10 S103 41% L555 S11 S103 58% L556 S12 S103 65% L557 S13 S103 35% L558 S14 S103 0 38% L559 S15 S103 53% L560 S1 S104 56% L561 S2 S104 36% L562 S3 S104 63% L563 S4 S104 36% L564 S5 S104 64% L565 S6 S104 65% L566 S7 S104 66% L567 S8 S104 58% L568 S9 S104 00 51% L569 S10 S104 01 60% L570 S11 S104 02 65% L571 S12 S104 03 55% L572 S13 S104 04 44% L573 S14 S104 05 40% L574 S15 S104 06 58% L575 S1 S105 07 38% L576 S2 S105 08 56% L577 S3 S105 09 70% L578 S4 S105 0 62% L579 S5 S105 34% L580 S6 S105 35% L581 S7 S105 69% L582 S8 S105 66% L583 S9 S105 50% L584 S10 S105 42% L585 S11 S105 60% L586 S12 S105 39% L587 S13 S105 48% L588 S14 S105 0 64% L589 S15 S105 49%

(28) ##STR00322##
General Methods:
Step 1: Coupling of an Aliphatic Ketone with Malonitrile

(29) The ketone (50 mmol), malonitrile (50 mmol, 1 eq), ammonium acetate (0.75 g, 10 mmol, 0.2 eq) and acetic acid (2.3 mL, 40 mmol, 0.8 eq) are initially charged, and 45 mL of anhydrous benzene are added. The reaction mixture is boiled under reflux on a water separator until no reactants are detectable any longer. After cooling, the mixture is washed with water and saturated NaHCO.sub.3 solution and dried over magnesium sulfate. The benzene is drawn off under reduced pressure and the residue is recrystallized from heptane.

(30) Example: Coupling of the Phenyl Ketone with Malonitrile

(31) ##STR00323##

(32) (1S,4R)-3-Phenylbicyclo[2.2.1]heptan-2-one (9.3 g, 50 mmol), malonitrile (3.3 g, 50 mmol), ammonium acetate (0.75 g, 10 mmol) and acetic acid (2.3 mL, 40 mmol) are initially charged, and 45 mL of anhydrous benzene are added. The reaction mixture is boiled reflux on a water separator for 4 h. After cooling, the mixture is washed with water and saturated NaHCO.sub.3 solution and dried over magnesium sulfate. The benzene is drawn off under reduced pressure and the residue is recrystallized from heptane. 5.8 g (40 mmol, 81%) of a colorless solid are obtained.

(33) Step 2: Cyclization

(34) The reactant (35 mmol) is dissolved gradually in concentrated sulfuric acid (25 mL) at 5° C. and stirred at room temperature overnight. The reaction mixture is added to ice and the precipitated solid is filtered off, washed with water and dried. The product is recrystallized repeatedly from methanol.

(35) Example: Cyclization

(36) ##STR00324##

(37) The reactant (5 g, 35 mmol) is dissolved gradually in concentrated sulfuric acid (25 mL) at 5° C. and stirred at room temperature overnight. The reaction mixture is added to ice and the precipitated solid is filtered off, washed with water and dried. The product is recrystallized repeatedly from methanol. 3.5 g (14 mmol, 40%) of the product are obtained.

(38) Step 3: Reduction of the o-Aminonitrile to o-Aminocarbaldehyde

(39) The ortho-aminonitrile (10 mmol) is dissolved in 25 mL of anhydrous dichloromethane and cooled to 0° C. A 1 M solution of DIBAL-H in toluene (15 mmol, 1.5 eq) is slowly added dropwise and the solution is stirred at room temperature for 24 h. The reaction mixture is diluted with anhydrous diethyl ether and cooled to 0° C. 0.6 mL of water, then 0.6 mL of a 15% aqueous NaOH solution, then another 1.5 mL of water are gradually and cautiously added dropwise, and the solution is stirred for 15 minutes. Anhydrous magnesium sulfate is added, and the mixture is stirred for a further 15 minutes and filtered. The solvents are removed under reduced pressure and the crude product is purified by column chromatography with a mixture of dichloromethane/heptane.

(40) Example: Hydrolysis

(41) ##STR00325##

(42) The ortho-aminonitrile (2.34 g, 10 mmol) is dissolved in 25 mL of anhydrous dichloromethane and cooled to 0° C. A 1 M solution of DIBAL-H in toluene (15 mL, 15 mmol, 1.5 eq) is slowly added dropwise and the solution is stirred at room temperature for 24 h. The reaction mixture is diluted with anhydrous diethyl ether and cooled to 0° C. 0.6 mL of water, then 0.6 mL of a 15% aqueous NaOH solution, then another 1.5 mL of water are gradually and cautiously added dropwise, and the solution is stirred for 15 minutes. Anhydrous magnesium sulfate is added, and the mixture is stirred for a further 15 minutes and filtered. The solvents are removed under reduced pressure and the crude product is purified by column chromatography with a mixture of dichloromethane/heptane (1:1). A colorless solid is obtained in 67% yield (1.69 g, 6.7 mmol).

(43) Step 4: Conversion of the Ortho-aminocarbaldehyde to the 5,6-substituted Benzo[h]Quinoline

(44) To an initial charge of the o-aminocarbaldehyde (4 mmol) and acetaldehyde (4 mmol, 1 eq) are added 15 mL of dry ethanol. Pulverulent potassium hydroxide (4.8 mmol, 1.2 eq) are added gradually and the reaction mixture is stirred under reflux for 24 h. On completion of conversion, the solution is cooled down, dichloromethane is added and the mixture is filtered through Celite. The organic phase is washed with water, dried over magnesium sulfate and freed of the solvent under reduced pressure. The product is purified by column chromatography.

(45) Example: Cyclization to Give L1000

(46) ##STR00326##

(47) To an initial charge of the o-aminocarbaldehyde (1 g, 4 mmol) and acetaldehyde (177 mg, 0.225 mL, 4 mmol) are added 15 mL of dry ethanol. Pulverulent potassium hydroxide (0.27 g, 4.8 mmol, 1.2 eq) are added gradually and the reaction mixture is stirred under reflux for 24 h. On completion of conversion, the solution is cooled down and dichloromethane is added and the mixture is filtered through Celite. The organic phase is washed with water, dried over magnesium sulfate and freed of the solvent under reduced pressure. The product is purified by column chromatography and gives 0.71 g (2.9 mmol, 74%) of a colorless solid.

(48) By conducting the general methods, it is possible to prepare the following ligands:

(49) TABLE-US-00005 Yield over Ex. Ketone Ligand 4 stages L1000 8.4% L1001 0 9.3% L1002 7.9%

7,8-substituted benzo[h]quinolines

(50) Reaction Scheme:

(51) ##STR00333##
Synthesis Methods:
General Method: Conversion of an o-phenol Carbaldehyde to an o-trifluoromethanesulfonic Acid Carbaldehyde

(52) The hydroxyquinolinecarbaldehyde (50 mmol) is dissolved in 25 mL of dichloromethane and cooled to 0° C. A solution, cooled to 0° C., of pyridine (12.6 mL, 75 mmol, 1.5 eq) and trifluoromethanesulfonic anhydride (8.1 mL, 100 mmol, 2 eq) is slowly added dropwise within 15 minutes and the reaction mixture is stirred at room temperature for 12-24 h. The reaction is stopped by adding 60 mL of water and the organic phase is removed. The aqueous phase is extracted repeatedly with diethyl ether and the combined organic phases are dried over magnesium sulfate. The solvent is removed under reduced pressure and the residue is purified by column chromatography.

(53) Example:

(54) ##STR00334##

(55) The 2-hydroxynaphthalenecarbaldehyde (8.61 g, 50 mmol) is dissolved in 25 mL of dichloromethane and cooled to 0° C. A solution, cooled to 0° C., of pyridine (12.6 mL, 75 mmol, 1.5 eq) and trifluoromethanesulfonic anhydride (8.1 mL, 100 mmol, 2 eq) is slowly added dropwise within 15 minutes and the reaction mixture is stirred at room temperature for 24 h. The reaction is stopped by adding 60 mL of water and the organic phase is removed. The aqueous phase is extracted repeatedly with diethyl ether and the combined organic phases are dried over magnesium sulfate. The solvent is removed under reduced pressure and the residue is purified by column chromatography. 11.4 g (75%, 37.5 mmol) of a colorless oil is obtained.

(56) Step 2: Conversion of the o-trifluoromethanesulfonic Acid Carbaldehyde to a Pinacolboranecarbaldehyde

(57) A mixture of PdCl.sub.2(dppf).sub.2 (220 mg, 0.3 mmol, 0.03 eq), the trifluoromethanesulfonic acid carbaldehyde (10 mmol), triethylamine (4.2 mL, 30 mmol) and pinacolborane (2.2 mL, 15 mmol) is carefully inertized and dissolved in 40 mL of dioxane. The reaction mixture is heated to 80° C. for 3-12 h, cooled down, diluted with water and extracted with toluene. The organic phases are washed with water and saturated NaCl solution, dried over magnesium sulfate and freed of the solvent under reduced pressure. The residue is purified by column chromatography.

(58) Example:

(59) ##STR00335##

(60) A mixture of PdCl.sub.2(dppf).sub.2 (220 mg, 0.3 mmol, 0.03 eq), 2-trifluoromethanesulfonylnaphthalenecarbaldehyde (2.48 g, 10 mmol), triethylamine (4.2 mL, 30 mmol) and pinacolborane (2.2 mL, 15 mmol) is carefully inertized and dissolved in 40 mL of dioxane. The reaction mixture is heated to 80° C. for 12 h, cooled down, diluted with water and extracted with toluene. The organic phases are washed with water and saturated NaCl solution, dried over magnesium sulfate and freed of the solvent under reduced pressure. The residue is purified by column chromatography (EA/heptane 1:10), and 1.84 g (65%, 6.5 mmol) of a colorless oil are obtained.

(61) Step 3: Coupling of the pinacolboranecarbaldehyde with the bromoalkenecarbaldehyde

(62) 5.5 mmol of the bromoalkenecarbaldehyde, 5.5 mmol (1 eq) of pinacolboranecarbaldehyde and 10.5 mmol (1.9 eq) of potassium phosphate are initially charged, suspended in 25 mL of toluene, 25 mL of dioxane and 25 mL of water, and inertized. Added to this suspension are 45 mg of tri-o-tolylphosphine (0.15 mmol) and then 6 mg of palladium(II) acetate (0.025 mmol), and the reaction mixture is heated under reflux for 24 h. After cooling, the reaction mixture is diluted with toluene, and the organic phases are removed, washed with water, filtered through silica gel and dried over magnesium sulfate. The solvent is removed under reduced pressure. The residue is purified by column chromatography.

(63) Example:

(64) ##STR00336##

(65) 1.27 g (5.5 mmol) of the bromoalkenecarbaldehyde S6, 1.55 g (5.5 mmol, 1 eq) of pinacolboranecarbaldehyde and 2.23 g (10.5 mmol, 1.9 eq) of potassium phosphate are initially charged, suspended in 25 mL of toluene, 25 mL of dioxane and 25 mL of water, and inertized. Added to this suspension are 45 mg (0.15 mmol) of tri-o-tolylphosphine and then 6 mg (0.025 mmol) of palladium(II) acetate, and the reaction mixture is heated under reflux for 24 h. After cooling, the reaction mixture is diluted with toluene, and the organic phases are removed, washed with water, filtered through silica gel and dried over magnesium sulfate. The toluene is removed under reduced pressure. The residue is separated by column chromatography (ethyl acetate/heptane 1:9), and 1.52 g (4.95 mmol, 95%) of a colorless solid are obtained.

(66) Step 4: McMurry Coupling of the Biscarbaldehyde

(67) To a suspension of activated zinc dust (3.2 g, 49 mmol) in 60 mL of THF which has been cooled to 0° C. and inertized are slowly added dropwise 3 mL (27.4 mmol) of TiCl.sub.4. The suspension is heated under reflux for 2 h and cooled to 0° C., and a solution of the bisaldehyde (5.3 mmol) in 20 mL of THF is added dropwise within 30 minutes. The reaction mixture is gradually warmed up to room temperature, then heated under reflux for two hours. After cooling, the solution is poured into a saturated potassium carbonate solution which has been cooled to 0° C. and extracted with dichloromethane. The organic phases are combined and washed with water and saturated NaCl solution. The mixture is dried over sodium sulfate, the solvent is removed under reduced pressure and purification is effected by column chromatography.

(68) Example L1500:

(69) ##STR00337##

(70) To a suspension of activated zinc dust (3.2 g, 49 mmol) in 60 mL of THF which has been cooled to 0° C. and inertized are slowly added dropwise 3 mL (27.4 mmol) of TiCl.sub.4. The suspension is heated under reflux for 2 h and cooled to 0° C., and a solution of the bisaldehyde (1.63 g, 5.3 mmol) in 20 mL of THF is added dropwise within 30 minutes. The reaction mixture is gradually warmed up to room temperature, then boiled under reflux for two hours. After cooling, the solution is poured into a saturated potassium carbonate solution which has been cooled to 0° C. and extracted with dichloromethane. The organic phases are combined and washed with water and saturated NaCl solution. The mixture is dried over sodium sulfate, the solvent is removed under reduced pressure, purification is effected by column chromatography (silica gel, ethyl acetate/heptane 1:5) and 1.13 g (4.09 mmol, 73%) of a colorless solid are obtained.

(71) By coupling the synthons S1-S15 with 7-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)quinoline-8-carbaldehyde, it is possible to obtain the following ligands:

(72) TABLE-US-00006 Yield Bromoalkene- over 4 Ex. carbaldehyde Ligand stages L1500 S6 55% L1501 S1 47% L1502 S2 0 48% L1503 S3 40% L1504 S4 54% L1505 S5 40% L1506 S7 55% L1507 S11 50% L1508 S12 57% L1509 S13 40% L1510 S14 51% L1511 S15 45%
Synthesis of the Metal Complexes
1) Homoleptic Tris-facial Iridium Complexes:
Variant A: Trisacetylacetonatoiridium(III) as Iridium Reactant

(73) A mixture of 10 mmol of trisacetylacetonatoiridium(III) [15635-87-7], 40-60 mmol of the ligand L, optionally 1 g of an inert high-boiling additive as melting aid or solvent, for example hexadecane, m-terphenyl, triphenylene, diphenyl ether, 3-phenoxytoluene, 1,2-, 1,3-, 1,4-bisphenoxybenzene, triphenylphosphine oxide, sulfolane, 18-crown-6, triethylene glycol, glycerol, polyethylene glycols, phenol, 1-naphthol, etc., and a glass-ensheathed magnetic stirrer bar are sealed by melting under reduced pressure (10.sup.−5 mbar) into a thick-wall 50 mL glass ampoule. 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 bar. In order to prevent sublimation of the ligands at colder points in the ampoule, the whole ampoule has to have the temperature specified. Alternatively, the synthesis can be effected in a stirred autoclave with a glass insert. 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 a suspension medium (the suspension medium is chosen such that the ligand has good solubility but the metal complex has sparing solubility therein; typical suspension media are methanol, ethanol, dichloromethane, acetone, THF, 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 solids are filtered off with suction, washed with 50 mL of the suspension medium and dried under reduced pressure. The dry solid is placed in a continuous hot extractor on an Alox bed of height 3-5 cm (Alox, basic, activity level 1) and then extracted with an extractant (initial charge of about 500 mL; the extractant is chosen such that the complex has good solubility in the hot extractant and sparing solubility in the cold extractant; particularly suitable extractants are hydrocarbons such as toluene, xylenes, mesitylene, naphthylene, o-dichlorobenzene, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chloroform, carbon tetrachloride). After the extraction has ended, the extractant is concentrated under reduced pressure to about 100 mL. Metal complexes having too good a solubility in the extractant are made to crystallize by dropwise addition of 200 mL of methanol. The solid from the suspension thus obtained 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 Alox bed from the 2nd extraction onward. Once the purity of 99.5%-99.9% has been attained, the metal complex is heat-treated or sublimed. The heat treatment is effected under high vacuum (p about 10.sup.−6 mbar) within the temperature range of about 200-300° C. The sublimation is effected under high vacuum (p about 10.sup.−6 mbar) within the temperature range of about 230-400° C., the sublimation preferably being conducted in the form of a fractional sublimation. Complexes having good solubility in organic solvents can alternatively also be chromatographed on silica gel.

(74) If ligands of the C1 point group are used in racemic form, the fac metal complexes derived are obtained as a diastereomer mixture. The enantiomer pair of the C3 point group generally has much lower solubility in the extractant than that of the C1 point group, which consequently accumulates in the mother liquor. Separation of the diastereomers in this way is frequently possible. In addition, the diastereomers can also be separated by chromatography. If the ligands of the C1 point group are used in enantiomerically pure form, the Δ-Λ-diastereomer pair of the C3 point group forms.

(75) Variant B: Tris(2,2,6,6,6-tetramethyl-3,5-heptanedionato)iridium(III) as iridium reactant

(76) Procedure analogous to variant A, except using 10 mmol of tris(2,2,6,6-tetramethyl-3,5-heptanedionato)iridium [99581-86-9] in place of 10 mmol of trisacetylacetonatoiridium(III) [15635-87-7]. The use of this reactant is advantageous since the purity of the crude product obtained is frequently better than in variant A. In addition, the pressure buildup in the ampoule is frequently not as significant.

(77) Variant C: Sodium [cis,trans-dichloro(bisacetylacetonato]irdate(III) as iridium reactant

(78) A mixture of 10 mmol of sodium [cis,trans-dichloro(bisacetylacetonato]iridate(II) [876296-21-8] and 60 mmol of the ligand in 50 mL of ethylene glycol, 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, washed three times with 30 mL each time of ethanol and then dried under reduced pressure. Purification by hot extraction or chromatography and fractional sublimation as described in A.

(79) TABLE-US-00007 Variant Reaction medium Reaction temperature Reaction time Susp. Ir complex medium Yield Ex. Ligand Diastereomer Extractant % Ir(L1).sub.3 L1 0 A — 270° C. 48 h acetone o-xylene 35 Ir(L2).sub.3 L2 Ir(L2).sub.3 as Ir(L1).sub.3 12 Ir(L8).sub.3 L8 A — 260° C. 48 h ethanol o-xylene 34 Ir(L9).sub.3 L9 A — 290° C. 48 h ethyl acetate o-xylene 14 Ir(L10).sub.3 L10 Ir(L10).sub.3 as Ir(L9).sub.3 32 Ir(L16).sub.3 L16 C — 320° C. 48 h ethanol o-xylene 27 Ir(L17).sub.3 L17 A — 300° C. 36 h ethanol o-xylene 33 Ir(L18).sub.3 L18 A — 280° C. ethyl acetate o-xylene 24 Ir(L19).sub.3 L19 A — 290° C. 60 h ethyl acetate o-xylene 27 Ir(L25).sub.3 L25 A — 260° C. 24 h ethyl acetate o-xylene 32 Ir(L26).sub.3 L26 A — 290° C. 48 h ethyl acetate o-xylene 27 Ir(L27).sub.3 L27 A — 290° C. 24 h methanol o-xylene 25 Ir(L28).sub.3 L28 0 A — 260° C. 60 h ethanol o-xylene 27 Ir(L29).sub.3 L29 C — 280° C. 60 h ethanol o-xylene 34 Ir(L35).sub.3 L35 C — 260° C. 48 h ethanol o-xylene 20 Ir(L36).sub.3 L36 C — 260° C. 48 h ethanol o-xylene 23 Ir(L500).sub.3 L500 A — 260° C. 24 h ethyl acetate o-xylene 24 Ir(L501).sub.3 L501 A — 280° C. 24 h ethyl acetate o-xylene 33 Ir(L502).sub.3 L502 A — 280° C. 24 h ethyl acetate o-xylene 22 Ir(L503).sub.3 L503 A — 280° C. 24 h ethanol o-xylene 27 Ir(L504).sub.3 L504 A — 280° C. 24 h ethanol o-xylene 28 Ir(L505).sub.3 L505 A — 260° C. 24 h ethanol o-xylene 28 Ir(L506).sub.3 L506 0 A — 300° C. 48 h ethyl acetate o-xylene 12 Ir(L507).sub.3 L507 B — 300° C. 48 h ethyl acetate o-xylene 9 Ir(L508).sub.3 L508 B — 300° C. 48 h ethyl acetate o-xylene 10 Ir(L509).sub.3 L509 A — 280° C. 24 h ethyl acetate o-xylene 37 Ir(L510).sub.3 L510 B — 300° C. 24 h ethyl acetate o-xylene 10 Ir(L511).sub.3 L511 A — 260° C. 24 h ethyl acetate o-xylene 22 Ir(L512).sub.3 L512 A — 260° C. 24 h ethyl acetate o-xylene 27 Ir(L513).sub.3 L513 A — 280° C. 24 h ethyl acetate o-xylene 25 Ir(L514).sub.3 L514 A — 260° C. 24 h ethyl acetate o-xylene 25 Ir(L515).sub.3 L515 C — 280° C. 24 h ethyl acetate o-xylene 31 Ir(L516).sub.3 L516 0 C — 280° C. 24 h ethyl acetate o-xylene 29 Ir(L517).sub.3 L517 C — 280° C. 24 h ethyl acetate o-xylene 30 Ir(L518).sub.3 L518 C — 280° C. 24 h ethyl acetate o-xylene 24 Ir(L519).sub.3 L519 C — 280° C. 24 h ethyl acetate o-xylene 27 Ir(L520).sub.3 L520 C — 280° C. 24 h ethyl acetate o-xylene 26 Ir(L521).sub.3 L521 C — 280° C. 36 h ethyl acetate o-xylene 12 Ir(L522).sub.3 L522 C — 300° C. 36 h ethyl acetate o-xylene 11 Ir(L523).sub.3 L523 C — 320° C. 36 h ethyl acetate o-xylene 8 Ir(L524).sub.3 L524 C — 280° C. 24 h ethyl acetate o-xylene 23 Ir(L525).sub.3 L525 C — 300° C. 24 h ethyl acetate o-xylene 11 Ir(L526).sub.3 L526 0 C — 300° C. 24 h ethyl acetate o-xylene 22 Ir(L527).sub.3 L527 C — 280° C. 24 h ethyl acetate o-xylene 27 Ir(L528).sub.3 L528 C — 280° C. 24 h ethyl acetate o-xylene 30 Ir(L529).sub.3 L529 C — 280° C. 24 h ethyl acetate o-xylene 26 Ir(L530).sub.3 L530 A — 280° C. 24 h ethyl acetate o-xylene 22 Ir(L531).sub.3 L531 A — 280° C. 24 h ethyl acetate o-xylene 27 Ir(L532).sub.3 L532 A — 280° C. 24 h ethyl acetate o-xylene 29 Ir(L533).sub.3 L533 A — 280° C. 24 h ethyl acetate o-xylene 32 Ir(L534).sub.3 L534 A — 280° C. 24 h ethyl acetate o-xylene 30 Ir(L535).sub.3 L535 A — 260° C. 24 h ethyl acetate o-xylene 27 Ir(L536).sub.3 L536 00 C — 300° C. 36 h ethyl acetate o-xylene 15 Ir(L537).sub.3 L537 01 B — 300° C. 36 h ethyl acetate o-xylene 12 Ir(L538).sub.3 L538 02 B — 300° C. 36 h ethyl acetate o-xylene 14 Ir(L539).sub.3 L539 03 C — 260° C. 24 h ethyl acetate o-xylene 27 Ir(L540).sub.3 L540 04 B — 300° C. 24 h ethyl acetate o-xylene 14 Ir(L541).sub.3 L541 05 C — 280° C. 24 h ethyl acetate o-xylene 22 Ir(L542).sub.3 L542 06 C — 280° C. 24 h ethyl acetate o-xylene 29 Ir(L543).sub.3 L543 07 C — 280° C. 24 h ethyl acetate o-xylene 32 Ir(L544).sub.3 L544 08 C — 280° C. 24 h ethyl acetate o-xylene 34 Ir(L545).sub.3 L545 09 A — 280° C. 24 h ethanol o-xylene 28 Ir(L546).sub.3 L546 0 A — 280° C. 24 h ethanol o-xylene 26 Ir(L547).sub.3 L547 A — 280° C. 24 h ethanol o-xylene 27 Ir(L548).sub.3 L548 A — 280° C. 24 h ethanol o-xylene 24 Ir(L549).sub.3 L549 A — 280° C. 24 h ethanol o-xylene 26 Ir(L550).sub.3 L550 C — 280° C. 24 h ethanol o-xylene 26 Ir(L551).sub.3 L551 C — 300° C. 24 h ethanol o-xylene 12 Ir(L552).sub.3 L552 B — 320° C. 36 h ethanol o-xylene 13 Ir(L553).sub.3 L553 B — 320° C. 36 h ethanol o-xylene 15 Ir(L554).sub.3 L554 C — 260° C. 24 h ethyl acetate o-xylene 18 Ir(L555).sub.3 L555 C — 300° C. 24 h ethanol o-xylene 14 Ir(L556).sub.3 L556 0 A — 280° C. 36 h ethanol o-xylene 18 Ir(L557).sub.3 L557 A — 280° C. 24 h ethanol o-xylene 12 Ir(L558).sub.3 L558 A — 280° C. 24 h ethanol o-xylene 12 Ir(L559).sub.3 L559 A — 280° C. 24 h ethanol o-xylene 11 Ir(L560).sub.3 L560 B — 300° C. 24 h ethanol o-xylene 33 Ir(L561).sub.3 L561 B — 300° C. 24 h ethanol o-xylene 30 Ir(L562).sub.3 L562 B — 300° C. 24 h ethanol o-xylene 32 Ir(L563).sub.3 L563 B — 300° C. 24 h ethanol o-xylene 29 Ir(L564).sub.3 L564 B — 300° C. 24 h ethanol o-xylene 34 Ir(L565).sub.3 L565 A — 280° C. 36 h ethanol o-xylene 37 Ir(L566).sub.3 L566 0 C — 300° C. 36 h ethanol o-xylene 18 Ir(L567).sub.3 L567 C — 320° C. 48 h ethanol o-xylene 15 Ir(L568).sub.3 L568 C — 320° C. 48 h ethanol o-xylene 12 Ir(L569).sub.3 L569 A — 280° C. 24 h ethanol o-xylene 19 Ir(L570).sub.3 L570 C — 340° C. 36 h ethanol o-xylene 14 Ir(L571).sub.3 L571 A — 260° C. 48 h ethyl acetate o-xylene 33 Ir(L572).sub.3 L572 A — 260° C. 24 h ethyl acetate o-xylene 35 Ir(L573).sub.3 L573 A — 260° C. 24 h ethyl acetate o-xylene 38 Ir(L574).sub.3 L574 A — 260° C. 24 h ethyl acetate o-xylene 36 Ir(L575).sub.3 L575 C — 280° C. 24 h ethanol o-xylene 19 Ir(L576).sub.3 L576 0 C — 280° C. 24 h ethanol o-xylene 21 Ir(L577).sub.3 L577 C — 280° C. 24 h ethanol o-xylene 20 Ir(L578).sub.3 L578 C — 280° C. 24 h ethanol o-xylene 21 Ir(L579).sub.3 L579 C — 280° C. 24 h ethanol o-xylene 16 Ir(L580).sub.3 L580 B — 280° C. 24 h ethanol o-xylene 21 Ir(L581).sub.3 L581 B — 300° C. 48 h ethyl acetate o-xylene 8 Ir(L582).sub.2 L582 C — 320° C. 48 h ethanol o-xylene 6 Ir(L583).sub.3 L583 C — 320° C. 48 h ethanol o-xylene 5 Ir(L584).sub.3 L584 C — 280° C. 24 h ethanol o-xylene 9 Ir(L585).sub.3 L585 C — 320° C. 24 h ethanol o-xylene 11 Ir(L586).sub.3 L586 0 A — 260° C. 24 h ethanol o-xylene 9 Ir(L587).sub.3 L587 A — 260° C. 24 h ethanol o-xylene 12 Ir(L588).sub.3 L588 A — 260° C. 24 h ethanol o-xylene 11 Ir(L589).sub.3 L589 A — 260° C. 24 h ethanol o-xylene 12 Ir(L1000).sub.3 L1000 C — 280° C. 24 h acetone o-xylene 27 Ir(L1001).sub.3 L1001 C — 280° C. 24 h acetone o-xylene 25 Ir(L1002).sub.3 L1002 C — 280° C. 24 h acetone o-xylene 29 Ir(L1500).sub.3 L1500 A — 260° C. 24 h ethyl acetate mesitylene 38 Ir(L1501).sub.3 L1501 A — 280° C. 24 h ethyl acetate mesitylene 35 Ir(L1502).sub.3 L1502 A — 280° C. 24 h ethyl acetate mesitylene 36 Ir(L1503).sub.3 L1503 0 A — 280° C. 24 h ethyl acetate mesitylene 32 Ir(L1504).sub.3 L1504 A — 280° C. 24 h ethyl acetate mesitylene 34 Ir(L1505).sub.3 L1505 A — 280° C. 24 h ethyl acetate mesitylene 31 Ir(L1506).sub.3 L1506 A — 300° C. 48 h ethyl acetate mesitylene 17 Ir(L1507).sub.3 L1507 A — 320° C. 36 h ethyl acetate mesitylene 12 Ir(L1508).sub.3 L1508 A — 260° C. 24 h ethanol mesitylene 29 Ir(L1509).sub.3 L1509 A — 260° C. 24 h ethanol mesitylene 33 Ir(L1510).sub.3 L1510 A — 260° C. 24 h ethanol mesitylene 31 Ir(L1512).sub.3 L1511 A — 260° C. 24 h ethanol mesitylene 36
2) Heteroleptic Iridium Complexes:
Variant A:
Step 1:

(80) A mixture of 10 mmol of sodium bisacetylacetonatodichloroindate(III) [770720-50-8] and 24 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 50 mL glass ampoule. 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 bar. 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 DCM, 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 solid (Ir(L).sub.2Cl].sub.2 which still contains about 2 eq of NaCl, referred to hereinafter as the crude chloro dimer) is filtered off with suction and dried under reduced pressure.

(81) Step 2

(82) The crude chloro dimer of the formula [Ir(L).sub.2Cl].sub.2 thus obtained is suspended in a mixture of 75 mL of 2-ethoxyethanol and 25 mL of water, and 13 mmol of the coligand CL or of the coligand compound CL and 15 mmol of sodium carbonate are added thereto. After 20 h under reflux, a further 75 mL of water are added dropwise, the mixture is cooled and then the solids are filtered off with suction, and these are washed three times with 50 mL each time of water and three times with 50 mL each time of methanol, and dried under reduced pressure. The dry solid is placed in a continuous hot extractor on an Alox bed of height 3-5 cm (Alox, basic, activity level 1) and then extracted with the extractant specified (initial charge of about 500 mL; the extractant is chosen such that the complex has good solubility in the hot extractant and sparing solubility in the cold extractant; suitable extractants are hydrocarbons such as toluene, xylenes, mesitylene, naphthylene, o-dichlorobenzene, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chloroform, carbon tetrachloride). After the extraction has ended, the extractant is concentrated under reduced pressure to about 100 mL. Metal complexes having too good a solubility in the extractant are made to crystallize by dropwise addition of 200 mL of methanol. The solid from the suspensions thus obtained 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. Once the purity of 99.5%-99.9% has been attained, the metal complex is heat-treated or sublimed. As well as the hot extraction process for purification, purification can also be effected by chromatography on silica gel or Alox. The heat treatment is effected under high vacuum (p about 10.sup.−6 mbar) within the temperature range of about 200-300° C. The sublimation is effected under high vacuum (p about 10.sup.−6 mbar) within the temperature range of about 300-400° C., the sublimation preferably being conducted in the form of a fractional sublimation.

(83) TABLE-US-00008 Ir complex Step 1: Reaction temp./ Reaction time/ Li- Co- Suspension medium gand ligand Steps 2: Ex. L CL Extractant Yield Ir(L3).sub.2(CL1) L3   123-54-6 CL1 0 28% 260° C./60 h/acetone xylene Ir(L4).sub.2(CL1) L4 CL1 25% 280° C./80 h/acetone xylene Ir(L5).sub.2(CL1) L5 CL1 16% 280° C./60 h/ethyl acetate xylene Ir(L6).sub.2(CL1) L6 CL1 15% 260° C./80 h/acetone xylene Ir(L7).sub.2(CL1) L7 CL1 16% 300° C./80 h/acetone xylene Ir(L10).sub.2(CL1) L10 CL1 15% 280° C./80 h/ethyl acetate xylene Ir(L11).sub.2(CL1) L11 CL1 16% 260° C./80 h/ethyl acetate xylene Ir(L12).sub.2(CL1) L12 CL1 25% 280° C./60 h/acetone xylene Ir(L13).sub.2(CL1) L13 CL1 16% 300° C./90 h/acetone xylene Ir(L14).sub.2(CL2) L14   1118-71-4 CL2 0 19% 300° C./90 h/ethyl acetate xylene Ir(L15).sub.2(CL2) L15 CL2 14% 320° C./80 h/acetone xylene Ir(L26).sub.2(CL2) L26 CL2 30% 280° C./60 h/acetone xylene Ir(L33).sub.2(CL2) L33 CL2 14% 280° C./60 h/acetone xylene Ir(L500).sub.2(CL2) L500 CL2 60% 280° C./80 h/acetone xylene Ir(L503).sub.2(CL2) L503 CL2 54% 280° C./60 h/acetone xylene Ir(L505).sub.2(CL2) L505 CL2 60% 280° C./60 h/acetone xylene Ir(L518).sub.2(CL3) L518   98-98-6 CL3 27% 280° C./80 h/acetone xylene Ir(L523).sub.2(CL3) L523 CL3 22% 280° C./80 h/acetone xylene Ir(L548).sub.2(CL3) L548 CL3 0 27% 280° C./80 h/acetone xylene Ir(L553).sub.2(CL3) L553 CL3 24% 280° C./80 h/acetone xylene Ir(L556).sub.2(CL3) L556 CL3 29% 280° C./80 h/acetone xylene Ir(L565).sub.2(CL4) L565   18653-75-3 CL4 44% 260° C./60 h/acetone xylene Ir(L568).sub.2(CL4) L568 CL4 44% 260° C./80 h/acetone xylene Ir(L586).sub.2(CL5) L586   14782-58-2 CL5 50% 260° C./80 h/acetone xylene Ir(L1508).sub.2(CL7) L1508   219508-27-7 CL6 47% 280° C./80 h/Aceton xylene
Variant B:
Step 1:

(84) See variant A, step 1.

(85) Step 2:

(86) The crude chloro dimer of the formula [Ir(L).sub.2Cl].sub.2 is suspended in 200 mL of THF, and to the suspension are added 20 mmol of the coligand CL, 20 mmol of silver(I) trifluoroacetate and 30 mmol of potassium carbonate, and the mixture is heated under reflux for 24 h. After cooling, the THF is removed under reduced pressure. The residue is taken up in 200 mL of a mixture of ethanol and conc. ammonia solution (1:1, v:v). The suspension is stirred at room temperature for 1 h, and the solids are filtered off with suction, washed twice with 50 mL each time of a mixture of ethanol and conc. ammonia solution (1:1, v:v) and twice with 50 mL each time of ethanol, and then dried under reduced pressure. Hot extraction and sublimation as in variant A.

(87) TABLE-US-00009 Ir complex Step 1: Reaction temp./ Reaction time/ Li- Co- Suspension medium gand ligand Steps 2: Ex. L CL Extractant Yield Ir(L3).sub.2(CL7) L3 00   391604/-55 CL7 01 39% as ex. Ir(L98).sub.2(CL2) Ir(L503).sub.2(CL8) L503 02   4350/-51 CL8 03 31% 90° C./48 h/acetone xylene Ir(L565).sub.2(CL8) L565 04   1093072- 00-4 CL9 05 39% 290° C./60 h/acetone xylene Ir(L1508).sub.2(CL10) L1508 06   152536-39-5 CL10 07 38% 300° C./80 h/acetone xylene
Variant C:
Step 1:

(88) See variant A, step 1.

(89) Step 2:

(90) The crude chloro dimer of the formula [Ir(L).sub.2C].sub.2 is suspended in 1000 mL of dichloromethane and 150 mL of ethanol, to the suspension are added 20 mmol of silver(I) trifluoromethanesulfonate, and the mixture is stirred at room temperature for 24 h. The precipitated solids (AgCl) are filtered off with suction using a short Celite bed and the filtrate is concentrated to dryness. The solids thus obtained are taken up in 100 mL of ethylene glycol, 20 mmol of the coligand CL added thereto and then the mixture is stirred at 130° C. for 30 h. After cooling, the solids are filtered off with suction, washed twice with 50 mL each time of ethanol and dried under reduced pressure. Hot extraction and sublimation as in variant A.

(91) TABLE-US-00010 Ir complex Step 1: Reaction temp./ Reaction time/ Li- Co- Suspension medium gand ligand Steps 2: Ex. L CL Extractant Yield Ir(L586).sub.2(CL11) L586 08   914306-48-2 CL11 09 46% 290° C./80 h/acetone xylene Ir(L588).sub.2(CL11) L588 CL11 0 39% 290° C./80 h/acetone xylene Ir(L553).sub.2(CL12) L553   39696-58-7 CL12 44% 300° C./80 h/acetone xylene
Variant E:

(92) A mixture of 10 mmol of the Ir complex Ir(L).sub.2(CL1 or CL2), 20 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 50 mL glass ampoule. 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 bar. Further workup, purification and sublimation as described in 1) Homoleptic tris-facial iridium complexes.

(93) TABLE-US-00011 Ir complex Step 1: Reaction temp./ Reaction time/ Li- Suspension medium Ir complex ligand Steps 2: Ex. Ir(L).sub.2(CL) L′ Extractant Yield Ir(L505).sub.2(L588) Ir(L505).sub.2(CL2) L588 39% 280° C./80 h/DCM mesitylene Ir(L548).sub.2(L26) Ir(L548).sub.2(CL3) L26 43% 300° C./70 h/DCM mesitylene Ir(L556).sub.2(L4) Ir(L556).sub.2(CL3) L4 44% 300° C./70 h/DCM mesitylene Ir(L13).sub.2(L1508) Ir(L13).sub.2(CL1) L1508 36% 305° C./70 h/DCM mesitylene
E: Derivatization of the Metal Complexes
1) Halogenation of the Iridium Complexes:

(94) To a solution or suspension of 10 mmol of a complex bearing A×C−H groups (with A=1, 2 or 3) in the para position to the iridium in 3000 mL of dichloromethane is added, in the dark and with exclusion of air, at 30° C., A ×11 mmol of N-halosuccinimide (halogen: Cl, Br, I), and the mixture is stirred for 20 h. Complexes of sparing solubility in DCM may also be converted in other solvents (TCE, THF, DMF, etc.) and at elevated temperature. Subsequently, the solvent is substantially removed under reduced pressure. The residue is extracted by boiling with 100 mL of MeOH, and the solids are filtered off with suction, washed three times with 30 mL of methanol and then dried under reduced pressure.

(95) Synthesis of Ir(L500-Br).sub.3:

(96) ##STR00517##

(97) To a suspension, stirred at 30° C., of 11.3 g (10 mmol) of Ir(L500).sub.3 in 3000 mL of DCM are added 5.9 g (33 mmol) of N-bromosuccinimide all at once and the mixture is stirred for 20 h. After removing about 2900 mL of the DCM under reduced pressure, 100 mL of methanol are added to the yellow suspension, and the solids are filtered off with suction, washed three times with about 30 mL of methanol and then dried under reduced pressure. Yield: 13.8 g (9.5 mmol), 95%; purity: about 99.6% by NMR.

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

(99) TABLE-US-00012 Ex. Complex Brominated complex Yield Ir(L8-Br).sub.3 93% Ir(L8).sub.3 Ir(L8-Br).sub.3 Ir(L16-Br).sub.3 0 95% Ir(L16).sub.3 Ir(L16-Br).sub.3 Ir(L505-Br).sub.3 97% Ir(L505).sub.3 Ir(L505-Br).sub.3
2) Suzuki Coupling with the Iridium Complexes:
Variant a, Biphasic Reaction Mixture:

(100) To a suspension of 10 mmol of a brominated complex, 40-80 mmol of the boronic acid or boronic ester and 80 mmol of tripotassium phosphate in a mixture of 300 mL of toluene, 100 mL of dioxane and 300 mL of water are added 0.6 mmol of tri-o-tolylphosphine and 0.1 mmol of palladium(II) acetate, and the mixture is heated under reflux for 16 h. After cooling, 500 mL of water and 200 mL of toluene are added, the aqueous phase is removed, and the organic phase is washed three times with 200 mL of water and once with 200 mL of saturated sodium chloride solution and dried over magnesium sulfate. The mixture is filtered through a Celite bed and washed through with toluene, the toluene is removed almost completely under reduced pressure, 300 mL of ethanol are added, and the precipitated crude product is filtered off with suction, washed three times with 100 mL each time of EtOH and dried under reduced pressure. The crude product is columned twice with toluene through silica gel. The metal complex is finally heat-treated or sublimed. The heat treatment is effected under high vacuum (p about 10.sup.−6 mbar) within the temperature range of about 200-300° C. The sublimation is effected under high vacuum (p about 10.sup.−6 mbar) within the temperature range of about 300-400° C., the sublimation preferably being conducted in the form of a fractional sublimation.

(101) Variant B, Monophasic Reaction Mixture:

(102) To a suspension of 10 mmol of a brominated complex, 40-80 mmol of the boronic acid or boronic ester and 60-100 mmol of the base (potassium fluoride, tripotassium phosphate, potassium carbonate, cesium carbonate etc., each in anhydrous form) and 100 g of glass beads (diameter 3 mm) in 100 mL-500 mL of an aprotic solvent (THF, dioxane, xylene, mesitylene, dimethylacetamide, NMP, DMSO, etc.) are added 0.6 mmol of tri-o-tolylphosphine and 0.1 mmol of palladium(II) acetate, and the mixture is heated under reflux for 1-24 h. Alternatively, it is possible to use other phosphines such as tri-tert-butylphosphine, di-tert-butylphosphine, S-Phos, Xanthphos, etc., the preferred phosphine:palladium ratio in the case of these phosphines being 2:1 to 1.2:1. The solvent is removed under reduced pressure, the product is taken up in a suitable solvent (toluene, dichloromethane, ethyl acetate, etc.) and purification is effected as described in A.

(103) Synthesis of Ir(L2000).sub.3:

(104) ##STR00524##
Variant B:

(105) Use of 11.6 g (10 mmol) of Ir(L500-Br).sub.3 and 14.0 g (40 mmol) of quaterphenylboronic acid [1233200-59-3], cesium carbonate, tri-ortho-tolylphosphine, NMP, 180° C., 2 h. Yield: 12.7 g (6.9 mmol), 69%; purity: about 99.8% by HPLC.

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

(107) TABLE-US-00013 Product Ex. Variant Yield Ir(L2001).sub.3 57% Ir(L8-Br).sub.3 + [952583-08-3] B, as Ir(2000).sub.3 Ir(L2002).sub.3 55% Ir(L8-Br).sub.3 + [1251825-65-6] A Ir(L2003).sub.3 46% Ir(L8-Br).sub.3 + [1071924-15-6] B, as Ir(2000).sub.3 Ir(L2004).sub.3 52% Ir(L16-Br).sub.3 + [100379-00-8] B, as Ir(2000).sub.3, dioxane rather than NMP Ir(L2005).sub.3 23% Ir(L505-Br).sub.3 + [1065663-52-6] B, as Ir(2000).sub.3 Ir(L2006).sub.3 0 25% Ir(L505-Br).sub.3 + [2156-04-9] B, as Ir(2000).sub.3, DMAC rather than NMP
3) Buchwald Coupling with the Iridium Complexes:

(108) To a mixture of 10 mmol of the brominated complex, 40 mmol of the diarylamine or carbazole, 45 mmol of sodium tert-butoxide in the case of the amines or 80 mmol of tripotassium phosphate (anhydrous) in the case of carbazoles, 100 g of glass beads (diameter 3 mm) and 300-500 mL of o-xylene or mesitylene are added 0.4 mmol of tri-tert-butylphosphine and then 0.3 mmol of palladium(III) acetate, and the mixture is heated under reflux with good stirring for 16 h. After cooling, the aqueous phase is removed, and the organic phase is washed twice with 200 mL of water and once with 200 mL of saturated sodium chloride solution and dried over magnesium sulfate. The mixture is filtered through a Celite bed and washed through with o-xylene or mesitylene, the solvent is removed almost completely under reduced pressure, 300 mL of ethanol are added, and the precipitated crude product is filtered off with suction, washed three times with 100 mL each time of EtOH and dried under reduced pressure. The crude product is columned twice with toluene on silica gel. The metal complex is finally heat-treated or sublimed. The heat treatment is effected under high vacuum (p about 10.sup.−6 mbar) within the temperature range of about 200-300° C. The sublimation is effected under high vacuum (p about 10.sup.−6 mbar) within the temperature range of about 300-400° C., the sublimation preferably being conducted in the form of a fractional sublimation.

(109) Synthesis of Ir(L2500).sub.3:

(110) ##STR00531##

(111) Use of 11.6 g (10 mmol) of Ir(L500-Br).sub.3 and 12.9 g (40 mmol) of p-biphenyl-o-biphenylamine [1372775-52-4], mesitylene. Yield: 11.1 g (5.3 mmol), 53%; purity: about 99.8% by HPLC.

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

(113) TABLE-US-00014 Ex. Product Yield Ir(L2501).sub.3 49% Ir(L500-Br).sub.3 + [1257220-47-5] Ir(L2502).sub.3 53% Ir(L8-Br).sub.3 + [244-78-0] Ir(L2503).sub.3 53% Ir(L505-Br).sub.3 + [244-78-0] Ir(L2504).sub.3 47% Ir(L505-Br).sub.3 + [1257220-47-5]
Production of the OLEDs
1) Vacuum-Processed Devices:

(114) 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). In the examples which follow, the results for various OLEDs are presented. Glass plaques with structured ITO (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 aluminum layer of thickness 100 nm.

(115) First of all, vacuum-processed OLEDs are described. For this purpose, all the materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the emission layer always consists of at least one matrix material (host material) and an emitting dopant (emitter) which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as M2:M1:Ir(L1).sub.3 (55%:35%:10%) mean here that the material M2 is present in the layer in a proportion by volume of 55%, M1 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 6.

(116) 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.3. According to the emission color, different starting brightnesses are 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.

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

(118) One use of the compounds of the invention is as phosphorescent emitter materials in the emission layer in OLEDs. The compound Ir(Ref1).sub.3 is used as a comparison according to the prior art. The results for the OLEDs are collated in Table 2.

(119) TABLE-US-00015 TABLE 1 Structure of the OLED HTL2 EBL HBL thick- thick- EML thick- ETL Ex. ness ness thickness ness thickness Yellow OLEDs D-Ref. HTM — M2:M1:Ir(Ref1).sub.3 HBM ETM1:ETM2 220 nm (75%:15%:10%) 10 nm (50%:50%) 20 nm 40 nm D-Ir(L1).sub.3 HTM — M2:M1:Ir(L1).sub.3 HBM ETM1:ETM2 220 nm (75%:15%:10%) 10 nm (50%:50%) 20 nm 40 nm D-Ir(L9).sub.3 HTM — M2:M1:Ir(L9).sub.3 HBM ETM1:ETM2 220 nm (75%:15%:10%) 10 nm (50%:50%) 20 nm 40 nm D-Ir(L505).sub.3 HTM — M2:M1:Ir(L505).sub.3 HBM ETM1:ETM2 220 nm (75%:15%:10%) 10 nm (50%:50%) 20 nm 40 nm D-Ir(L527).sub.3 HTM — M2:M1:Ir(L527).sub.3 HBM ETM1:ETM2 220 nm (75%:15%:10%) 10 nm (50%:50%) 20 nm 40 nm D-Ir(L1001).sub.3 HTM — M2:M1:Ir(L1001).sub.3 HBM ETM1:ETM2 220 nm (75%:15%:10%) 10 nm (50%:50%) 20 nm 40 nm D-Ir(L1500).sub.3 HTM — M2:M1:Ir(L1500).sub.3 HBM ETM1:ETM2 220 nm (75%:15%:10%) 10 nm (50%:50%) 20 nm 40 nm D-Ir(L3).sub.2(CL1) HTM — M2:M1: HBM ETM1:ETM2 220 nm Ir(L3).sub.2(CL1) 10 nm (50%:50%) (75%:15%:10%) 40 nm 20 nm D- HTM — M2:M1: HBM ETM1:ETM2 Ir(L500).sub.2(CL2) 220 nm Ir(L500).sub.2(CL2) 10 nm (50%:50%) (75%:15%:10%) 40 nm 20 nm D- HTM — M2:M1: HBM ETM1:ETM2 Ir(L565).sub.2(CL4) 220 nm Ir(L565).sub.2(CL4) 10 nm (50%:50%) (75%:15%:10%) 40 nm 20 nm D- HTM — M2:M1: HBM ETM1:ETM2 Ir(L503).sub.2(CL8) 220 nm Ir(L503).sub.2(CL8) 10 nm (50%:50%) (75%:15%:10%) 40 nm 20 nm

(120) TABLE-US-00016 TABLE 2 Results for the vacuum-processed OLEDs EQE (%) CIE x/y 1000 Voltage (V) 1000 LD50 (h) Ex. cd/m.sup.2 1000 cd/m.sup.2 cd/m.sup.2 1000 cd/m.sup.2 Yellow OLEDs D-Ref. 19.7 3.1 0.44/0.55 210000 D-Ir(L1).sub.3 22.7 3.2 0.50/0.48 330000 D-Ir(L9).sub.3 13.1 3.0 0.30/0.69 — D-Ir(L505).sub.3 23.0 3.2 0.48/0.50 320000 D-Ir(L527).sub.3 19.8 3.6 0.61/0.38 — D-Ir(L1001).sub.3 22.3 3.1 0.46/0.53 340000 D-Ir(L1500).sub.3 21.9 3.4 0.54/0.44 390000 D-Ir(L3).sub.2(CL1) 23.3 3.2 0.47/0.51 230000 D-Ir(L500).sub.2(CL2) 22.7 3.3 0.48/0.51 250000 D-Ir(L565).sub.2(CL4) 19.5 3.2 0.60/0.38 — D-Ir(L503).sub.2(CL8) 21.8 3.4 0.51/0.48 —
2) Solution-Processed Devices
A: From Soluble Functional Materials

(121) The iridium complexes of the invention may also be processed from solution and lead therein 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 4083sp.) 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 fulfill 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 g/I 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 solution-processed devices contain an emission layer composed of (polystyrene):M4:M5:Ir(L).sub.3 (25%:25%:40%:10%). 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 aluminum (100 nm) (high-purity metals from Aldrich, particularly barium 99.99% (cat. no. 474711); vapor deposition systems from Lesker or the like, typical vapor deposition pressure 5×10$ mbar) is applied by vapor 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/AI) by vapor 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.

(122) TABLE-US-00017 TABLE 3 Results with materials processed from solution EQE (%) CIE x/y 1000 Voltage (V) 1000 Ex. Ir(L).sub.3 cd/m.sup.2 1000 cd/m.sup.2 cd/m.sup.2 Yellow OLEDs S-Ir(L25).sub.3 Ir(L25).sub.3 17.8 5.6 0.59/0.40 S-Ir(L28).sub.3 Ir(L28).sub.3 19.0 5.3 0.48/0.48 S-Ir(L510).sub.3 Ir(L510).sub.3 19.5 5.4 0.48/0.50 S-Ir(L520).sub.3 Ir(L520).sub.3 18.4 5.5 0.60/0.38 S-Ir(L550).sub.3 Ir(L550).sub.3 17.8 5.2 0.47/0.52 S-Ir(L562).sub.3 Ir(L562).sub.3 20.4 5.5 0.48/0.50 S-Ir(L1000).sub.3 Ir(L1000).sub.3 19.7 5.3 0.46/0.53 S-Ir(L1507).sub.3 Ir(L1507).sub.3 18.0 5.5 0.54/0.44 S-Ir(L7).sub.2(CL1) Ir(L7).sub.2(CL1) 19.8 5.4 0.45/0.53 S-Ir(L505).sub.2(CL2) Ir(L505).sub.2(CL2) 19.4 5.3 0.46/0.52 S-Ir(L565).sub.2(CL8) Ir(L565).sub.2(CL8) 16.5 5.4 0.60/0.38 S-Ir(L556).sub.2(L4) Ir(L556).sub.2(L4) 17.6 5.5 0.48/0.49 S-Ir(L2000).sub.3 Ir(L2000).sub.3 18.9 5.4 0.49/0.50 S-Ir(L2504).sub.3 Ir(L2504).sub.3 14.3 5.2 0.53/0.46
3) White-Emitting OLEDs

(123) According to the general methods from 1), a white-emitting OLED having the following layer structure is produced:

(124) TABLE-US-00018 TABLE 4 Structure of the white OLEDs HTL2 EML red EML blue EML green HBL ETL Ex. thickness thickness thickness thickness thickness thickness D-W1 HTM EBM:Ir—R M3:M2:Ir—B M2:Ir(L527).sub.3 HBM ETM1:ETM2 230 nm (97%:3%) (40%:50%:10%) (90%:10%) 10 nm (50%:50%) 9 nm 8 nm 7 nm 30 nm

(125) TABLE-US-00019 TABLE 5 Device results EQE (%) CIE x/y LD50 1000 Voltage (V) 1000 cd/m.sup.2 (h) Ex. cd/m.sup.2 1000 cd/m.sup.2 CRI 1000 cd/m.sup.2 D-W1 20.3 6.5 0.43/0.4377 3000

(126) TABLE-US-00020 TABLE 6 Structural formulae of the materials used HTM EBM M1 M2 0 M3 HBM M4 M5 Ir-R Ir-B ETM1 ETM2 [337526-98-4] Ir(Ref1).sub.3