Metal complexes for use as emitters in organic electroluminescence devices

Abstract

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

Claims

1. A compound of formula (1):
MAr.sub.pBAr.sub.p.sub.mR.sup.B.sub.nFormula (1) wherein M is the same or different in each instance and is an organometallic iridium complex comprising one tripodal, hexadentate, trianionic ligand; Ar is the same or different in each instance and is a linear-bonded arylene group which has 6 to 30 aromatic ring atoms or a linear-bonded heteroarylene group which has 6 to 30 aromatic ring atoms and is optionally substituted by one or more R radicals; B is a group of formula (2): ##STR00216## wherein the dotted lines denote the linkages of this group to Ar or to R.sup.B; Y.sup.1, Y.sup.2, and Y.sup.3 are the same or different in each instance and are CR.sub.2, CRr.sub.2CR.sub.2, CR.sub.2CR.sub.2CR.sub.2, CR.sub.2CR.sub.2CR.sub.2CR.sub.2, CR?CR, or an ortho-bonded phenylene group which is optionally substituted by one or more R radicals; and wherein the Y.sup.1, Y.sup.2, and/or Y.sup.3 groups are optionally joined to one another by a single bond or via R radicals so as to define an oligocyclic group; R.sup.B is the same or different in each instance and is M or H, D, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl group is optionally substituted in each case by one or more R.sup.1 radicals, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals; 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, OR, SR, COOH, C(?O)N(R).sub.2, Si(R.sup.1).sub.3, B(OR).sub.2, C(?O)R, P(?O)(R).sub.2, S(?O)R, S(?O).sub.2R, OSO.sub.2R.sup.1, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl group is optionally substituted in each case 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, C?C, Si(R.sup.1).sub.2, C?O, NR.sup.1, 0, S, or CONR.sup.1, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals; and wherein two R radicals together optionally define a 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).sup.2, CN, NO.sub.2, OR.sup.2, SR.sup.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(?O)R.sup.2, P(?O)(R.sup.2).sub.2, S(?O)R.sup.2, S(?O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl group is optionally substituted in each case 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.sub.2, C?C, Si(R.sup.2).sub.2, C?O, NR.sup.2, O, S, or CONR.sup.2 or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.2 radicals; and wherein two or more R.sup.1 radicals together optionally define a ring system; R.sup.2 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, or heteroaromatic organic radical having 1 to 20 carbon atoms, wherein one or more hydrogen atoms are optionally replaced by F; n is 1, 2, 3, 4, 5, or 6; p is the same or different in each instance and has a value from 1 to 100; q is the same or different in each instance and has a value from 0 to 100; and m is the same or different in each instance and has a value from 1 to 100; wherein the tripodal, hexadentate ligand comprises three bidentate sub-ligands, which are the same or different, and coordinate to an iridium atom and the three bidentate sub-ligands are joined via a bridge of formula (3) or (4): ##STR00217## wherein the dotted line denotes the bond of the bidentate sub-ligands to this structure; X.sup.1 is the same or different in each instance and is CR or N; A.sup.1 is the same or different in each instance and is C(R).sub.2 or O; A.sup.2 is the same or different in each instance and is CR, P(?O), B, or SiR, with the proviso that, when A.sup.2 is P(?O), B, or SiR, A.sup.1 is O and the A bonded to said A.sup.2 is not C(?O)NR.sup.1 or C(?O)O; A is the same or different in each instance and is CR?CR, C(?O)NR.sup.1, C(?O)O, CR.sub.2CR.sub.2, or a group of formula (5): ##STR00218## wherein the dotted line denotes the position of the direct bond of the bidentate sub-ligands to this structure and * denotes the position of the direct bond of the group of formula (5) to the central cyclic group in formula (3) or formula (4); wherein in formula (3) and formula (4) at least one group A is a group of formula (5); X.sup.2 is the same or different in each instance and is CR or N or two adjacent X.sup.2 groups together are NR, O, or S, so as to define a five-membered ring, and the remaining X.sup.2 groups are the same or different in each instance and are CR or N; or two adjacent X.sup.2 groups together are CR or N when one of the X.sup.3 groups in the cycle is N so as to define a five-membered ring; with the proviso that not more than two adjacent X.sup.2 groups are N; X.sup.3 is C in each instance or one X.sup.3 group is N and the other X.sup.3 group in the same cycle is C, with the proviso that two adjacent X.sup.2 groups together are CR or N when one of the X.sup.3 groups in the cycle is N; R is the same or different in each instance and is H, D, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl group in each case is optionally substituted by one or more R.sup.1 radicals and wherein one or more nonadjacent CH.sub.2 groups are optionally replaced by Si(R.sup.1).sub.2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals; and wherein the three bidentate sub-ligands, in addition to via the bridges of formulae (3) or (4), are also optionally closed via a further bridge to form a cryptate.

2. The compound of claim 1, wherein the triplet energy of M is not more than 0.1 eV greater than the triplet energy of [[Ar].sub.pB].sub.mR.sup.B when q is 0 or greater than that of [[Ar].sub.pB[Ar].sub.q].sub.mR.sup.B when q has a value from 1 to 100.

3. The compound of claim 1, wherein the bidentate sub-ligands are the same or different in each instance and are selected from the group consisting of structures formulae (L-1), (L-2), and (L-3): ##STR00219## wherein the dotted lines denotes the bond of the sub-ligand to the bridge of formulae (3) or (4); CyC is the same or different in each instance and is a substituted or unsubstituted aryl or heteroaryl group which has 5 to 14 aromatic ring atoms, each of which coordinates to the metal via a carbon atom and which is bonded in each case to CyD via a covalent bond; CyD is the same or different in each instance and is a substituted or unsubstituted heteroaryl group which has 5 to 14 aromatic ring atoms and coordinates to the metal via a nitrogen atom or via a carbene carbon atom and which is bonded to CyC via a covalent bond; and wherein two or more of the optional substituents together optionally define a ring system.

4. The compound of claim 3, wherein M is an iridium complex wherein three bidentate sub-ligands, which are optionally the same or different, coordinate to one iridium atom, wherein the [[Ar].sub.pB[Ar].sub.q].sub.mR.sup.B group binds to one of the three bidentate ligands or, when n is greater than 1, the [[Ar].sub.pB[Ar].sub.q].sub.mR.sup.B group also binds to two or three of the bidentate sub-ligands, wherein the bidentate sub-ligands are selected from the group consisting of structures formulae (L-1) and (L-3): ##STR00220##

5. The compound of claim 1, wherein Ar is the same or different in each instance and is selected from the group consisting of groups of formulae (Ar-1) through (Ar-10): ##STR00221## ##STR00222## wherein the dotted lines denote the linkages of these groups; X is the same or different in each instance and is CR or N, wherein not more than two X per Ar group are N; and W is the same or different in each instance and is NR, O, or S.

6. The compound of claim 1, wherein the Y.sup.1, Y.sup.2 and Y.sup.3 groups are the same and are CH.sub.2, CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2CH.sub.2 or an unsubstituted ortho-phenylene group.

7. The compound of claim 1, wherein the groups of formula (2) are selected from the group consisting of structures (B-1) through (B-6): ##STR00223## wherein the dotted lines in each case represent the linkages of these groups.

8. The compound of claim 1, wherein R.sup.B is selected from the group consisting of H, M, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the straight-chain alkyl group, the branched alkyl group or the cyclic alkyl group is optionally substituted in each case by one or more R.sup.1 radicals, or an aromatic or heteroaromatic ring system which has 6 to 24 aromatic ring atoms and is optionally substituted in each case by one or more R.sup.1 radicals.

9. The compound of claim 8, wherein the straight-chain alkyl group, the branched alkyl group or the cyclic alkyl group is unsubstituted.

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

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

12. A formulation comprising an oligomer, polymer, or dendrimer of claim 10 and at least one further compound.

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

14. An electronic device comprising at least one oligomer, polymer, or dendrimer of claim 12.

15. 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, oxygen sensors, and organic laser diodes.

16. The electronic device of claim 14, wherein the electronic device is selected from the group consisting 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, oxygen sensors, and organic laser diodes.

17. The electronic device of claim 13, wherein the electronic device is an organic electroluminescent device, wherein the organic electroluminescent device comprises one or more emitting layers comprising the at least one compound.

18. The compound of claim 1, wherein R.sup.2 is a hydrocarbyl radical.

19. The compound of claim 1, wherein said Ar is linear-bonded arylene or heteroarylene group which is para-bonded six-membered arylene or heteroarylene group.

20. The compound of claim 1, wherein the group of formula (3) is selected from the group consisting of structures of formulae (6) through (9) and wherein the group of formula (4) is selected from the group consisting of structures of formulae (10) through (14): ##STR00224## ##STR00225##

21. The compound of claim 1, wherein two A groups are the same and also have the same substitution and the third A group is different from the first two A groups, or wherein all three A groups are the same and also have the same substitution, or wherein A is the same or different in each instance and is selected from the group consisting of (?O)O, C(?O)NR.sup.1, or a group of formulae (15) through (39): ##STR00226## ##STR00227## ##STR00228##

Description

EXAMPLES

(1) General Method for Determining Orbital Energies and Electronic States

(2) The HOMO and LUMO energies and the triplet level and singlet levels of the materials are determined via quantum-chemical calculations. For this purpose, in the present case, the Gaussian09, Revision D.01 software package (Gaussian Inc.) is used. For calculation of organic substances without metals (referred to as the org. method), a geometry optimization is first conducted by the semi-empirical method AM1 (Gaussian input line # AM1 opt) with charge 0 and multiplicity 1. Subsequently, on the basis of the optimized geometry, a single-point energy calculation is effected for the electronic ground state and the triplet level. This is done using the TDDFT (time dependent density functional theory) method B3PW91 with the 6-31G(d) basis set (Gaussian input line # B3PW91/6-31G(d) td=(50-50,nstates=4)) (charge 0, multiplicity 1). For organometallic compounds (referred to as the M-org. method), the geometry is optimized by the Hartree-Fock method and the LanL2 MB basis set (Gaussian input line #HF/LanL2 MB opt) (charge 0, multiplicity 1). The energy calculation is effected, as described above, analogously to that for the organic substances, except that the LanL2DZ basis set is used for the metal atom and the 6-31G(d) basis set for the ligands (Gaussian input line #B3PW91/gen pseudo=lanl2 td=(50-50,nstates=4)). From the energy calculation, the HOMO is obtained as the last orbital occupied by two electrons (alpha occ. eigenvalues) and LUMO as the first unoccupied orbital (alpha virt. eigenvalues) in Hartree units, where HEh and LEh represent the HOMO energy in Hartree units and the LUMO energy in Hartree units respectively. This is used to determine the HOMO and LUMO value in electron volts, calibrated by cyclic voltammetry measurements, as follows:
HOMO(eV)=(HEh*27.212)*0.8308?1.118
LUMO(eV)=(LEh*27.212)*1.0658?0.5049

(3) These values are to be regarded as HOMO and as LUMO of the materials.

(4) The triplet level T1 of a material is defined as the relative excitation energy (in eV) of the triplet state having the lowest energy which is found by the quantum-chemical energy calculation.

(5) The singlet level S1 of a material is defined as the relative excitation energy (in eV) of the singlet state having the second-lowest energy which is found by the quantum-chemical energy calculation.

(6) The energetically lowest singlet state is referred to as S0.

(7) The method described herein is independent of the software package used and always gives the same results. Examples of frequently utilized programs for this purpose are Gaussian09 (Gaussian Inc.) and Q-Chem 4.1 (Q-Chem, Inc.). In the present case, the energies are calculated using the software package Gaussian09, Revision D.01.

(8) 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.

(9) A. Organic Synthons

(10) 1. Synthons LS Known from the Literature

(11) The following synthons are known from the literature and are used in the preparation of the compounds of the invention:

(12) ##STR00089## ##STR00090## ##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095##

(13) 2. Synthesis of Iodides by Iodination

Example S1

(14) ##STR00096##

(15) To a solution of 22.0 g (100 mmol) of LS1 in 1000 ml of chloroform in the dark are added 43.0 g (100 mmol) of bis(trifluoroacetoxy)iodobenzene [2712-78-9] and then 12.7 g (50 mmol) of iodine [7553-56-2], and the mixture is stirred at room temperature for 2 h. The reaction mixture is poured onto 500 ml of saturated sodium thiosulfate solution while stirring and stirred for a further 10 min. The organic phase is removed and dried over magnesium sulfate. The desiccant is filtered off and the filtrate is concentrated to dryness. The residue was purified by flash chromatography (CombiFlash Torrent from Axel Semrau). Yield: 7.6 g (22 mmol), 22%; purity: 95% by .sup.1H NMR.

(16) The following compounds can be prepared in an analogous manner:

(17) TABLE-US-00002 Ex. Reactant Product Yield S2 68% S3 72% S4 76% S5 00 54% S6 01 77%

(18) 3. Synthesis of Boronic Esters by Borylation

(19) General Method:

(20) To a mixture of 100 mmol of the monobromides/-iodides or 50 mmol of the dibromides/-iodides, 105 mmol of bis(pinacolato)diborane [73183-34-3], 200 mmol potassium acetate [127-08-2], anhydrous, and 300 ml of dioxane are added, while stirring, 2 mmol of tricyclohexylphosphine [2622-14-2] and 1 mmol of palladium(II) acetate [3375-31-3], and then the mixture is stirred at 100? C. for 16 h. After cooling, the dioxane is substantially removed under reduced pressure, and the residue is taken up in 500 ml of toluene and washed three times with 300 ml of water and once with 300 ml of saturated NaCl solution, and the organic phase is dried over magnesium sulfate. After the desiccant has been filtered off through a Celite bed in the form of a toluene slurry and the toluene has been removed under reduced pressure, the residue is recrystallized twice from ethyl acetate/methanol. Diboronic esters obtained in this way that are used as monomers for preparation of oligomers or polymers are brought to a purity of >99.9% by HPLC by repeated recrystallization and subsequent sublimation.

Example S20

(21) ##STR00102##

(22) Use of 34.6 g (100 mmol) of S1, 26.6 g (105 mol) of bis(pinacolato)-diborane, 19.6 g (200 mmol) of potassium acetate, 561 mg (2 mmol) of tricyclohexylphosphine and 225 mg (1 mmol) of palladium(II) acetate.

(23) Yield: 15.2 g (44 mmol), 44%; purity: >99% by .sup.1H NMR.

(24) The following compounds can be prepared in an analogous manner:

(25) TABLE-US-00003 Reactant Ex. Product Yield S21 S2 46% 03 S22 S3 41% 04 S23 LS6 45% 05 S24 LS4 33% 06 S25 LS9 89% 07 S26 LS12 90% 08 S27 LS13 81% 09 S28 LS14 94% 0 S29 S4 85% S30 S5 76% S31 S6 80% S32 LS16 84% S33 S100 33% S34 S101 40% S35 S102 93% S36 S103 91% S37 S104 85% S38 S105 85% 0 S39 S106 76% S40 S107 94% S41 S108 89% S42 S109 90% S43 S110 93% S44 S111 90% S45 S112 95% S46 S113 86% S90 LS219 45% S91 LS220 78% 0 S92 S114 85% S93 S115 87%

(26) 4. Synthesis of Bromide/Iodides by Suzuki Coupling

Example S100

(27) ##STR00133##

(28) To a mixture of 39.6 g (100 mmol) of LS4, 36.0 g (100 mmol) of S21, 63.7 g (300 mmol) of tripotassium phosphate [7778-53-2], 500 ml of toluene, 200 ml of dioxane and 500 ml of water are added 1.83 g (6 mmol) of tri-o-tolylphosphine [6163-58-2] and 225 mg (1 mmol) of palladium(II) acetate [3975-31-3], and the mixture is stirred well at 100? C. for 18 h. After cooling, the precipitated solids are filtered off (a portion of the double-coupling product). The organic phase of the mother liquor is separated off, washed twice with 300 ml each time of water and once with 300 ml of saturated sodium chloride solution and dried over magnesium sulfate. The residue obtained after the desiccant has been filtered off with suction through a Celite bed in the form of a toluene slurry and the toluene has been removed is purified by flash chromatography (CombiFlash Torrent from Axel Semrau). Yield: 27.8 g (48 mmol), 48%; purity: 97% by HPLC.

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

(30) TABLE-US-00004 Reactants Ex. Product Yield S101 LS10 + S21 34% S102 LS10 + S25 49% S103 LS10 + S26 53% S104 LS10 + S27 48% S105 LS10 + S29 50% S106 S6 + S27 51% S107 LS16 + S27 49% 0 S108 LS100 + S25 56% S109 LS101 + S25 51% S110 LS105 + S27 49% S111 LS108 + S36 37% S112 LS109 + S28 55% S113 LS110 + S37 43% S114 LS10 + S90 21% S115 LS10 + S91 40% S116 LS101 + S92 47%

(31) 5. Synthesis of Boronic Esters by Suzuki Coupling:

Example S200

(32) ##STR00150##

(33) To a mixture of 47.2 g (100 mmol) of S24, 57.9 g (100 mmol) of S100, 23.0 g (100 mmol) of tripotassium phosphate monohydrate [27176-10-9] and 500 ml of DMSO are added 1.16 g (1 mmol) of tetrakis(triphenylphosphino)-palladium(0) [14221-01-3], and the mixture is stirred well at 80? C. for 18 h. After cooling, the DMSO is substantially removed under reduced pressure, and the residue is taken up in 1000 ml of hot toluene, filtered through a silica gel bed in the form of a hot toluene slurry and washed through with 500 ml of hot toluene, and then the organic phase is concentrated to dryness under reduced pressure. The residue is boiled with 500 ml of isopropanol. After the crude product has been filtered off with suction and dried under reduced pressure, it is purified by flash chromatography (CombiFlash Torrent from Axel Semrau) gereinigt. Yield: 22.3 g (28 mmol), 28%; purity about 97% by .sup.1H NMR.

(34) The following compounds can be prepared in an analogous manner:

(35) TABLE-US-00005 Reactants Ex. Product Yield S201 LS11 + S102 33% S202 LS11 + S104 29% S203 S32 + S107 35% S204 LS11 + S108 42% S205 LS11 + S109 34% S206 S32 + S110 36% S207 LS11 + S92 27% S208 LS11 + S93 24%

(36) 6. Synthesis of the Hexadentate Ligand 1:

Example L1

(37) ##STR00159##

(38) A mixture of 54.1 g (100 mmol) of 1,3,5-tris(2-bromophenyl)benzene [380626-56-2], 98.4 g (350 mmol) of 2-phenyl-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl) pyridine [879291-27-7], 106.0 g (1 mol) of sodium carbonate, 5.8 g (5 mmol) of tetrakis(triphenylphosphino)palladium(0), 750 ml of toluene, 200 ml of ethanol and 500 ml of water is heated under reflux with very good stirring for 24 h. After 24 h, 300 ml of 5% by weight aqueous acetylcysteine solution are added, the mixture is stirred under reflux for a further 16 h and allowed to cool, the aqueous phase is removed and the organic phase is concentrated to dryness. After the organic phase from the Suzuki coupling has been concentrated, the brown foam is taken up in 300 ml of a mixture of dichloromethane:ethyl acetate (8:1, v/v) and filtered through a silica gel bed in the form of a dichloromethane:ethyl acetate slurry (8:1, v/v) (diameter 15 cm, length 20 cm), in order to remove brown components. After concentration, the remaining foam is recrystallized from 800 ml of ethyl acetate with addition of 400 ml of methanol at boiling and then for a second time from 1000 ml of pure ethyl acetate and then subjected to Kugelrohr sublimation under high vacuum (p about 10.sup.?5 mbar, T 280? C.). Yield: 50.6 g (66 mmol), 66%. Purity: about 99.7% by .sup.1H NMR.

Example L2

(39) ##STR00160##

(40) Ligand L2 can be prepared in an analogous manner. Rather than 2-phenyl-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)pyridine [879291-27-7], 2-[4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl]pyridine [908350-80-1] is used. Yield: 56.0 g (73 mmol), 73%. Purity: about 99.7% by .sup.1H NMR.

Example L3

(41) ##STR00161##

(42) L3-intermediate1:

(43) A mixture of 22.6 g (100 mmol) of (6-methoxy-[1,1-biphenyl]-3-yl)boronic acid [459423-16-6], 16.6 g (105 mmol) of 2-bromopyridine [109-04-6], 21.2 g (200 mmol) of sodium carbonate, 1.2 g (1 mmol) of tetrakis(triphenylphosphino)palladium [14221-01-3], 300 ml of toluene, 100 ml of ethanol and 300 ml of water is heated under reflux with good stirring for 18 h. After cooling, the organic phase is removed, washed twice with 300 ml each time of water and once with 300 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The oil obtained after concentration of the organic phase is dried on an oil-pump vacuum at 80? C. and converted without further purification. Yield: 25.6 g (98 mmol), 98%; purity: about 95% by .sup.1H NMR.

(44) L3-intermediate2:

(45) ##STR00162##

(46) A mixture of 26.1 g (100 mmol) of L3-intermediate1 and 81.9 g (700 mmol) of pyridinium hydrochloride is heated to 190? C. for 3 h. After cooling, the reaction mixture is poured into 500 ml of water and extracted five times with 200 ml each time of dichloromethane, the organic phase is washed twice with 200 ml of water and once with 200 ml of saturated NaCl solution, the solvent is removed under reduced pressure, 300 ml of toluene are added for azeotropic drying and the latter is distilled off completely under reduced pressure. The viscous oil thus obtained is converted without further purification. Yield: 21.0 g (85 mmol), 85%; purity: about 95% by .sup.1H NMR.

(47) L3-intermediate3:

(48) ##STR00163##

(49) To a solution, cooled to 0? C., of 24.7 g (100 mmol) of L3-intermediate2 in a mixture of 300 ml of dichloromethane and 80 ml of pyridine are added dropwise, with good stirring, 34 ml (200 mmol) of trifluoromethanesulfonic anhydride [358-23-6]. The reaction mixture is allowed to warm up to RT and stirred for a further 16 h, poured into 1000 ml of ice-water while stirring and then extracted three times with 300 ml each time of dichloromethane. The combined organic phases are washed twice with 300 ml each time of ice-water and once with 500 ml of saturated NaCl solution and then dried over sodium sulfate. The wax that remains after removal of the dichloromethane under reduced pressure is recrystallized from acetonitrile.

(50) Yield: 32.6 g (86 mmol), 86%; purity: about 95% by .sup.1H NMR.

(51) L3-intermediate4:

(52) ##STR00164##

(53) To a solution of 37.9 g (100 mmol) of L3-intermediate3 und 2.2 g (3 mmol) of (DPPF)PdCl.sub.2 in 250 ml of dioxane are added, while stirring, 41.6 ml (300 mmol) of triethylamine and then 29.0 ml (200 mmol) of 4,4,5,5-tetramethyl-[1,3,2]dioxaborolane [25015-63-8], and then the mixture is heated under reflux for 18 h. After cooling, the solvent is largely removed under reduced pressure, and the residue is taken up in 300 ml of ethyl acetate, washed three times with 100 ml each time of water and once with 200 ml of saturated sodium chloride solution, and dried over magnesium sulfate. After the desiccant has been filtered off, the solvent is removed under reduced pressure. The oily residue thus obtained is converted further without purification. Yield: 33.9 g (95 mmol), 95%; purity: about 95% by .sup.1H NMR.

(54) L3-intermediate5:

(55) ##STR00165##

(56) A mixture of 35.7 g (100 mmol) of L3-intermediate4, 28.3 g (100 mmol) of 1-bromo-2-iodobenzene [583-55-1], 31.8 g (300 mmol) of sodium carbonate, 787 mg (3 mmol) of triphenylphosphine, 225 mg (1 mmol) of palladium(II) acetate, 300 ml of toluene, 100 ml of ethanol and 300 ml of water is heated under reflux for 48 h. after cooling, the organic phase is removed, washed three times with 100 ml each time of water and once with 100 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The desiccant is filtered off through a Celite bed in the form of a toluene slurry, the toluene is removed under reduced pressure and excess 1-bromo-2-iodobenzene is removed at 80? C. under reduced pressure (about 0.1 mbar).

(57) Yield: 36.7 g (95 mmol), 95%; purity: about 95% by .sup.1H NMR.

(58) L3:

(59) A mixture of 66.3 g (100 mmol) of 2-[4-[2-[3-[2-[4-(2-pyridyl)phenyl]phenyl]-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]phenyl]-phenyl]pyridine [1989597-72-9], 38.6 g (100 mmol) of L3-intermediate5, 63.7 g (300 mmol) of tripotassium phosphate, 1.6 g (4 mmol) of SPhos, 449 mg (2 mmol) of palladium(II) acetate, 500 ml of toluene, 250 ml of dioxane and 500 ml of water is heated under reflux for 18 h. After cooling, the organic phase is separated off, washed three times with 200 ml each time of water and once with 200 ml saturated sodium chloride solution and dried over magnesium sulfate, the desiccant is filtered off using a Celite bed in the form of a toluene slurry, the solvent is removed under reduced pressure, and the residue is recrystallized from 300 ml of acetonitrile with addition of about 80 ml of ethyl acetate at boiling. Yield: 69.9 g (83 mmol), 83%; purity: about 95% by .sup.1H NMR.

Example L4

(60) ##STR00166##

(61) L4 can be obtained analogously to L3, except using 2-bromo-4-tert-butylpyridine [50488-34-1] rather than 2-bromopyridine.

Example L5

(62) ##STR00167##

(63) L5 can be obtained analogously to L3, except using 4-tert-butyl-2-[4-[2-[3-[2-[4-(4-tert-butyl-2-pyridyl)phenyl]phenyl]-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]phenyl]phenyl]pyridine [1989597-75-2] rather than 2-[4-[2-[3-[2-[4-(2-pyridyl)phenyl]phenyl]-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]phenyl]phenyl]pyridine [1989597-72-9].

(64) B: Organometallic Synthons

(65) 1. Metal Complex Synthons MS Known from the Literature:

(66) ##STR00168## ##STR00169## ##STR00170## ##STR00171##

(67) 2. Synthesis of the Metal Complex Ir(L1):

Example Ir(L1)

(68) ##STR00172##

(69) A mixture of 7.66 g (10 mmol) of ligand L1, 4.90 g (10 mmol) of trisacetylacetonatoiridium(III) [15635-87-7] and 120 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 250-260? 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 250-260? C., in the course of which a small amount of condensate is distilled off and collects in the water separator. After cooling, the melt cake is mechanically comminuted and extracted by boiling with 500 ml of methanol. The beige suspension thus obtained is filtered through a double-ended frit, and the beige solid is washed once with 50 ml of methanol and then dried under reduced pressure. Crude yield: quantitative. The solid thus obtained is dissolved in 1500 ml of dichloromethane and filtered through about 1 kg of silica gel in the form of a dichloromethane slurry (column diameter about 18 cm) with exclusion of air in the dark, leaving dark-coloured components at the start. The core fraction is cut out, substantially concentrated on a rotary evaporator, with simultaneous continuous dropwise addition of MeOH until crystallization. After removal with suction, washing with a little MeOH and drying under reduced pressure, the yellow product is purified further by continuous hot extraction three times with toluene/acetonitrile (3:1, v/v) and 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. Yield: 8.52 g (8.9 mmol), 89%. Purity: >99.9% by HPLC.

Example Ir(L2)

(70) ##STR00173##

(71) Analogously, Ir(L2) can be prepared using L2 rather than L1. The purification is effected by recrystallization from NMP three times with addition of methanol in the cooling of the solution. Yield: 8.04 g (8.4 mmol), 84%. Purity: >99.7% by HPLC.

(72) In an analogous manner, it is possible to prepare the following metal complexes, with purification as described for Ir (L1).

(73) TABLE-US-00006 Ex. Ligand Complex Yield Ir(L3) L3 87% Ir(L4) L4 89% Ir(L5) L5 86%

(74) 3. Halogenation of the Metal Complex Ir (L1):

(75) General Procedure:

(76) To a solution or suspension of 10 mmol of a complex bearing A?CH groups in the para position to the iridium in 500 ml to 2000 ml of DCM (dichloromethane) according to the solubility of the metal complex is added, in the dark and with exclusion of air, at ?30 to +30? C., A?10.5 mmol of N-halosuccinimide (halogen: Cl, Br, I; A=1 corresponds to monohalogenation, A=2 corresponds to dihalogenation, A=3 corresponds to trihalogenation), and the mixture is stirred for 20 h. Complexes of sparing solubility in DCM may also be converted in other solvents (TCE, THF, DMF, chlorobenzene, etc.) and at elevated temperature. Subsequently, the solvent is substantially removed under reduced pressure. The residue is extracted by boiling with 100 ml of methanol, and the solids are filtered off with suction, washed three times with about 30 ml of methanol and then dried under reduced pressure. Substoichiometric brominations, for example mono- and dibrominations of complexes having 3 CH groups in the para position to iridium, usually proceed less selectively than the stoichiometric brominations. The crude products of these brominations can be separated by chromatography (CombiFlash Torrent from A. Semrau).

Example Ir(L1-3Br)

(77) ##STR00177##

(78) To a suspension, stirred at 0? C., of 9.6 g (10 mmol) of Ir(L1) in 2000 ml of DCM are added 5.6 g (31.5 mmol) of N-bromosuccinimide all at once and then the mixture is stirred for a further 20 h. After removing about 1900 ml of the DCM under reduced pressure, 100 ml of methanol are added to the yellow suspension, which is boiled while stirring, and the solids are filtered off with suction, washed three times with about 30 ml of methanol and then dried under reduced pressure. Yield: 11.3 g (9.5 mmol), 95%; purity: >99.0% by NMR.

(79) In an analogous manner, it is possible to prepare the following complexes:

(80) TABLE-US-00007 Ex. Reactant > brominated complex Yield Tribromination Ir(L2-3Br) 94% Ir(L2) + 40 mmol NBS > Ir(L2-3Br) solvent DCM Dibromination Ir(L1-2Br) 33% Ir(L1) + 21 mmol NBS > Ir(L1-2Br) solvent MSO Ir(L2-2Br) 0 26% Ir(L2) + 21 mmol NBS > Ir(L2-2Br) solvent DMSO/60? C. Ir(L3-2Br) 95% Ir(L3) + 21 mmol NBS > Ir(L3-2Br) solvent DCM/RT Ir(L4-2Br) 96% Ir(L4) + 21 mmol NBS > Ir(L4-2Br) solvent DCM/RT Ir(L5-2Br) 95% Ir(L5) + 21 mmol NBS > Ir(L5-2Br) solvent DCM/RT Monobromination Ir(L1-1Br) 24% Ir(L1) + 10.5 mmol NBS > Ir(L1-1Br) solvent DMSO Ir(L2-1 Br) 19% Ir(L2) + 10.5 mmol NBS > Ir(L2-1Br) solvent DMSO/60? C.

(81) 4. Preparation of the Metal Complexes of the Invention

(82) Variant 1: Suzuki Coupling in a Biphasic Aqueous-Organic Medium

(83) To a mixture of 10 mmol of the brominated metal complex, A?11 mmol of the monoboronic ester with A=1, 2 or 3 for mono-, di- or tribromides, A?30 mmol of tripotassium phosphate [7778-53-2], 300 ml of toluene, 100 ml of dioxane and 100 ml of water are added A?0.6 mmol of tri-o-tolylphosphine [6163-58-2] and A?0.1 mmol of palladium(II) acetate [3975-31-3], and the mixture is stirred well at 100? C. for 18 h. After cooling, the precipitated solids are filtered off with suction. If no solid precipitates out, the organic phase is removed, washed twice with 300 ml each time of water and once with 300 ml of saturated sodium chloride solution and then dried over magnesium sulfate, the magnesium sulfate is filtered off, and the filtrate is concentrated to dryness. The crude product thus obtained is purified by chromatography or flash chromatography (CombiFlash Torrent from Axel Semrau). Further purification is effected by repeated continuous hot extraction, wherein the product is introduced into a cellulose thimble (from Whatman) in a hot extractor and repeatedly hot-extracted (typically 3-6 times) with a suitable hot extractant, for example toluene, chlorobenzene, anisole, ethyl acetate, butyl acetate, acetonitrile, dichloromethane, etc. (initial amount about 150-200 ml), until a purity of >99.5%, preferably >99.9%, is attained.

(84) Variant 2: Suzuki Coupling in a Monophasic Dipolar Aprotic Medium

(85) To a mixture of 10 mmol of the metal complex, A?11 mmol of the monoboronic ester with A=1, 2 or 3 for mono-, di- or tribromides, A?30 mmol of tripotassium phosphate trihydrate [22763-03-7] and 200 ml of DMSO are added A?0.1 mmol of tetrakis(triphenylphosphino)palladium(0) [14221-01-3], and the mixture is stirred well at 80? C. for 18 h. After cooling, the DMSO is substantially removed under reduced pressure, the residue is taken up in 1000 ml of dichloromethane and filtered through a silica gel bed in the form of a dichloromethane slurry, the bed is washed through with 500 ml of dichloromethane and then the organic phase is concentrated to dryness under reduced pressure. The further purification of the crude product thus obtained is effected as described under variant 1.

Example Ir1: MS1+3?S20?(MS1-3?S20)=Ir1

(86) ##STR00186##

(87) Procedure according to variant 1. Use of 8.92 g (10.0 mmol) of MS1, 11.43 g (33.0 mmol) of S20, 19.12 g (90.0 mmol) of tripotassium phosphate, 548 mg (1.8 mmol) of tri-o-tolylphosphine, 67 mg (0.3 mmol) of palladium(II) acetate. Hot extraction: 5? from toluene. Yield: (4.8 mmol), 48%. Purity: >99.8% by HPLC.

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

(89) TABLE-US-00008 Reactants .fwdarw. Product Ex. Hot extractant* Yield Ir2 MS1 + 3xS26 .fwdarw. (MS1-3xS26) = Ir2 44% xylene Ir3 MS1 + 3xS27 .fwdarw. (MS1-3xS27) = Ir3 45% Ir4 MS1 + 3xS41 .fwdarw. (MS1-3xS41) = Ir4 41% Ir5 MS1 + 3xS92 .fwdarw. (MS1-3xS92) = Ir5 46% Ir6 MS1 + 3xS208 .fwdarw. (MS1-3xS208) = Ir6 39% Ir7 MS2 + 2xS37 .fwdarw. (MS2-2xS37) = Ir7 59% Ir8 MS2 + 2xS46 .fwdarw. (MS3-2xS46) = Ir8 61% Ir9 MS3 + 1xS25 .fwdarw. (MS3-1xS25) = Ir9 70% Ir10 MS3 + 1xS92 .fwdarw. (MS3-1xS92) = Ir10 68% Ir11 MS3 + 1xS212 .fwdarw. (MS3-1xS212) = 101 71% Ir12 MS4 + 1xS205 .fwdarw. (MS4-1xS205) = Ir12 75% Ir13 MS5 + 1xS29 .fwdarw. (MS51xS29) = Ir13 67% Ir14 MS6 + 1xS39 .fwdarw. (MS6-1xS39) = Ir14 70% Ir15 MS7 + 1xS42 .fwdarw. (MS7-1xS42) = Ir15 72% Ir16 MS8 + 6S28 .fwdarw. (MS8-6xS28) = Ir16 24% Ir17 MS9 + 1xS211 .fwdarw. (MS9-1xS211) = Ir17 66% Ir18 MS10 + 1xS46 .fwdarw. (MS10-1xS46) = Ir18 67% Ir19 MS11 + 1xS43 .fwdarw. (MS11-1xS43) = Ir19 70% Ir20 MS12 + 1xS93 .fwdarw. (MS12-1xS93) = Ir20 67% mesitylene Ir21 MS13 + 2xS26 .fwdarw. (MS13-2xS26) = Ir21 53% Ir22 MS14 + 1xS210 .fwdarw. (MS14-1xS210) = Ir22 62% Ir23 MS15 + 1xS207 .fwdarw. (MS15-1xS207) = Ir23 66% Ir24 MS16 + 2xS27 .fwdarw. (MS16-2xS27) = Ir24 53% Ir25 MS17 + 2xS205 .fwdarw. (MS17-2xS205) = Ir25 51% Ir26 MS18 + 2xS209 .fwdarw. (MS18-2xS209) = Ir26 54% Ir27 MS19 + 1xS203 .fwdarw. (MS19-1xS203) = Ir27 68% 0 Ir28 MS20 + 2xS91 .fwdarw. (MS20-2xS91) = Ir28 50% Ir29 MS21 + 1xS204 .fwdarw. (MS21-1xS204) = Ir29 62% Ir30 MS22 + 3xS22 .fwdarw. (MS22-3xS22) = Ir30 43% Ir31 MS23 + 2xS45 .fwdarw. (MS23-2xS45) = Ir31 49% Ir32 MS24 + 3xS41 .fwdarw. (MS24-3xS41) = Ir32 54% Pt2 MS27 + 1xS37 .fwdarw. (MS27-1xS37) = Pt2 56% Pt3 MS28 + 2xS205 .fwdarw. (MS28-2xS205) = Pt3 34% Butyl acetate Ir37 Ir(L1-3Br) + 3xS28 .fwdarw. Ir(L1-3xS28) = Ir37 44% Variant 2 - also Ir38 to Ir55 Ir38 Ir(L1-3Br) + 3xS26 .fwdarw. Ir(L1-3xS26) = Ir38 46% Ir39 Ir(L1-3Br) + 3xS42 .fwdarw. Ir(L1-3xS42) = Ir39 40% Ir40 Ir(L1-3Br) + 3xS205 .fwdarw. Ir(L1-3xS205) = Ir40 41% Ir41 Ir(L1-2Br) + 2xS29 .fwdarw. Ir(L1-2xS29) = Ir41 57% Variant 2 Ir42 Ir(L1-2Br) + 2xS40 .fwdarw. Ir(L1-2xS40) = Ir42 55% Ir43 Ir(L1-2Br) + 2xS44 .fwdarw. Ir(L1-2xS44) = Ir43 55% Ir44 Ir(L1-2Br) + 2xS2052 .fwdarw. Ir(L1-2xS205) = Ir44 58% Ir45 Ir(L1-1Br) + 1xS29 .fwdarw. Ir(L1-1xS29) = Ir45 64% Variant 2 Ir46 Ir(L1-1Br) + 1xS35 .fwdarw. Ir(L1-1xS35) = Ir46 66% Ir47 Ir(L1-1Br) + 1xS40 .fwdarw. Ir(L1-1xS40) = Ir47 70% Ir48 Ir(L1-1Br) + 1xS44 .fwdarw. Ir(L1-1xS44) = Ir48 72% Ir49 Ir(L1-1Br) + 1xS92 .fwdarw. Ir(L1-1xS92) = Ir49 67% Ir50 Ir(L1-1Br) + 1xS202 .fwdarw. Ir(L1-1xS202) = Ir50 65% Ir51 Ir(L1-1Br) + 1xS203 .fwdarw. Ir(L1-1xS203) = Ir51 70% Ir52 Ir(L1-1Br) + 1xS205 .fwdarw. Ir(L1-1xS205) = Ir52 71% Ir53 Ir(L1-1Br) + 1xS207 .fwdarw. Ir(L1-1xS207) = Ir53 76% Ir54 Ir(L1-1Br) + 1xS210 .fwdarw. Ir(L1-1xS210) = Ir54 73% Ir55 Ir(L1-1Br) + 1xS212 .fwdarw. Ir(L1-1xS212) = Ir55 69% Ir56 Ir(L2-3Br) + 3xS27 .fwdarw. Ir(L1-3xS27) = Ir56 42% Variant 2 - also Ir57 to Ir60 Ir57 Ir(L2-2Br) + 2xS26 .fwdarw. Ir(L2-2xS26) = Ir57 54% Ir58 Ir(L2-1Br) + 1xS23 .fwdarw. Ir(L1-1xS23) = Ir58 69% Ir59 Ir(L2-1Br) + 1xS210 .fwdarw. Ir(L1-1xS10) = Ir59 67% Ir60 Ir(L2-1Br) + 1xS212 .fwdarw. Ir(L1-1xS212) = Ir60 69% Ir61 MS29 + 2xS205 .fwdarw. (MS29-2xS205) = Ir61 55% Ir62 Ir(L3-2Br) + 2xS26 .fwdarw. Ir(L3-2xS26) = Ir62 53% Ir63 Ir(L3-2Br) + 2xS42 .fwdarw. Ir(L3-2xS42) = Ir63 49% Ir64 Ir(L4-2Br) + 2xS37 .fwdarw. Ir(L4-2xS37) = Ir64 51% Ir65 Ir(L5-2Br) + 2xS46 .fwdarw. Ir(L5-2xS46) = Ir65 57% IrRef4 Ir(L3-2Br) + 2x[5122-95-2] = IrRef4 00 IrRef5 Ir(L4-2Br) + 2x[5122-94-1] = IrRef5 01 IrRef6 Ir(L5-2Br) + 2x[100124-06-9] = IrRef6 02 IrRef7 Ir(L5-2Br) + 2x[395087-89-5] = IrRef7 03 *: if different from Example Ir1

(90) 5) Oligomeric/Polymeric Metal Complexes

(91) General Polymerization Method for the Bromides or Boronic Acid Derivatives as Polymerizable Group, Suzuki Polymerization

(92) Variant ABiphasic Reaction Mixture

(93) The procedure is in accordance with WO 2002/077060 and WO 2003/048225 under inert conditions with carefully degassed solvents. The monomers (bromides and boronic acids or boronic esters, purity by HPLC >99.8%) are converted in the composition specified in the following table in a total concentration of about 100 mmol/I in a mixture of 3 parts by volume of toluene:6 parts by volume of dioxane:2 parts by volume of water. The monomer M1 and the monomer M2 are always initially charged in full. Then 2 molar equivalents of tripotassium phosphate are added per Br functionality used overall, the mixture is stirred for a further 5 min, then 0.06 molar equivalent of tri-ortho-tolylphosphine and then 0.01 molar equivalent of palladium(II) acetate per Br functionality used are added and the mixture is heated under reflux with very good stirring. After 1 h, the rest of the monomers according to the table are added all at once and the mixture is heated under reflux for a further 4 h. If the viscosity of the mixture rises too significantly, dilution is possible with a mixture of 2 parts by volume of toluene:3 parts by volume of dioxane. After a total reaction time of 4-6 h, for end-capping, 0.05 molar equivalent per boronic acid functionality used of a monobromoaromatic, 3-bromobiphenyl [2113-57-7] here, and then, after 30 min, 0.05 molar equivalent per Br functionality used of a monoboronic acid or a monoboronic ester, 3-biphenylboronic acid pinacol ester [912844-88-3] here, are added and the mixture is boiled for a further 1 h. After cooling, the mixture is diluted with 500 ml of toluene, the aqueous phase is removed and the organic phase is washed twice with 300 ml each time of water. The organic phase is stirred at 80? C. with 300 ml of an aqueous 5% by weight N-acetylcysteine solution for 16 h, and the organic phase is removed, dried over magnesium sulfate, filtered through a Celite bed and then concentrated to dryness. The crude polymer is dissolved in THF (concentration about 10-30 g/l) and the solution is allowed to run gradually into twice the volume of methanol with very good stirring. The polymer is filtered off with suction and washed three times with methanol and dried. The reprecipitation operation is repeated five times, then the polymer is dried under reduced pressure to constant weight at 30-50? C.

(94) Variant BMonophasic Reaction Mixture

(95) The monomers (bromides and boronic acids or boronic esters, purity by HPLC >99.8%) are dissolved or suspended in the composition specified in the table below in a total concentration of about 100 mmol/l in a solvent (THF, dioxane, xylene, mesitylene, dimethylacetamide, NMP, DMSO, etc.). Then 3 molar equivalents of base (potassium fluoride, tripotassium phosphate (anhydrous, monohydrate or trihydrate), potassium carbonate, caesium carbonate, etc., each in anhydrous form) per Br functionality and the equivalent weight of glass beads (diameter 3 mm) are added, the mixture is stirred for a further 5 min, then 0.03 to 0.003 molar equivalent of tri-ortho-tolylphosphine and then 0.005 to 0.0005 molar equivalent of palladium(II) acetate (ratio of phosphine to Pd preferably 6:1) per Br functionality are added and the mixture is heated up to 80? C. to reflux with very good stirring for 2-3 h. Alternatively, it is possible to use other phosphines such as tri-tert-butylphosphine, SPhos, XPhos, RuPhos, XanthPhos, etc., the preferred phosphine:palladium ratio in the case of these phosphines being 2:1 to 1.3:1. After a total reaction time of 4-12 h, for end-capping, 0.05 molar equivalent of a monobromoaromatic (see above) and then, 30 min thereafter, 0.05 molar equivalent of a monoboronic acid or a monoboronic ester (see above) are added and the mixture is boiled for a further 1 h thereafter. The solvent is substantially removed under reduced pressure, the residue is taken up in toluene and the polymer is purified as described in Variant A.

(96) Oligomer/polymer P and the composition thereof composed of monomers M1 M5, figures in mmol:

(97) TABLE-US-00009 Ex. M1 M2 M3 M4 M5 Yield IrP1 MS5 LS11 LS101 89% 20 mmol 100 mmol 90 mmol IrP2 Ir(L1-Br) LS11 LS105 94% 10 mmol 100 mmol 95 mmol IrP3 Ir(L1-Br) LS11 LS106 90% 2 mmol 100 mmol 99 mmol IrP4 Ir(L1-Br) S32 LS106 LS109 95% 10 mmol 100 mmol 50 mmol 45 mmol IrP5 Ir(L1-Br) LS11 LS202 LS101 LS107 96% 20 mmol 70 mmol 30 mmol 45 mmol 45 mmol IrP6 Ir(L2-Br) LS11 LS106 88% 1 mmol 100 mmol 99 mmol IrP7 Ir(L2-Br) LS208 LS10 90% 6 mmol 100 mmol 97 mmol IrP8 S210 LS11 LS101 MS9 92% 10 mmol 95 mmol 95 mmol 10 mmol IrP9 MS9 LS11 LS113 92% 20 mmol 100 mmol 90 mmol

(98) Stereochemistry:

(99) Typically, the mononuclear complex synthesis units are used in the form of a racemate of the ? and ? isomers. This leads to diastereomer mixtures in the polynuclear compounds of the invention, for example to ?,?/?,? and (meso)-?,? forms for dinuclear compounds. Unless stated otherwise, these are converted or used further as a diastereomer mixture. In addition, it is possible to separate these by chromatographic methods or by fractional crystallization.

Example: Production of the OLEDs

(100) 1) Vacuum-Processed Devices:

(101) OLEDs of the invention and OLEDs according to the prior art are produced by a general method according to WO 04/058911, which is adapted to the circumstances described here (variation in layer thickness, materials used).

(102) In the examples which follow, the results for various OLEDs are presented. Glass plaques coated with structured ITO (indium tin oxide) of thickness 50 nm form the substrates to which the OLEDs are applied. The OLEDs basically have the following layer structure: substrate/hole transport layer 1 (HTL) consisting of HTN doped with 5% 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.

(103) There will first be a description of vacuum-processed OLEDs. For this purpose, all 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-evaporation. Details given in such a form as M3:M2:Ir(L2) (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 by volume of 35% and Ir(L2) in a proportion of 10%. In an analogous manner, 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 4.

(104) The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A) and the voltage (measured at 1000 cd/m.sup.2) are determined from current-voltage-luminance characteristics (IUL characteristics). For selected experiments, the lifetime is determined. The lifetime is defined as the time after which the luminance has dropped from a particular starting luminance to a certain fraction. The lifetime LD50 means that the lifetime quoted 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 are chosen. The values for the lifetime can be converted to a figure for other starting luminances with the aid of conversion formulae known to the person skilled in the art. In this context, the lifetime for a starting luminance of 1000 cd/m.sup.2 is a customary figure.

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

(106) The compounds of the invention can be used inter alia as phosphorescent emitter materials in the emission layer in OLEDs. The comparison used according to the prior art is the iridium compounds according to Table 4. The results for the OLEDs are summarized in Table 2.

(107) TABLE-US-00010 TABLE 1 Structure of the OLEDs HTL2 EBL EML HBL ETL thick- thick- thick- thick- thick- Ex. ness ness ness ness ness Ref.- HTM M1:IrPPy ETM1:ETM2 D1 40 nm (90%:10%) (50%:50%) 30 nm 30 nm Ref.- HTM M1:IrPPy HBM1 ETM1:ETM2 D2 40 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm Ref.- HTM M1:IrPPy HBM1 ETM1:ETM2 D3 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D1 HTM M1:Ir9 ETM1:ETM2 40 nm (90%:10%) (50%:50%) 30 nm 30 nm D2 HTM M1:Ir9 HBM1 ETM1:ETM2 40 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm D3 HTM M1:Ir9 HBM1 ETM1:ETM2 40 nm (85%:15%) 10 nm (50%:50%) 30 nm 30 nm D4 HTM M1:M3:Ir9 HBM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm D5 HTM M1:M2:Ir13 HBM1 ETM1:ETM2 40 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm

(108) TABLE-US-00011 TABLE 2 Results for the vacuum-processed OLEDs EQE (%) Voltage (V) CIE x/y LD50 (h) Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 Ref.-D1 15.8 2.7 0.33/062 55000 Ref.-D2 15.6 3.3 0.33/062 70000 Ref.-D3 16.0 3.3 0.33/062 85000 D1 20.6 2.9 0.36/061 100000 D2 21.5 3.4 0.36/062 105000 D3 22.0 3.2 0.37/060 125000 D4 21.8 3.1 0.37/061 185000 D5 22.3 3.3 0.36/061 175000

(109) Solution-Processed Devices

(110) A: Made from Soluble Functional Materials of Low Molecular Weight

(111) The iridium complexes of the invention can also be processed from solution and lead to OLEDs which are significantly simpler in process terms compared to the vacuum-processed OLEDs but nevertheless have very 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/hole injection layer (60 nm)/interlayer (20 nm)/emission layer (60 nm)/hole blocker layer (10 nm)/electron transport layer (40 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 a cleanroom, a 20 nm hole injection layer is applied by spin-coating. The required spin rate depends on the degree of dilution and the specific spin-coater geometry. In order to remove residual water from the layer, the substrates are baked on a hotplate at 200? C. for 30 minutes. The interlayer used serves for hole transport; in this case, HL-X092 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 triplet emitters of the invention are dissolved together with the matrix materials in toluene or chlorobenzene. The typical solids content of such solutions is between 16 and 25 g/I if, like here, the a device is to attain the typical layer thickness of 60 nm by means of spin-coating. The solution-processed type 1a devices contain an emission layer composed of M4:M5:IrL (42%:45%:13%), the type 1b devices contain and emission layer composed of M4:M5:IrL (40%:32%:28%), and the type 2 devices contain an emission layer composed of M4:M5:IrLa:IrLb (30%:35%:30%:5%), meaning that they contain two different Ir complexes. The emission layer is spun on in an inert gas atmosphere, argon in the present case, and baked at 160? C. for 10 min. Vapour-deposited above the latter are the hole blocker layer (10 nm ETM1) and the electron transport layer (40 nm ETM1 (50%)/ETM2 (50%)) (vapour deposition systems from Lesker or the like, typical vapour deposition pressure 5?10.sup.?6 mbar). Finally, a cathode of aluminium (100 nm) (high-purity metal from Aldrich) is applied by vapour deposition. In order to protect the device from air and air humidity, the device is finally encapsulated and then characterized. The OLED examples cited have not yet been optimized. Table 1 summarizes the data obtained.

(112) TABLE-US-00012 TABLE 3 Results with materials processed from solution EQE (%) Voltage (V) LD50 (h) Emitter 1000 1000 1000 Ex. Device cd/m.sup.2 cd/m.sup.2 CIE x/y cd/m.sup.2 Sol-Ref- IrRef3 15.0 6.2 0.61/0.38 4000 Red1 Typ1a Sol-Ref- IrRef1 17.3 6.4 0.61/0.39 240000 Red2 IrRef3 Typ2 Sol- IrRef1 19.9 6.2 0.64/0.35 310000 RedD1 Ir17 Typ2 Sol- IrRef1 20.4 6.3 0.61/0.38 160000 RedD2 Ir18 Typ2 Sol-Ref- IrRef1 19.6 5.2 0.36/0.61 190000 Green1 Typ1a Sol-Ref- IrRef1 19.8 4.9 0.36/0.61 210000 Green2 Typ1b Sol-Ref- IrRef4 22.0 5.3 0.33/0.64 310000 Green3 Typ1b Sol-Ref- IrRef5 21.9 5.4 0.33/0.62 340000 Green4 Typ1b Sol-Ref- IrRef6 21.7 5.4 0.34/0.62 320000 Green5 Typ1b Sol-Ref- IrRef7 21.9 5.5 0.34/0.62 300000 Green6 Typ1b Sol- Ir5 20.4 5.7 0.38/0.58 170000 GreenD1 Typ1a Sol- Ir6 21.4 5.1 0.37/0.60 270000 GreenD2 Typ1b Sol- Ir11 21.4 5.1 0.37/0.60 190000 GreenD3 Typ1b Sol- Ir12 22.1 5.1 0.37/0.60 250000 GreenD4 Typ1b Sol- Ir15 22.0 5.1 0.37/0.60 260000 GreenD5 Typ1b Sol- Ir19 21.5 5.0 0.40/0.58 300000 GreenD6 Typ1b Sol- Ir23 22.1 5.3 0.39/0.58 180000 GreenD7 Typ1b Sol- Ir25 24.6 5.2 0.43/0.55 290000 GreenD8 Typ1b Sol- Ir29 23.1 5.2 0.40/0.58 270000 GreenD9 Typ1b Sol- Pt3 25.0 5.0 0.29/0.64 GreenD10 Typ1b Sol- Ir37 20.3 5.3 0.37/0.60 340000 GreenD11 Typ1b Sol- Ir44 24.3 5.2 0.37/0.60 380000 GreenD12 Typ1b Sol- Ir54 25.2 5.2 0.37/0.60 400000 GreenD13 Typ1b Sol- Ir55 24.0 5.4 0.38/0.58 340000 GreenD14 Typ1b Sol- IrP1 22.9 5.5 0.37/0.60 300000 GreenD15 Typ1b Sol- IrP3 25.1 5.6 0.37/0.59 210000 GreenD16 Typ1b Sol- Ir61 22.3 5.3 0.39/0.59 280000 GreenD17 Typ1b Sol- Ir62 22.8 5.3 0.34/0.62 300000 GreenD18 Typ1b Sol- Ir63 22.9 5.4 0.34/0.62 330000 GreenD19 Typ1b Sol- Ir64 23.4 5.2 0.34/0.62 360000 GreenD20 Typ1b Sol- Ir65 23.6 5.1 0.34/0.61 320000 GreenD21 Typ1b

(113) TABLE-US-00013 TABLE 4 Structural formulae of the materials used 04 HTM = M9 1450933-44-4 05 M1 1257248-13-7 06 M2 1615703-29-1 07 M3 1357150-54-9 08 M4 1616231-60-7 09 M5 1246496-85-4 0 ETM1 = HBM1 = M10 1233200-52-6 ETM2 25387-93-3 IrPPy 693794-98-8 IrRef1 1269508-30-6 IrRef2 1215692-34-4 IrRef3 1202823-72-0