Electronic device comprising metal complexes

Abstract

Electronic devices, in particular organic electroluminescent devices, comprising metal complexes of the formula (1). ##STR00001##

Claims

1. An electronic device comprising an anode, a cathode and at least one compound of the formula (1) ##STR00076## containing a metal M coordinated to a ligand L of the formula (2) ##STR00077## where the following applies to the symbols and indices used: M is selected from Cu(I), Ag(I), Au(I), Ni(0), or Pd(0); a is 0 and V is N or P, and V is coordinated to M through an electron lone pair, or a is 1 and V is not coordinated to M, and is selected from B, BR.sup., CR, CO.sup., SiR, NR.sup.+, or P(O); or V is a cyclic group of one of the formulae (31) to (34) ##STR00078## Y is, identically or differently on each occurrence, a divalent group selected from CR.sub.2, BR, SiR.sub.2, NR, PR, P(O)R, O or S; b is 1; L1 is selected from the groups of the formulae (3) to (30): ##STR00079## ##STR00080## ##STR00081## ##STR00082## X is on each occurrence, identically or differently, CR or N; D is on each occurrence, identically or differently, O.sup., S.sup., NR.sup., PR.sup., NR.sub.2, PR.sub.2, COO.sup., SO.sub.3.sup., C(O)R, CR(NR) or N(CR.sub.2); and the groups are coordinated to the metal M via the position denoted by *; the position denoted by # indicates the position at which the part-ligand is bonded to Y or to V, and the position denoted by (#) indicates the position at which the part-ligand is optionally bonded to Y or to L4, and if a further bond of this type to Y or to L4 is present, the corresponding symbol X(#) is C, and there is no group R bonded to the symbol N(#) in the formulae (7), (8), (9), (21) and (23); L2 and L3 are selected, identically or differently on each occurrence, from the group consisting of NR.sub.2, NR.sup., NC(R.sup.1).sub.2, PR.sub.2, PR(OR), P(OR).sub.2, S.sup., SR and L1; L4 is a carbon monoxide, nitrogen monoxide, alkyl cyanide, aryl cyanide, alkyl isocyanide, aryl isocyanide, amine, halophosphine, trialkylphosphine, triarylphosphine, alkylarylphosphine, phosphite, arsine, stibene, neutral or anionic nitrogen-containing heterocycles, carbene, hydride, deuteride, F.sup., Cl.sup., Br.sup., alkylacetylide, arylacetylide, cyanide, cyanate, isocyanate, thiocyanate, isothiocyanate, aliphatic or aromatic alcoholate, aliphatic or aromatic thioalcoholates, amide, carboxylate, or ##STR00083## wherein, in formula (56), X and D are as defined for formulae (3) to (30), * indicates the position of the coordination to M, and the position denoted by (#) indicates the position at which L4 is optionally bonded, optionally via (Y).sub.n, one of the part-ligands L1, L2 and L3 and if L4 is bonded to the part-ligand L1, L2 or L3 directly or through Y.sub.n, the corresponding symbol X(#) is C; n is on each occurrence, identically or differently, 0, 1 or 2; R is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(O)R.sup.1, P(O)(R.sup.1).sub.2, S(O)R, S(O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sup.1, where one or more non-adjacent CH.sub.2 groups is optionally replaced by R.sup.1CCR.sup.1, CC, Si(R.sup.1).sub.2, Ge(R.sup.1).sub.2, Sn(R.sup.1).sub.2, CO, CS, CSe, CNR.sup.1, P(O)(R.sup.1), SO, SO.sub.2, NR.sup.1, O, S or CONR.sup.1 and where one or more H atoms is optionally replaced by F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1, or an aryloxy, heteroaryloxy, aralkyl or heteroaryalkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.1; two or more substituents R here may also form a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one another; R.sup.1 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, OH, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(O)R.sup.2, P(O)(R.sup.2).sub.2, S(O)R.sup.2, S(O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, each of which may be substituted by one or more radicals R.sup.2, where one or more non-adjacent CH.sub.2 groups is optionally replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, Ge(R.sup.2).sub.2, Sn(R.sup.2).sub.2, CO, CS, CSe, CNR.sup.2, P(O)(R.sup.2), SO, SO.sub.2, NR.sup.2, O, S or CONR.sup.2 and where one or more H atoms is optionally replaced by F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.2, or an aryloxy, heteroaryloxy, aralkyl or heteroaryalkyl group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2; two or more substituents R.sup.1 here may also form a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one another; R.sup.2 is on each occurrence, identically or differently, H, D, F, or an aliphatic, aromatic or heteroaromatic radical having 1 to 20 C atoms, in which, in addition, one or more H atoms is optionally replaced by F; two or more substituents R.sup.2 here may also form a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one another.

2. The electronic device according to claim 1, wherein the device is an organic electroluminescent device, organic integrated circuit (O-IC), organic field-effect transistor (O-FET), organic thin-film transistor (O-TFT), organic light-emitting transistor (O-LET), organic solar cell (O-SC), organic optical detector, organic photoreceptor, organic field-quench device (O-FQD), light-emitting electrochemical cell (LEC) or organic laser diode (O-laser).

3. The electronic device according to claim 1, wherein the device is an organic light-emitting diode.

4. The electronic device according to claim 1, wherein the device is an organic electroluminescent device and the compound of the formula (1) is employed as emitting compound in an emitting layer.

5. The electronic device according to claim 4, wherein the compound of the formula (1) is employed in combination with one or more matrix materials which are selected from the group consisting of ketone, phosphine oxide, sulfoxide, sulfone, triarylamine, carbazole derivative, indolocarbazole derivative, indenocarbazole derivative, azacarbazole, bipolar matrix material, silane, azaborole, boronic ester, triazine derivative, zinc complex, diaza- or tetraazasilole derivative and diazaphosphole derivative.

6. The electronic device according to claim 1, wherein the compound of the formula (1) is used as matrix material for an emitting compound in an emitting layer and/or as hole-blocking material in a hole-blocking layer and/or as electron-transport material in an electron-transport layer and/or as hole-transport material in a hole-transport- or -injection layer and/or as electron-blocking material is an electron-blocking layer.

7. A compound of the formula ML, containing a metal M tetra-coordinated to a ligand L, where the ligand L conforms to one of the formulae (62) to (66) and each of the part-ligands L1, L2, L3 and L4 is coordinated to M: ##STR00084## M is selected from Cu(I), Ag(I), Au(I), Ni(0), or Pd(0); V is selected from B, BR.sup., CR, CO.sup., SiR, NR.sup.+, or P(O); or V is a cyclic group of one of the formulae (31) to (34); ##STR00085## Y is, identically or differently on each occurrence, a divalent group selected from CR.sub.2, BR, SiR.sub.2, NR, PR, P(O)R, O or S; L1 is selected from the groups of the formulae (3) to (30): ##STR00086## ##STR00087## ##STR00088## X is on each occurrence, identically or differently, CR or N; D is on each occurrence, identically or differently, O.sup., S.sup., NR.sup., PR.sup., NR.sub.2, PR.sub.2, COO.sup., SO.sub.3.sup., C(O)R, CR(NR) or N(CR.sub.2); and the groups are coordinated to the metal M via the position denoted by *; the position denoted by # indicates the position at which the part-ligand is bonded to Y or to V, and the position denoted by (#) indicates the position at which the part-ligand is optionally bonded to Y or to L4, and if a further bond of this type to Y or to L4 is present, the corresponding symbol X(#) is C, and there is no group R bonded to the symbol N(#) in the formulae (7), (8), (9), (21) and (23); L2 and L3 are selected, identically or differently on each occurrence, from the group consisting of NR.sub.2, NR.sup., NC(R.sup.1).sub.2, PR.sub.2, PR(OR), P(OR).sub.2, S.sup., SR and L1; L4 is a carbon monoxide, nitrogen monoxide, alkyl cyanide, aryl cyanide, alkyl isocyanide, aryl isocyanide, amine, halophosphine, trialkylphosphine, triarylphosphine, alkylarylphosphine, phosphite, arsine, stibene, neutral or anionic nitrogen-containing heterocycles, carbene, hydride, deuteride, F.sup., Cl.sup., Br.sup., I.sup., alkylacetylide, arylacetylide, cyanide, cyanate, isocyanate, thiocyanate, isothiocyanate, aliphatic or aromatic alcoholate, aliphatic or aromatic thioalcoholates, amide, carboxylate, or ##STR00089## wherein, in formula (56), X and D are as defined for formulae (3) to (30), * indicates the position of the coordination to M, and the position denoted by (#) indicates the position at which L4 is optionally bonded, optionally via (Y).sub.n, one of the part-ligands L1, L2 and L3 and if L4 is bonded to the part-ligand L1, L2 or L3 directly or through Y.sub.n, the corresponding symbol X(#) is C; n is on each occurrence, identically or differently, 0, 1 or 2; R is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R.sup.1).sub.2, CN, NO.sub.2, OH, Si(R.sup.1).sub.3, B(OR.sup.1).sub.2, C(O)R.sup.1, P(O)(R.sup.1).sub.2, S(O)R.sup.1, S(O).sub.2R.sup.1, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sup.1, wherein one or more non-adjacent CH.sub.2 groups is optionally replaced by R.sup.1CCR.sup.1, CC, Si(R.sup.1).sub.2, Ge(R.sup.1).sub.2, Sn(R.sup.1).sub.2, CO, CS, CSe, CNR.sup.1, P(O)(R.sup.1), SO, SO.sub.2, NR.sup.1, O, S or CONR.sup.1 and where one or more H atoms is optionally replaced by F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.1, or an aryloxy, heteroaryloxy, aralkyl or heteroaryalkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R.sup.1, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.1; two or more substituents R here may also form a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one another; R.sup.1 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, OH, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(O)R.sup.2, P(O)(R.sup.2).sub.2, S(O)R.sup.2, S(O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, each of which may be substituted by one or more radicals R.sup.2, where one or more non-adjacent CH.sub.2 groups is optionally replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, Ge(R.sup.2).sub.2, Sn(R.sup.2).sub.2, CO, CS, CSe, CNR.sup.2, P(O)(R.sup.2), SO, SO.sub.2, NR.sup.2, O, S or CONR.sup.2 and where one or more H atoms is optionally replaced by F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R.sup.2, or an aryloxy, heteroaryloxy, aralkyl or heteroaryalkyl group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2; two or more substituents R.sup.1 here may also form a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one another; R.sup.2 is on each occurrence, identically or differently, H, D, F, or an aliphatic, aromatic or heteroaromatic radical having 1 to 20 C atoms, in which, in addition, one or more H atoms is optionally replaced by F; two or more substituents R.sup.2 here may also form a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one another.

8. A process for the preparation of the compound according to claim 7, which comprises reacting the corresponding free ligands with metal salts or metal complexes of the corresponding metal M.

9. The electronic device according to claim 1, wherein the neutral or anionic nitrogen-containing heterocycles are selected from formulae (35)-(37), (41)-(55) and (57)-(61), or the carbene is selected from formulae (38)-(40), ##STR00090## ##STR00091## ##STR00092## * indicates the position of the coordination to M, and the position denoted by (#) indicates the position at which L4 is optionally bonded, optionally via (Y).sub.n, to one of the part-ligands L1, L2 and L3, and if L4 is bonded to the part-ligand L1, L2 or L3 directly or through Y.sub.n, the corresponding symbol X(#) is C, and there is no group R bonded to the symbol N(#) in the formulae (38)-(40) and (55); and wherein X and D are as defined for formulae (3) to (30).

10. The electronic device according to claim 9, wherein the ligand L has a structure of one of the formulae (62) to (66): ##STR00093##

11. The compound according to claim 7, wherein the neutral or anionic nitrogen-containing heterocycles are selected from formulae (35)-(37), (41)-(55) and (57)-(61), or the carbene is selected from formulae (38)-(40), ##STR00094## ##STR00095## ##STR00096## * indicates the position of the coordination to M, and the position denoted by (#) indicates the position at which L4 is optionally bonded, optionally via (Y).sub.n, to one of the part-ligands L1, L2 and L3, and if L4 is bonded to the part-ligand L1, L2 or L3 directly or through Y.sub.n, the corresponding symbol X(#) is C, and there is no group R bonded to the symbol N(#) in the formulae (38)-(40) and (55); and wherein X and D are as defined for formulae (3) to (30).

12. The electronic device of claim 1, wherein the at least one compound of the formula (1) is electrically neutral when, if a is 0 the sum of charge of ligands L1, L2 and L3 compensate the charge of the metal M, or if a is 1 the sum of the charge of ligands L1, L2, L3 and L4 compensate for the charge of the metal M.

13. The compound of claim 7, wherein the at least one compound of the formula ML is electrically neutral as the sum of charge of ligands L1, L2, L3 and L4 compensate for the charge of the metal M.

14. The electronic device of claim 12, wherein M is Cu(I) or Ag(I).

15. The compound of claim 7, wherein M is Cu(I) and the compound is selected from the group consisting of ##STR00097## ##STR00098## ##STR00099## ##STR00100## ##STR00101##

Description

EXAMPLES

(1) The following syntheses are carried out, unless indicated otherwise, under a protective-gas atmosphere in dried solvents. The solvents and reagents can be purchased from ALDRICH or ABCR. The numbers indicated in the following syntheses for the starting materials known from the literature are the CAS numbers of these compounds.

Example 1

Cu Complex 1

(2) ##STR00028##

A): Tris(6-phenylpyridin-2-yl)fluoromethane

(3) ##STR00029##

(4) 809 mg (4 mmol) of tris-tert-butylphosphine and then 674 mg (3 mmol) of palladium(II) acetate are added to a mixture of 50.2 g (100 mmol) of tris(6-bromopyridin-2-yl)fluoromethane [760177-68-2], 61.0 g (500 mmol) of phenylboronic acid, 58.1 g (1 mol) of potassium fluoride, anhydrous, in 1000 ml of THF, and the mixture is subsequently stirred under reflux for 5 h. After cooling, 300 ml of water are added to the reaction mixture, the aqueous phase is separated off, and the organic phase is filtered through Celite and evaporated to dryness. The solid obtained in this way is recrystallised twice from chloroform (about 50 ml) with addition of ethanol (about 200 ml). Yield: 38.5 g (78 mmol), 78%, 99.0% pure according to .sup.1H-NMR.

B): Cu Complex 1

(5) A mixture of 4.9 g (10 mmol) of tris(6-phenylpyridin-2-yl)fluoromethane, 1.0 g (10 mmol) of copper(I) chloride in 50 ml of THF is stirred at 60 C. for 24 h. The reaction mixture is evaporated to a volume of 5 ml in vacuo, 20 ml of methanol are added, and the precipitated solid is filtered off with suction, washed three times with 10 ml of methanol each time and dried in vacuo. Yield: 3.9 g (6.6 mmol), 66%, 99.5% pure according to .sup.1H-NMR.

(6) The following compounds are obtained analogously by using the corresponding Cu salts (table).

(7) TABLE-US-00001 Ex. No. Cu(I) salt Complex Yield [%] Cu complex 2 CuBr 0 61 Cu complex 3 CuI 66 Cu complex 4 CuCN 73 Cu complex 5 CuSCH.sub.3 [4856-13-7] 56 Cu complex 6 CuCH.sub.3 [30645-13-7] 43

Example 7

Cu Complex 7

(8) ##STR00035##

A): (6-Bromopyridin-2-yl)bis(6-methylpyridin-2-yl)methanol

(9) ##STR00036##

(10) 40.0 ml (100 mmol) of n-butyllithium (2.5 N) are added dropwise to a suspension, cooled to 78 C., of 26.1 g (110 mmol) of 2,6-dibromopyridine in 150 ml of diethyl ether, and the mixture is stirred at 78 C. until a yellow solution forms. This solution is diluted dropwise with 200 ml of diethyl ether, and a solution of 23.3 g (110 mmol) of bis(6-methyl-2-pyridinyl)methanone in 80 ml of THF is then added in one portion with vigorous stirring. After warming to 0 C., a mixture of 50 ml of water and 6 ml of glacial acetic acid is added dropwise, and the precipitated solid is then filtered off with suction, washed once with 25 ml of diethyl ether and once with 25 ml of ethanol and dried in vacuo. Yield: 17.8 g (48 mmol), 48%, 98% pure according to .sup.1H-NMR.

B): (6-Bromopyridin-2-yl)bis(6-methylpyridin-2-yl)methoxymethane

(11) ##STR00037##

(12) A solution of 18.5 g (50 mmol) of (6-bromopyridin-2-yl)bis(6-methylpyridin-2-yl)methanol in 50 ml of DMF is added at 40 C. to a suspension of 1.4 g (60 mmol) of sodium hydride in 50 ml of DMF, and the mixture is stirred for a further 30 min. A mixture of 8.5 g (60 mmol) of methyl iodide and 10 ml of DMF is then added, the mixture is stirred at room temperature for a further 20 h, 5 ml of ethanol are added dropwise, the mixture is diluted with 500 ml of dichloromethane, the org. phase is washed five times with 300 ml of water each time, the organic phase is dried over magnesium sulfate, and the solvent is then stripped off completely in vacuo. The residue is recrystallised from ethanol with addition of a little ethyl acetate. Yield: 16.5 g (43 mmol), 86% pure according to .sup.1H-NMR.

C): (6-(Phenyl-2-thiol)pyridin-2-yl)bis(6-methylpyridin-2-yl)methoxymethane

(13) ##STR00038##

(14) 405 mg (2 mmol) of tris-tert-butylphosphine and then 337 mg (1.5 mmol) of palladium(II) acetate are added to a mixture of 38.4 g (100 mmol) of (6-bromopyridin-2-yl)bis(6-methylpyridin-2-yl)methoxymethane, 41.9 g (130 mmol) of diisopropyl [2-tetrahydro-2H-pyran-2-yl]thio]phenylboronate [620988-03-6], 19.2 g (330 mmol) of potassium fluoride (anhydrous) in 500 ml of THF, and the mixture is subsequently stirred under reflux for 5 h. After cooling, 300 ml of water and 15 ml of glacial acetic acid are added to the reaction mixture, the mixture is stirred at 50 C. for 2 h, the aqueous phase is separated off, and the organic phase is filtered through Celite and evaporated to dryness. The solid obtained in this way is recrystallised from acetone (20 ml) with addition of ethanol (150 ml). Yield: 27.3 g (66 mmol), 66%, 99.0% pure according to .sup.1H-NMR.

D): Cu Complex 7

(15) 10.0 ml (10 mmol) of sodium methoxide solution, 1 N in methanol, are added to a solution of 4.1 g (10 mmol) of (6-(phenyl-2-thiol)pyridin-2-yl)bis(6-methylpyridin-2-yl)methoxymethane in 50 ml of THF, and the mixture is stirred at 40 C. for 1 h. 1.0 g (10 mmol) of solid copper(I) chloride is then added, and the mixture is stirred for a further 24 h. The reaction mixture is evaporated to a volume of 5 ml in vacuo, 50 ml of methanol are added, and the precipitated solid is filtered off with suction, washed three times with 10 ml of methanol each time and dried in vacuo. After recrystallisation twice from DMSO/isopropanol, the product is sublimed in a high vacuum (p=110.sup.6 mbar, T=320 C.). Yield: 3.4 g (7.0 mmol), 71%, 99.8% pure according to HPLC.

Example 8

Cu Complex 8

(16) ##STR00039##

A): (6-Bromopyridin-2-yl)bis(6-methylpyridin-2-yl)fluoromethane

(17) ##STR00040##

(18) 46.6 g (350 mmol) of dimethylaminosulfur trifluoride are added with stirring to a solution of 37.0 g (100 mmol) of (6-bromopyridin-2-yl)bis(6-methylpyridin-2-yl)methanol in 300 ml of chloroform, and the mixture is then stirred under reflux for 1 h. After the reaction mixture has been cooled to +5 C., a solution of 65 g of sodium hydroxide in 500 ml of water is slowly added (note: exothermic!), the mixture is stirred for a further 30 min., the aqueous phase is separated off, and the organic phase is dried over calcium chloride. After removal of the solvent in vacuo, the oil is taken up in 100 ml of hot methanol, the mixture is cooled, and the colourless solid is filtered off with suction, washed once with 30 ml of methanol and dried in vacuo. Yield: 33.1 g (8.9 mmol), 89%, 97% pure according to .sup.1H-NMR.

B): (6-Formylpyridin-2-yl)bis(6-methylpyridin-2-yl)fluoromethane

(19) ##STR00041##

(20) 20 ml (50 mmol) of n-butyllithium (2.5 N in hexane) are added rapidly to a solution, cooled to 78 C., of 16.6 g (50 mmol) of 6-bromopyridin-2-yl)bis(6-methylpyridin-2-yl)fluoromethane in 200 ml of THF, and the mixture is stirred at 78 C. for 10 min. 4.4 g (60 mmol) of DMF in 10 ml of THF are then added in one portion, and the mixture is stirred for a further 30 min. and then allowed to warm to room temperature. 55 ml of 1 N hydrochloric acid are added, and the mixture is stirred for a further 1 h and evaporated to dryness in vacuo. The residue is taken up in 500 ml of dichloromethane, the solution is washed with 100 ml of 1 N sodium hydroxide solution and then with 100 ml of water, the organic phase is dried over magnesium sulfate, the organic phase is evaporated to about 30 ml in vacuo, 100 ml of isopropanol are added, the mixture is stirred for a further 1 h, and the precipitated solid is filtered off with suction, washed with methanol and dried in vacuo. Yield: 10.3 g (32 mmol), 64%, 95.0% pure according to .sup.1H-NMR.

C): (6-(Benzimidazol-2-yl)pyridin-2-yl)bis(6-methylpyridin-2-yl)fluoromethane

(21) ##STR00042##

(22) 3.0 ml of thionyl chloride are added dropwise to a suspension of 12.0 g of silica gel in 50 ml of dichloromethane, and the mixture is then stirred at room temperature for 1 h. A solution of 6.4 g (20 mmol) of (6-formylpyridin-2-yl)bis(6-methylpyridin-2-yl)fluoromethane and 2.4 g (22 mmol) of o-phenylenediamine is subsequently added dropwise, and the mixture is stirred for a further 6 h. 50 ml of dichloromethane and 50 ml of ethanol are added, the mixture is filtered through silica gel with suction, the latter is rinsed with dichloromethane, the organic phase is evaporated in vacuo, and the residue is recrystallised from about 50 ml of ethanol with addition of 5 ml of triethylamine. Yield: 4.9 g (12 mmol), 60%, 99.0% pure according to .sup.1H-NMR.

D): Cu Complex 8

(23) 1.3 g (10 mmol) of diisopropylethylamine are added to a mixture of 4.1 g (10 mmol) of (6-(benzimidazol-2-yl)pyridin-2-yl)bis(6-methylpyridin-2-yl)fluoromethane and 1.0 g (10 mmol) of copper(I) chloride in 50 ml of THF, and the mixture is stirred at 40 C. for 24 h. The reaction mixture is evaporated to a volume of 5 ml in vacuo, 30 ml of methanol are added, and the precipitated solid is filtered off with suction, washed three times with 10 ml of methanol each time and dried in vacuo. After recrystallisation twice from acetonitrile, the product is sublimed in a high vacuum (p=110.sup.6 mbar, T=310 C.). Yield: 3.3 g (7.0 mmol), 70%, 99.9% pure according to HPLC.

Example 9

Cu Complex 9

(24) ##STR00043##

A): 2-(1-Methoxymethyl-1H-imidazol-2-yl)pyridine

(25) ##STR00044##

(26) 600 ml of toluene, 84.2 g (580 mmol) of 1H-imidazol-2-ylpyridine [18653-75-3] and 14.8 g (40 mmol) of tetrabutylammonium bromide are added to a solution of 400.0 g (10 mol) of sodium hydroxide in 400 ml of water at room temperature with vigorous stirring, a mixture of 50.0 g (621 mmol) of chloromethyl methyl ether and 100 ml of toluene is then slowly added dropwise, and the mixture is stirred at room temperature for a further 16 h. The reaction mixture is extended with 800 ml of toluene and 800 ml of water, the organic phase is separated off and dried over magnesium sulfate, and the solvent is removed in vacuo. Yield: 99.0 g (90 mmol), 98%, 96% pure according to .sup.1H-NMR.

B): Bis(6-methylpyridin-2-yl)-(1-methoxymethyl-2-pyridin-2-yl-3H-imidazol-4-yl)methanol

(27) ##STR00045##

(28) 40 ml (100 mmol) of n-butyllithium (2.5 M in hexane) are added dropwise to a solution, cooled to 78 C., of 18.9 g (100 mmol) of 2-(1-methoxymethyl-1H-imidazol-2-yl)pyridine in 500 ml of THF, and the mixture is stirred for a further 30 min. A solution of 21.2 g (100 mmol) of bis(6-methyl-2-pyridinyl)methanone in 50 ml of THF is subsequently added in one portion, and the reaction mixture is allowed to warm to room temperature. After addition of a mixture of 100 ml of water and 6.0 ml of glacial acetic acid, the mixture is stirred for a further 1 h, and the organic phase is then separated off, dried over potassium carbonate and then evaporated to dryness in vacuo. Yield: 23.0 g (57 mmol), 57%, 95.0% pure according to .sup.1H-NMR.

C): Bis(6-methylpyridin-2-yl)-(2-pyridin-2-yl-3H-imidazol-4-yl)methane

(29) ##STR00046##

(30) 20.1 g (50 mmol) of bis(6-methylpyridin-2-yl)-(1-methoxymethyl-2-pyridin-2-yl-3H-imidazol-4-yl)methanol are suspended in 300 ml of glacial acetic acid. 20 ml of aqueous hypophosphorous acid (50% by weight) and 40 ml of aqueous hydroiodic acid (57% by weight) are added to the suspension, and the reaction mixture is stirred at 80 C. for 24 h. After cooling, the precipitated solid is filtered off with suction and washed once with 20 ml of glacial acetic acid and three times with 20 ml of methanol each time. The solid is suspended in 300 ml of dichloromethane, 100 ml of saturated ammonium chloride solution and then 50 ml of ammonia solution are added, the mixture is stirred until the solid has dissolved, the organic phase is separated off and washed with saturated sodium chloride solution, and the organic phase is dried over magnesium sulfate and then evaporated in vacuo. The residue is recrystallised twice from ethyl acetate. Yield: 10.9 g (32 mmol), 64%, 99.0% pure according to .sup.1H-NMR.

D): Cu Complex 9

(31) 1.3 g (10 mmol) of diisopropylethylamine are added to a mixture of 3.4 g (10 mmol) of bis(6-methylpyridin-2-yl)-(2-pyridin-2-yl-3H-imidazol-4-yl)methane and 1.0 g (10 mmol) of copper(I) chloride in 50 ml of THF, and the mixture is stirred at 40 C. for 24 h. The reaction mixture is evaporated to a volume of 5 ml in vacuo, and the precipitated solid is filtered off with suction, washed three times with 10 ml of methanol each time and dried in vacuo. After recrystallisation twice from DMF/EtOH, the product is sublimed in a high vacuum (p=110.sup.6 mbar, T=320 C.). Yield: 2.1 g (5.2 mmol), 52%, 99.8% pure according to HPLC.

Example 10

Cu Complex 10

(32) ##STR00047##

A): Tris(6-phenylpyridin-2-yl)phosphine oxide

(33) ##STR00048##

(34) 809 mg (4 mmol) of tris-tert-butylphosphine and then 674 g (3 mmol) of palladium(II) acetate are added to a mixture of 51.8 g (100 mmol) of tris-(6-bromopyridin-2-yl)phosphine oxide [197776-47-9], 61.0 g (500 mmol) of phenylboronic acid and 58.1 g (1 mol) of potassium fluoride (anhydrous) in 1000 ml of THF, and the mixture is subsequently stirred under reflux for 5 h. After cooling, 300 ml of water are added to the reaction mixture, the aqueous phase is separated off, and the organic phase is filtered through Celite and evaporated to dryness. The solid obtained in this way is recrystallised from chloroform (50 ml) with addition of ethanol (250 ml). Yield: 38.4 g (75 mmol), 75%, 99.0% pure according to .sup.1H-NMR.

B): Cu Complex 10

(35) A mixture of 5.1 g (10 mmol) of tris(6-phenylpyridin-2-yl)phosphine oxide and 891 mg (10 mmol) of copper(I) cyanide in 50 ml of THF is stirred at 60 C. for 24 h. The reaction mixture is evaporated to a volume of 5 ml in vacuo, 20 ml of methanol are added, and the precipitated solid is filtered off with suction, washed three times with 10 ml of methanol each time and dried in vacuo. Yield: 3.7 g (6.2 mmol), 62%, 99.0% pure according to .sup.1H-NMR.

Example 11

Cu Complex 11

(36) ##STR00049##

A): 2-[6-(Fluorobis(6-methylpyridin-2-yl)methyl)pyridin-2-yl]phenol

(37) ##STR00050##

(38) A mixture of 37.2 g (100 mmol) of (6-bromopyridin-2-yl)bis(6-methylpyridin-2-yl)fluoromethane, 16.5 g (120 mmol) of 2-hydroxyphenylboronic acid [89466-08-0], 17.4 g (300 mmol) of potassium fluoride (anhydrous), 263 mg (1.3 mmol) of tri-tert-butylphosphine and 225 mg (1 mmol) of palladium(II) acetate in 500 ml of THF is heated under reflux for 5 h. After cooling, the salts are filtered off and rinsed twice with 100 ml of THF each time, the THF is removed in vacuo, the oily residue is taken up in 500 ml of dichloromethane, and the organic phase is washed three times with 200 ml of water each time and dried over magnesium sulfate. After the magnesium sulfate has been filtered off via a Celite bed, the organic phase is evaporated to dryness, and the residue is recrystallised from ethyl acetate/heptane. Yield: 27.4 g (71 mmol), 71%, 99.0% pure according to .sup.1H-NMR.

B): Cu Complex 11

(39) 1.3 g (10 mmol) of diisopropylethylamine are added to a mixture of 3.9 g (10 mmol) of 2-[6-(fluorobis(6-methylpyridin-2-yl)methyl)pyridin-2-yl]phenol and 1.0 g (10 mmol) of copper(I) chloride in 50 ml of THF, and the mixture is stirred at 40 C. for 24 h. The reaction mixture is evaporated to a volume of 5 ml in vacuo, 30 ml of methanol are added, and the precipitated solid is filtered off with suction, washed three times with 10 ml of methanol each time and dried in vacuo. After recrystallisation twice from DMF/EtOH, the product is sublimed in a high vacuum (p=110.sup.6 mbar, T=340 C.). Yield: 1.4 g (3.1 mmol), 31%, 99.5% pure according to NMR.

Example 12

Cu Complex 12

(40) ##STR00051##

A): Bis(6-tert-butylpyridin-2-yl)methanone

(41) ##STR00052##

(42) 80 ml (200 mmol) of n-butyllithium (2.5 N) are added dropwise to a suspension, cooled to 78 C., of 45.0 g (210 mmol) of 2-bromo-6-tert-butylpyridine [195044-14-5] in 500 ml of diethyl ether, and the mixture is stirred at 78 C. until a yellow solution forms. The yellow solution is stirred at 78 C. for a further 30 min., 9.2 ml (100 mmol) of N,N-dimethylcarbamoyl chloride [79-44-7] are then added, and the mixture is again stirred at 78 C. for a further 30 min. After warming to 0 C., a mixture of 100 ml of water and 2 ml of glacial acetic acid is added dropwise, the mixture is stirred for a further 30 min., and the precipitated solid is then filtered off with suction, washed once with 25 ml of diethyl ether and once with 25 ml of ethanol and dried in vacuo. Yield: 19.9 g (67 mmol), 67%, 97% pure according to .sup.1H-NMR.

B): (6-Bromopyridin-2-yl)bis(6-tert-butylpyridin-2-yl)methanol

(43) ##STR00053##

(44) 40.0 ml (100 mmol) of n-butyllithium (2.5 N) are added dropwise to a suspension, cooled to 78 C., of 26.1 g (110 mmol) of 2,6-dibromopyridine in 200 ml of diethyl ether, and the mixture is stirred at 78 C. until a yellow solution forms. This solution is diluted dropwise with 200 ml of diethyl ether, and a solution of 29.6 g (100 mmol) of bis(6-tert-butylpyridin-2-yl)methanone in 150 ml of THF is then added in one portion with vigorous stirring. After warming to 0 C., a mixture of 50 ml of water and 6 ml of glacial acetic acid is added dropwise, the mixture is stirred for a further 30 min., and the precipitated solid is then filtered off with suction, washed once with 25 ml of diethyl ether and once with 25 ml of ethanol and dried in vacuo. Yield: 23.2 g (51 mmol), 51%, 98% pure according to .sup.1H-NMR.

C): (6-Carboxypyridin-2-yl)bis(6-tert-butylpyridin-2-yl)methanol

(45) ##STR00054##

(46) 40.0 ml (100 mmol) of n-butyllithium (2.5 N) are added dropwise to a suspension, cooled to 78 C., of 22.7 g (50 mmol) of (6-bromopyridin-2-yl)bis(6-tert-butylpyridin-2-yl)methanol in 500 ml of THF. After the mixture has been stirred for a further 45 min., a vigorous stream of carbon dioxide is passed in for 30 min., the reaction mixture is then allowed to warm to room temperature and is evaporated to dryness in vacuo, the residue is taken up in 500 ml of ethyl acetate, 200 ml of water and 6 ml of acetic acid are added, and the organic phase is separated off, washed twice with 200 ml of water each time and once with 200 ml of saturated sodium chloride solution and then dried over magnesium sulfate. After removal of the solvent, the residue is recrystallised from methanol. Yield: 13.8 g (33 mmol), 66%, 95% pure according to .sup.1H-NMR.

D): (6-Carboxypyridin-2-yl)bis(6-tert-butylpyridin-2-yl)methane

(47) ##STR00055##

(48) 21.0 g (50 mmol) of (6-carboxypyridin-2-yl)bis(6-tert-butylpyridin-2-yl)methanol are suspended in 300 ml of glacial acetic acid. 20 ml of aqueous hypophosphorous acid (50% by weight) and 40 ml of aqueous hydroiodic acid (57% by weight) are added to the suspension, and the reaction mixture is stirred at 80 C. for 24 h. After cooling, the precipitated solid is filtered off with suction, washed once with 20 ml of glacial acetic acid and three times with 20 ml of methanol each time. The solid is suspended in 300 ml of dichloromethane, 100 ml of saturated ammonium chloride solution and then 3 ml of ammonia solution are added, the mixture is stirred until the solid has dissolved, the organic phase is separated off and washed with saturated sodium chloride solution, and the organic phase is dried over magnesium sulfate and then evaporated in vacuo. The residue is recrystallised twice from methanol. Yield: 16.6 g (41 mmol), 41%, 98.0% pure according to .sup.1H-NMR.

E): 1-(6-Carboxypyridin-2-yl)bis-1,1-(6-tert-butylpyridin-2-yl)ethane

(49) ##STR00056##

(50) 40.0 ml (100 mmol) of n-butyllithium (2.5 N) are added dropwise to a suspension, cooled to 78 C., of 20.2 g (50 mmol) of (6-carboxypyridin-2-yl)bis(6-tert-butylpyridin-2-yl)methane in 300 ml of THF. After the mixture has been stirred for a further 45 min., 3.7 ml (60 mmol) of methyl iodide are added, and the mixture is stirred at 78 C. for a further 30 min. After slow warming to room temperature, the solvent is removed in vacuo, the residue is taken up in 300 ml of ethyl acetate, 200 ml of saturated ammonium chloride solution are added, and the organic phase is separated off, washed twice with 100 ml of water each time and once with 100 ml of saturated sodium chloride solution and then dried over magnesium sulfate.

(51) After removal of the solvent, the residue is recrystallised from methanol. Yield: 9.7 g (23 mmol), 46%, 98.0% pure according to .sup.1H-NMR.

F): Cu Complex 12

(52) 1.3 g (10 mmol) of diisopropylethylamine are added to a mixture of 4.2 g (10 mmol) of 1-(6-carboxypyridin-2-yl)bis-1,1-(6-tert-butylpyridin-2-yl)ethane and 1.0 g (10 mmol) of copper(I) chloride in 50 ml of THF, and the mixture is stirred at 60 C. for 24 h. The reaction mixture is evaporated to a volume of 5 ml in vacuo, 30 ml of methanol are added, and the precipitated solid is filtered off with suction, washed three times with 10 ml of methanol each time and dried in vacuo. After recrystallisation twice from THF/MeOH, the product is sublimed in a high vacuum (p=110.sup.6 mbar, T=340 C.). Yield: 1.4 g (2.9 mmol), 29%, 99.8% pure according to HPLC.

Example 13

Cu Complex 13

(53) ##STR00057##

A): Bis(6-tert-butylpyridin-2-yl)-(1-methoxymethyl-2-pyridin-2-yl-3H-imidazol-4-yl)methanol

(54) ##STR00058##

(55) 40 ml (100 mmol) of n-butyllithium (2.5 M in hexane) are added dropwise to a solution, cooled to 78 C., of 18.9 g (100 mmol) of 2-(1-methoxymethyl-1H-imidazol-2-yl)pyridine in 500 ml of THF, and the mixture is stirred for a further 30 min. A solution of 29.6 g (100 mmol) of bis(6-tert-butyl-2-pyridinyl)methanone in 150 ml of THF is subsequently added in one portion, and the reaction mixture is allowed to warm to room temperature. After addition of 100 ml of saturated ammonium chloride solution, the mixture is stirred for a further 15 min., and the organic phase is separated off, dried over potassium carbonate and then evaporated to dryness in vacuo. Yield: 32.5 g (67 mmol), 67%, 97.0% pure according to .sup.1H-NMR.

B): Bis(6-tert-butylpyridin-2-yl)-(2-pyridin-2-yl-3H-imidazol-4-yl)methane

(56) ##STR00059##

(57) 24.3 g (50 mmol) of bis(6-tert-butylpyridin-2-yl)-(1-methoxymethyl-2-pyridin-2-yl-3H-imidazol-4-yl)methanol are suspended in 300 ml of glacial acetic acid. 20 ml of aqueous hypophosphorous acid (50% by weight) and 40 ml of aqueous hydroiodic acid (57% by weight) are added to the suspension, and the reaction mixture is stirred at 80 C. for 24 h. After cooling, the precipitated solid is filtered off with suction and washed once with 20 ml of glacial acetic acid and three times with 20 ml of methanol each time. The solid is suspended in 300 ml of dichloromethane, 100 ml of saturated ammonium chloride solution and then 50 ml of ammonia solution are added, the mixture is stirred until the solid has dissolved, the organic phase is separated off and washed with saturated sodium chloride solution, and the organic phase is dried over magnesium sulfate and then evaporated in vacuo. The residue is recrystallised twice from ethyl acetate. Yield: 18.7 g (44 mmol), 88%, 99.8% pure according to .sup.1H-NMR.

C): Cu Complex 13

(58) 1.3 g (10 mmol) of diisopropylethylamine are added to a mixture of 4.3 g (10 mmol) of bis(6-tert-butylpyridin-2-yl)-(2-pyridin-2-yl-3H-imidazol-4-yl)-methane and 1.0 g (10 mmol) of copper(I) chloride in 80 ml of THF, and the mixture is stirred at 40 C. for 14 h. The reaction mixture is evaporated to a volume of 5 ml in vacuo, 30 ml of methanol are added, and the precipitated solid is filtered off with suction, washed three times with 10 ml of methanol each time and dried in vacuo. After recrystallisation twice from THF/MeOH, the product is sublimed in a high vacuum (p=110.sup.6 mbar, T=330 C.). Yield: 1.8 g (3.7 mmol), 37%, 99.8% pure according to HPLC.

Example 14

Cu Complex 14

(59) ##STR00060##

A): Bis(6-phenylpyridin-2-yl)-(1-methoxymethyl-2-pyridin-2-yl-3H-imidazol-4-yl)methanol

(60) ##STR00061##

(61) 40 ml (100 mmol) of n-butyllithium (2.5 M in hexane) are added dropwise to a solution, cooled to 78 C., of 18.9 g (100 mmol) of 2-(1-methoxymethyl-1H-imidazol-2-yl)pyridine in 500 ml of THF, and the mixture is stirred for a further 30 min. A solution of 33.6 g (100 mmol) of bis(6-phenyl-2-pyridinyl)methanone [217177-35-0] in 150 ml of THF is subsequently added in one portion, and the reaction mixture is allowed to warm to room temperature. After addition of 100 ml of saturated ammonium chloride solution, the mixture is stirred for a further 15 min., and the organic phase is separated off, dried over potassium carbonate and then evaporated to dryness in vacuo. Yield: 34.2 g (65 mmol), 65%, 97.0% pure according to .sup.1H-NMR.

B): Bis(6-phenylpyridin-2-yl)-(2-pyridin-2-yl-3H-imidazol-4-yl)methane

(62) ##STR00062##

(63) 26.3 g (50 mmol) of bis(6-phenylpyridin-2-yl)-(1-methoxymethyl-2-pyridin-2-yl-3H-imidazol-4-yl)methanol are suspended in 300 ml of glacial acetic acid. 20 ml of aqueous hypophosphorous acid (50% by weight) and 40 ml of aqueous hydroiodic acid (57% by weight) are added to the suspension, and the reaction mixture is stirred at 80 C. for 24 h. After cooling, the precipitated solid is filtered off with suction and washed once with 20 ml of glacial acetic acid and three times with 20 ml of methanol each time. The solid is suspended in 300 ml of dichloromethane, 100 ml of saturated ammonium chloride solution and then 50 ml of ammonia solution are added, the mixture is stirred until the solid has dissolved, the organic phase is separated off and washed with saturated sodium chloride solution, and the organic phase is dried over magnesium sulfate and then evaporated in vacuo. The residue is recrystallised twice from ethyl acetate. Yield: 16.2 g (34 mmol), 69%, 99.0% pure according to .sup.1H-NMR.

C): Cu Complex 14

(64) 1.3 g (10 mmol) of diisopropylethylamine are added to a mixture of 4.7 g (10 mmol) of bis(6-phenylpyridin-2-yl)-(2-pyridin-2-yl-3H-imidazol-4-yl)methane and 1.0 g (10 mmol) of copper(I) chloride in 100 ml of THF, and the mixture is stirred at 40 C. for 24 h. The reaction mixture is evaporated to a volume of 5 ml in vacuo, 30 ml of methanol are added, and the precipitated solid is filtered off with suction, washed three times with 10 ml of methanol each time and dried in vacuo. After recrystallisation twice from THF/MeOH, the product is sublimed in a high vacuum (p=110.sup.6 mbar, T=340 C.). Yield: 2.4 g (4.5 mmol), 45%, 99.8% pure according to HPLC.

Example 15

Cu Complex 15

(65) ##STR00063##

A): 2-Bromo-6-(2,2-dipyridin-2-yl)propyl)pyridine

(66) ##STR00064##

(67) 40 ml (100 mmol) of n-butyllithium (2.5 M in hexane) are added dropwise to a solution, cooled to 78 C., of 18.4 g (100 mmol) of 2,2-ethylidenebis-pyridine [29280-41-9] in 500 ml of THF, and the mixture is stirred for a further 30 min. A solution of 20.6 g (100 mmol) of 2-bromo-6-chloromethylpyridine [727356-19-6] in 100 ml of THF is then added dropwise, and the mixture is then stirred at 78 C. for a further 15 min. After warming to room temperature, the solvent is removed in vacuo, the residue is taken up in 300 ml of dichloromethane, and the organic phase is washed twice with 100 ml of water each time and dried over magnesium sulfate. The residue is recrystallised twice from ethyl acetate/heptane. Yield: 19.5 g (55 mmol), 55%, 95.0% pure according to .sup.1H-NMR.

B): 7-[6-(2,2-Dipyridin-2-yl)propyl)pyridin-2-yl]-1-H-indole

(68) ##STR00065##

(69) A mixture of 35.4 g (100 mmol) of 2-bromo-6-(2,2-di-pyridin-2-yl)propyl)pyridine, 19.3 g (120 mmol) of indol-7-ylboronic acid [210889-31-9], 17.4 g (300 mmol) of potassium fluoride (anhydrous), 263 mg (1.3 mmol) of tritert-butylphosphine and 225 mg (1 mmol) of palladium(II) acetate in 500 ml of THF is heated under reflux for 5 h. After cooling, the salts are filtered off and washed twice with 100 ml of THF each time, the THF is removed in vacuo, the oily residue is taken up in 500 ml of dichloromethane, and the organic phase is washed three times with 200 ml of water each time and dried over magnesium sulfate. After the magnesium sulfate has been filtered off via a Celite bed, the organic phase is evaporated to dryness, and the residue is recrystallised from ethyl acetate/heptane. Yield: 29.3 g (75 mmol), 75%, 99.0% pure according to .sup.1H-NMR.

C): Cu Complex 15

(70) 1.3 g (10 mmol) of diisopropylethylamine are added to a mixture of 3.9 g (10 mmol) of 7-[6-(2,2-dipyridin-2-yl)propyl)pyridin-2-yl]-1-H-indole and 1.0 g (10 mmol) of copper(I) chloride in 100 ml of THF, and the mixture is stirred at 40 C. for 24 h. The reaction mixture is evaporated to a volume of 5 ml in vacuo, 30 ml of methanol are added, and the precipitated solid is filtered off with suction, washed three times with 10 ml of methanol each time and dried in vacuo. After recrystallisation twice from THF/MeOH, the product is sublimed in a high vacuum (p=110.sup.6 mbar, T=340 C.). Yield: 1.3 g (2.9 mmol), 29%, 99.7% pure according to HPLC.

Example 16

Ag Complexes

(71) 1.3 g (10 mmol) of diisopropylethylamine are added to a mixture of 10 mmol of ligands and 2.5 g (10 mmol) of silver hexafluorophosphate in 100 ml of THF, and the mixture is stirred at 40 C. for 24 h. The reaction mixture is evaporated to a volume of 5 ml in vacuo, 30 ml of methanol are added, and the precipitated solid is filtered off with suction, washed three times with 10 ml of methanol each time and dried in vacuo. After recrystallisation twice from THF/MeOH, the product is sublimed in a high vacuum (p=110.sup.6 mbar).

(72) TABLE-US-00002 Ex. Ligand Complex Yield 17 27% 18 23% 19 0 24% 20 31%

Example 21

Production and Characterisation of Organic Electroluminescent Devices from the Gas Phase

(73) Electroluminescent devices according to the invention can be produced as described, for example, in WO 05/003253. The results for various OLEDs are compared here. The basic structure, the materials used, the degree of doping and their layer thicknesses are identical for better comparability.

(74) The following device structure is used here:

(75) TABLE-US-00003 Hole-injection layer (HIL) 20 nm of 2,2,7,7-tetrakis(di-para-tolyl- amino)spiro-9,9-bifluorene Hole-transport layer (HTL1) 5 nm of NPB (N-naphthyl-N-phenyl-4,4- diaminobiphenyl) Electron-blocking layer (EBL) EBM1, 10 nm or EBM2, 10 nm Emission layer (EML) matrix M1, M2, M3 or M4 or combinations thereof, 40 nm; emitter: 10% by vol. doping; compounds, see Table 1. Electron conductor (ETL) 20 nm of BAlq Cathode 1 nm of LiF, 100 nm of Al on top.

(76) The structures of EBM, M and TEB are depicted below for clarity.

(77) ##STR00074## ##STR00075##

(78) These as yet unoptimised OLEDs are characterised by standard methods; for this purpose, the electroluminescence spectra, the external quantum efficiency (measured in %) as a function of the luminance, calculated from current/voltage/luminance characteristic lines (IUL characteristic lines), are determined.

(79) TABLE-US-00004 TABLE 1 Device results EQE at Voltage at Matrix 100 cd/m.sup.2 100 cd/m.sup.2 CIE Ex. EBL Emitter [%] [V] x/y 22 EBM1 M3 7.8 6.3 0.24/0.62 Cu complex 7 23 EBM1 M1 (40%) 6.8 5.7 0.25/0.59 M3 (50%) Cu complex 7 24 EBM2 M3 9.5 5.5 0.17/0.46 Cu complex 8 25 EBM2 M3 (50%) 8.9 5.8 0.19/0.48 M4 (40%) Cu complex 8 26 EBM2 M3 7.5 6.1 0.17/0.39 Ex. 27 Cu complex 9 27 EBM1 M2 8.3 7.4 0.17/0.38 Cu complex 9 28 EBM2 M1 (20%) 9.4 6.4 0.25/0.55 M3 (70%) Cu complex 11 29 EBM2 M1 (30%) 10.5 6.2 0.25/0.53 M3 (60%) Cu complex 11 30 EBM2 M1 (20%) 6.1 6.5 0.56/0.42 M3 (70%) Cu complex 12 31 EBM2 M1 (20%) 7.8 5.9 0.35/0.60 M3 (70%) Cu complex 13 32 EBM2 M1 (20%) 8.0 6.0 0.37/0.60 M3 (70%) Cu complex 14 33 EBM1 M1 (10%) 6.5 6.8 0.67/0.31 M3 (80%) Cu complex 15 34 EBM2 M1 (20%) 4.2 6.0 0.30/0.59 M3 (70%) Ag complex 18 35 EBM2 M1 (20%) 5.0 5.7 0.32/0.61 M3 (70%) Ag complex 19

Example 36

Production and Characterisation of Organic Electroluminescent Devices from Solution

(80) LEDs are produced by the general process outlined below. This must of course be adapted in individual cases to the particular circumstances (for example layer-thickness variation in order to achieve optimum efficiency or colour).

(81) General Process for the Product Ion of OLEDs:

(82) The production of components of this type is based on the production of polymeric light-emitting diodes (OLEDs), which has already been described many times in the literature (for example in WO 04/037887 A2). In the present case, the compounds according to the invention are dissolved in toluene, chlorobenzene or DMF together with the matrix materials or matrix-material combinations mentioned. The typical solids content of such solutions is between 10 and 25 g/l if, as here, the typical layer thickness of 80 nm for a device is to be achieved by means of spin coating.

(83) OLEDs having the following structure are produced analogously to the general process indicated above:

(84) TABLE-US-00005 PEDOT 20 nm (applied by spin-coating from water; PEDOT purchased from BAYER AG; poly[3,4-ethylenedioxy- 2,5-thiophene] Matrix + emitter 80 nm, 10% by weight emitter concentration (applied by spin-coating from toluene, chlorobenzene or DMF) Ba/Ag 10 nm of Ba/150 nm of Ag as cathode.

(85) Structured ITO substrates and the material for the so-called buffer layer (PEDOT, actually PEDOT:PSS) are commercially available (ITO from Technoprint and others, PEDOT:PSS as Clevios Baytron P aqueous dispersion from H.C. Starck). The emission layer is applied by spin-coating in an inert-gas atmosphere, in the present case argon, and dried by heating at 120 C. for 10 min. Finally, a cathode comprising barium and aluminium is applied by vacuum vapour deposition. The solution-processed devices are characterised by standard methods; the OLED examples mentioned have not yet been optimised. Table 2 shows the efficiency and voltage at 100 cd/m.sup.2 and the colour.

(86) TABLE-US-00006 TABLE 2 Device results EQE at Voltage at Matrix 100 cd/m.sup.2 100 cd/m.sup.2 CIE Ex. Emitter [%] [V] x/y 37 M1 (30%) 2.1 8.9 0.35/0.61 M4 (60%) Cu complex 1 38 M3 (45%) 3.4 6.2 0.17/0.55 M4 (45%) Cu complex 6 39 M1 (30%) 4.9 7.7 0.30/0.42 M4 (60%) Cu complex 10 40 M1 (30%) 3.0 6.9 0.51/0.40 M4 (60%) Cu complex 17 41 M1 (30%) 4.1 6.8 0.65/0.30 M4 (60%) Cu complex 20