Metal complexes comprising condensed heteroaromatic rings

Abstract

The present invention relates inter alia to a new class of heteroleptic metal complexes comprising condensed aromatic heterocyclic rings, their preparation and use.

Claims

1. A compound of the general Formula (1) ##STR00409## wherein A and B together represent a condensed heteroaromatic ring system wherein both A and B can be unsubstituted or identically or differently be substituted with one or more R.sup.1; wherein A can be any aromatic or heteroaromatic ring or any aromatic or heteroaromatic polycyclic ring system; wherein B represents any monocyclic heteroaromatic ring; wherein C represents a chemical structure having the Formula (2) which is condensed to ring D at any positions via the positions indicated by the sign # in Formula (2); ##STR00410## and where the remaining indices and symbols are defined as follows: a is 0, 1 or 2; b is 0, 1 or 2; c is 0, 1, 2, 3 or 4; M is a metal selected from the group consisting of iridium, rhodium, platinum and palladium; n is 2 for M equal to iridium or rhodium and n is 1 for M equal to platinum or palladium; if n is 2, the two ligands comprising the rings A, B, C and D can be identical or different from each other; R.sup.1 is identical or different from each other on each occurrence and selected from H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(R.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 straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which may be substituted by one or more substituents R.sup.2, where one or more non-adjacent CH.sub.2 groups may be 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 may be replaced by D, 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 substituents R.sup.2, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more substituents R.sup.2, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more substituents R.sup.2, or a combination of two or more of these groups; two or more groups R.sup.1 here may also form a mono- or poly-cyclic, aliphatic, aromatic and/or benzo-fused ring system with one another; R.sup.2 is, identical or different on each occurrence, H, D, F, Cl, Br, I, N(R.sup.3).sub.2, CN, NO.sub.2, Si(R.sup.3).sub.3, B(R.sup.3).sub.2, C(O)R.sup.3, P(O)(R.sup.3).sub.2, S(O)R.sup.3, S(O).sub.2R.sup.3, OSO.sub.2R.sup.3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which may be substituted by one or more substituents R.sup.3, where one or more non-adjacent CH.sub.2 groups may be replaced by R.sup.3CCR.sup.3, CC, Si(R.sup.3).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, CO, CS, CSe, CNR.sup.3, P(O)(R.sup.3), SO, SO.sub.2, NR.sup.3, O, S or CONR.sup.3 and where one or more H atoms may be replaced by D, 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 substituents R.sup.3, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more substituents R.sup.3, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more substituents R.sup.3, or a combination of two or more of these groups; two or more adjacent substituents R.sup.2 here may form a mono- or polycyclic, aliphatic or aromatic ring system with one another; R.sup.3 is identical or different on each occurrence and selected from H, D, F or an aliphatic, aromatic and/or heteroaromatic hydrocarbon having 1 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by F; two or more substituents R.sup.3 here may also form a mono-or polycyclic, aliphatic or aromatic ring system with one another; Q is identical or different on each occurrence and selected from R.sup.1CCR.sup.1, R.sup.1CN, O, S, SO.sub.2, SiR.sup.1.sub.2, Se or NR.sup.1; X.sup.1 and X.sup.2 are identical or different on each occurrence, selected from CR.sup.1 or N, wherein at least one of X.sup.1 and X.sup.2 is N; V is identical or different on each occurrence and selected from NR.sup.1, O, S, SO.sub.2, SiR.sup.1.sub.2, BR.sup.1 or Se.

2. The compound according to claim 1, wherein ring A is a ring or ring system according to Formula (3) ##STR00411## wherein X is identical or different on each occurrence and selected from CR.sup.1 or N, and wherein the signs # indicate the positions in ring A which are condensed to ring B.

3. The compound according to claim 1, wherein the compound has one of the following general Formulae (9) to (26) ##STR00412## ##STR00413## ##STR00414## ##STR00415## ##STR00416##

4. The compound according to claim 1, wherein the compound has the following general Formula (65) ##STR00417## wherein compound of Formula (66) is condensed via positions #1 and #2 to compound of Formula (65) via positions*1, *2 or *3 ##STR00418##

5. The compound according to claim 4, wherein condensation occurs via position #1 to *1 or to *3 and #2 to *2.

6. The compound according to claim 4, wherein condensation occurs via position #1 to *1 and #2 to *2.

7. The compound according to claim 1, wherein X.sup.1 is N and X.sup.2 is CR.sup.1.

8. The compound according to claim 1, wherein both X.sup.1 and X.sup.2 are N.

9. The compound according to claim 1, wherein the substituents R.sup.1 do not form mono or polycyclic, aliphatic and/or aromatic and/or benzo-fused ring systems with one another.

10. A composition comprising at least one compound according to claim 1 and at least one further organic functional material selected from hole transport material (HTM), hole injection material (HIM), electron transport material (ETM), electron injection material (EIM), hole blocking material (HBM), exciton blocking material (ExBM), host or matrix material, fluorescent emitter, phosphorescent emitter.

11. The composition according to claim 10, wherein the at least one organic functional material is a matrix material selected from ketones, phosphinoxides, sulfoxides, sulfones, triarylamines, carbazoles, indolocarbazoles, indenocarbazoles, azacarbazoles, bipolar matrix materials, silanes, azaborolenes, boronesters, triazines, zinc complexes, diaza- or tetraazasiloles or diazaphospholes or mixtures thereof.

12. A formulation comprising at least one compound according to claim 1 and at least one solvent.

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

14. The electronic device as claimed in claim 13, wherein the device is organic electroluminescent device (OLED), organic light emitting diode, PLED(polymer light emitting diode), organic integrated cicuit (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 quenching device (O-FQD), light emitting electrochemical cell (LEC, OLEC, LEEC) or organic laser diode (O-Laser).

15. An electronic device which comprises the composition according to claim 10 in one or more light emitting layers.

16. An electroluminescent device comprising at least one compound according to claim 1.

17. A method for the medical treatment which comprises phototherapy with the electroluminescent device as claimed in claim 16.

18. The compound according to claim 1, wherein M is iridium; Q is R.sup.1CCR.sup.1; and V is O.

19. The compound according to claim 2, wherein X is CR.sup.1.

20. A process for a cosmetic application which comprises irradiation of the skin by means of phototherapy using the electroluminescent device according to claim 16.

21. The process according to claim 20, wherein the cosmetic application is an application in the area of acne, cellulite, skin reddening, skin wrinkling or skin rejuvenation.

22. A method for the treatment of the skin which comprises treating the skin by means of phototherapy through the use of a luminescent comprising the composition according to claim 16.

Description

WORKING EXAMPLES

(1) Materials (Acronyms)

(2) TABLE-US-00001 Structure Name (acronym) 2-(dibenzo[b,d]furan-4-yl)quinoline (dbfqH) 2-(dibenzo[b,d]furan-4-yl)-4-methylquinoline (dbfmqH) 2-dibenzothiophene-4-yl-quinoline (dbtqH) (2-(3-(trifluoromethyl)-1H-pyrazol-5-yl)pyridine) (fppzH) 2-(3-(trifluoromethyl)-1H-1,2,4-triazol-5-yl)pyridine (fptzH) 2-(3-methyl-1H-pyrazol-5-yl)pyridine (mppzH) 2-(3-(tert-butyl)-1H-pyrazol-5-yl)pyridine (bppzH) 00 2-(3-(perfluorobutyl)-1H-pyrazol-5-yl)pyridine (hppzH) 01 2-(3-(perfluorobutyl)-1H-1,2,4-triazol-5-yl)pyridine (hptzH) 02 2-(3-phenyl-1H-1,2,4-triazol-5-yl)pyridine (pptzH) 03 2-(3-methyl-1H-1,2,4-triazol-5-yl)pyridine (mptzH) 04 2-(3-tert-butyl)-1H-1,2,4-triazol-5-yl)pyridine (tptzH) 05 2-(3-trifluoromethyl)-1H-[1,2,4]triazol-4-yl)-4- methyl-5-pyridin iodide (ftmpiH) 06 picolinic acid (pic)

(3) Chemical syntheses of the ligands bppzH and mppzH are well known to one skilled in the art. They can be prepared according to Yu, Wei-Shan et al., JAGS, 125(36), 10800-10801; 2003.

(4) Chemical syntheses of the ligands pptzH and mptzH are well known to one skilled in the art. They can be prepared according to Orselli, Enrico et al, Inorg. Chem., 46(26), 11082-11093; 2007.

(5) ##STR00107## ##STR00108## ##STR00109##

(6) The compounds V1, V2, V4, SSM-1, SSM-2, SSM-3, ET-1 and ET-2 are well known from the prior art. As an example, the compounds V1, V2, V4, SSM-1, SSM-2, SSM-3 and ET-1 have been disclosed in WO 2005/033244, WO 2004/026886, JP 2012/77069, WO 2011/137922, WO 2012/048778, WO 2011/032626 and WO 2010/072300, respectively. Compound ET-2 can be purchased from ABCR GmbH & Co. KG, Karlsruhe. Compound V3 ([(dbfq).sub.2Ir(pic)]) is a complex showing deep red light emission. V3 can be prepared according to the procedure as outlined in Example 8, wherein pic (30 mg, 0.24 mmol) is used instead of fppzH. V4 can be obtained with 74% yield.

Example 1

Synthesis of 2-(dibenzo[b,d]furan-4-yl)quinoline (dbfqH)

(7) ##STR00110##

(8) To a mixture of 2-chloroisoquinoline (1.73 g, 10.5 mmol) and Pd(PPh.sub.3).sub.4 (403 mg, 0.349 mmol) in 1,2-dimethoxyethane (50 mL) a solution of dibenzofuran-4-ylboronic acid (2.30 g, 10.9 mmol) in degassed ethanol (50 mL) is added, followed by addition of 2.6 M aqueous sodium carbonate solution (50 mL). Then, the mixture is heated under reflux for 19 h under inert atmosphere. After cooling, ethyl acetate (50 mL) and water (100 mL) are added, and the insoluble materials are removed by filtration. The filtrate is treated with a standard aqueous workup. The solvent is removed and the residue is purified by column chromatography to render a yellow solid.

(9) Recrystallization from chloroform/hexane yields a white crystalline solid of the titled compound dbfqH in 84% yield (2.62 g, 8.87 mmol).

Example 2

Synthesis of ligands L1 to L44

(10) In analogy to the preparation of (dbfqH) according to Example 1 the Suzuki coupling reaction can be used to prepare a variety of similar compounds such as compounds L1 to L44. The general preparation method is as follows: To a mixture of the halogen-compound (10.5 mmol; educt 2) and Pd(PPh.sub.3).sub.4 (0.35 mmol, 1/30 eq.) in 1,2-dimethoxyethane (50 mL) a solution of boronic acid (11 mmol; educt 1) in degassed ethanol (50 mL) is added, followed by addition of 2.6 M aqueous sodium carbonate solution (50 mL). Then, the mixture is heated under reflux for 20 h under inert atmosphere. After cooling, ethyl acetate (50 mL) and water (100 mL) are added, and the insoluble materials are removed by filtration. The filtrate is treated with a standard aqueous workup. The solvent is removed and the residue is purified by column chromatography. Recrystallization from chloroform/hexane yields a white crystalline solid of the compound in about 65 to 90% yield.

(11) The following ligands can be prepared according to the method provided herein:

(12) TABLE-US-00002 Educt 1 Educt 2 Product Yield 84% 78% 81% 0 73% 69% 81% 0 86% 74% 86% 0 71% 83% 82% 78% 0 79% 85% 89% 0 76% 90% 95% 0 86% 79% 76% 84% 0 91% 83% 77% 0 76% 85% 71% 00 80% 01 02 03 83% 04 05 06 78% 07 08 09 72% 0 86% 81% 83% 0 75% 92% 77% 0 73% 79% 70% 91% 0 85%

Example 3

Synthesis of 2-(3-(trifluoromethyl)-1H-pyrazol-5-yl)pyridine (fppzH) and 2(3-(perfluorobutyl)-1H-pyrazol-5-yl)pyridine (hppzH)

(13) ##STR00243##

(14) Concentrations used in the reaction are provided for both fppzH and hppzH in the following description.

(15) NaOEt (in case of fppzH: 1.82 g, 26.8 mmol; in case of hppzH: 1.23 g, 18.0 mmol) is dispersed in 50 mL of dry tetrahydrofuran (THF). To this solution either ethyl trifluoroacetate (3.2 mL, 26.8 mmol) for fppzH or nonafluoropentanoic acid ethyl ester (3.0 ml, 15.1 mmol) for hppzH is added slowly at 0 C. The mixture is stirred for 2 h followed by the addition of 2-acetylpyridine (in case of fppzH: 2.0 mL, 17.9 mmol; in case of hppzH: 1.87 mL, 16.7 mmol) at 0 C. The reaction is then heated to 50 C. for 4 h. Removal of the solvent renders a brown oily residue, which is dispersed in de-ionized water (50 mL). The mixture is neutralized with 2 N HCl.sub.(aq) (pH=4), followed by extraction with ethyl acetate (350 mL). The combined organic residue is dried over anhydrous Na.sub.2SO.sub.4. After filtration, a brown oil, the diketone, is obtained which is used without further purification. It is dissolved in 50 mL EtOH and treated with hydrazine monohydrate (in case of fppzH: 10 eq; in case of hppzH: 5 eq). The mixture is refluxed for 12 h. After cooling to room temperature, evaporation of the solvent at reduced pressure renders a brown residue, which is then dissolved in ethyl acetate. The organic phase is washed with water (20 mL3), dried over Na.sub.2SO.sub.4, and then filtered. Removal of ethyl acetate gives a pale-yellow solid. Finally the solid is recrystallized from CH.sub.2Cl.sub.2/hexane. Compound fppzH is obtained with 62% yield (2.4 g, 11 mmol). Compound hppzH is obtained in 68% yield (3.7 g, 10.2 mmol).

Example 4

Synthesis of 2-(3-(trifluoromethyl)-1H-1,2,4-triazol-5-yl)pyridine (fptzH) and 2-(3-(perfluorobutyl)-1H-1,2,4-triazol-5-yl)pyridine (hptzH)

(16) ##STR00244##

(17) A mixture of 2-cyanopyridine (3.15 g, 30.3 mmol) and NaOCH.sub.3 (0.16 g, 3 mmol) is prepared in 10 mL ethanol and stirred at RT for 4 h under inert atmosphere. After 4 h, NH.sub.4Cl (1.81 g, 33.8 mmol) is added to the solution. The mixture is refluxed for 6 hours, cooled down and filtered to remove excess salt. Ethanol is removed and a white solid of 2-pyridinecarboximidamidehydro-chloride (3.99 g, 25.2 mmol) is obtained.

(18) In case of fptzH:

(19) A solution of ethyl trifluoroacetate (3.52 g, 24.77 mmol) and hydrazine monohydrate (1.14 mL, 23.50 mmol) in 50 mL THF is refluxed for 1 h. Upon cooling to room temperature, 2-pyridinecarboximidamidehydro-chloride (3.99 g, 25.32 mmol) and NaOH (1.01 g, 25.32 mmol) are added to the solution. The mixture is refluxed for 6 h and cooled to room temperature. Afterwards a white solid is obtained by extraction with ethyl acetate. The product is purified via column chromatography and obtained with 56% yield (2.82 g, 13.16 mmol).

(20) In case of hptzH:

(21) A solution of nonafluoropentanoic acid ethyl ester (4.35 g, 14.9 mmol) and hydrazine monohydrate (0.73 mL, 15.8 mmol) in 50 mL THF is refluxed for 1 h. Upon cooling to room temperature, 2-pyridinecarboximidamide hydrochloride (2.49 g, 15.7 mmol) and NaOH (0.63 g, 15.8 mmol) are added to the solution. The mixture is refluxed for 6 h and cooled to room temperature. After the reaction is finished, a white solid is obtained by ethyl acetate extraction. The product is purified via column chromatography and is obtained in 62% yield (3.36 g, 9.23 mmol).

Example 5

Synthesis of 2-(3-(tert-butyl)-1H-1,2,4-triazol-5-yl)pyridine (tptzH)

(22) ##STR00245##

(23) A mixture of 2-cyanopyridine (3.15 g, 30.3 mmol) and NaOCH.sub.3 (0.16 g, 3 mmol) is prepared in 10 mL ethanol and stirred at RT for 4 h under inert atmosphere. After 4 h, NH.sub.4Cl (1.81 g, 33.8 mmol) is added to the solution. The mixture is refluxed for 6 h, cooled down and filtered to remove excess salt. Ethanol is removed and a white solid of 2-pyridinecarboximidamidehydro-chloride (3.99 g, 25.2 mmol) is obtained.

(24) A solution of pivalic acid chloride (3.54 g, 29.3 mmol) in 10 mL CH.sub.2Cl.sub.2 is added drop wise to 2-pyridinecarboximidamidehydrochloride (4 g, 29.3 mmol) and Na.sub.2CO.sub.3 (3.1 g, 29.3 mmol) in 100 mL H.sub.2O. The reaction mixture is stirred at RT for 2 h, yielding a white precipitate. The precipitate is filtered, and the solid washed with water and ethanol. The solid then is suspended in 5 mL of ethylene glycol and heated to 200 C. for 2 h, yielding a pale yellow solution. Upon cooling to room temperature, a white solid is formed, filtered of and washed with de-ionized water. The solid is dried under vacuum and used without further purification (3.2 g, 15.8 mmol, 53.8%).

Example 6

Synthesis of 2-(3-trifluoromethyl)-1H-[1,2,4]triazol-4-yl)-4-methyl-5-pyridin iodide (ftmpiH)

(25) ##STR00246##

(26) A mixture of ftptz (500 mg, 3.12 mmol) and methyl iodide (1 ml, 2.27 g, 16 mmol) is refluxed for 8 h, then anhydrous diethylether (100 ml) is added and the precipitate is filtered off. Recrystallisation from acetone renders a colorless product (424 mg, 1.40 mmol, 45% yield).

Example 7

Synthesis of (dbfq)2Ir(-Cl)2Ir(dbfq)2 (I)

(27) ##STR00247##

(28) A solution of dbfq-H (0.34 g, 1.15 mmol) and IrCl.sub.3.3H.sub.2O (205 mg, 0.585 mmol) in 2-ethoxyethanol (15 mL) is refluxed for 24 h. After cooling, water (50 mL) is added and the precipitate is collected by filtration. The solid is washed with ethanol (20 mL) and hexane (20 mL) to obtain the titled compound (I) as a red powder (0.36 g, 0.23 mmol, 78% yield). This material is used without further purification.

Example 8

Synthesis of further chloro-gridged dimers

(29) In analogy to the preparation of (dbfq).sub.2Ir(-Cl).sub.2Ir(dbfq).sub.2 (I) according to Example 7 further dimers can be produced. The general preparation method is as follows:

(30) A solution of ligand (1 mmol) and IrCl.sub.3.3H.sub.2O (180 mg, 0.513 mmol) in 2-ethoxyethanol (15 mL) is refluxed for 24 h. After cooling, water (50 mL) is added and the precipitate is collected by filtration. The solid is washed with ethanol (20 mL) and hexane (20 mL) to obtain the chloro-bridged dimer as a powder. This material is used without further purification.

(31) ##STR00248## ##STR00249## ##STR00250## ##STR00251## ##STR00252## ##STR00253## ##STR00254## ##STR00255## ##STR00256## ##STR00257## ##STR00258## ##STR00259## ##STR00260##

Example 9

Synthesis of compound (Ir(L1)fppz) (III)

(32) ##STR00261##

(33) A mixture of (dbfq).sub.2Ir(-Cl).sub.2Ir(dbfq).sub.2 (I) (200 mg, 0.122 mmol), fppzH (53 mg, 0.248 mmol) and Na.sub.2CO.sub.3 (120 mg, 1.13 mmol) in ethoxyethanol (10 mL) is heated at 130 C. for 2 h under inert atmosphere. After cooling, the reaction mixture is poured into water (50 mL) and the precipitate is collected by filtration. The solid is purified via column chromatography using CH.sub.2Cl.sub.2 as eluent. Further purification is carried out by recrystallization from CH.sub.2Cl.sub.2/methanol to obtain compound (III) as a red powder (180 mg, 0.18 mmol, 74% yield).

Example 10

Synthesis of compound (XIII) [(dbfq)2Ir(ftmpi)]

(34) ##STR00262##

(35) A mixture of (dbfq).sub.2Ir(-Cl).sub.2Ir(dbfq).sub.2 (I) (200 mg, 0.122 mmol), ftmpiH (89 mg, 0.250 mmol) and Na.sub.2CO.sub.3 (120 mg, 1.13 mmol) in ethoxyethanol (10 mL) is heated to 130 C. for 2 h in an inert atmosphere. After cooling, the reaction mixture is poured into water (50 mL) and the aqueous phase is extracted with dichloromethane. After removing the solvent, the product is purified via column chromatography using CH.sub.2Cl.sub.2 as eluent. Further purification is carried out by crystallization to obtain compound (XIII) as a red powder (185 mg, 0.17 mmol, 70% yield).

Example 11

Preparation of further complexes

(36) In analogy to the preparation according to Example 10 further complexes can be produced. The general preparation method is as follows:

(37) A mixture of the chloro-bridged dimer (Ir(Lxx).sub.2)Cl.sub.2 (0.177 mmol) wherein Lxx is defined as being one of the ligands L1 to L44, the third ligand (fppz, fptz, mppz, bppz, hppz, hptz, pptz, mptz, tptz, or ftmpi) (0.365 mmol) and Na.sub.2CO.sub.3 (0.85 mmol) are solved in ethoxyethanol (10 mL) and the reaction mixture is heated at 130 C. for 5 h in an inert atmosphere. After cooling, the reaction mixture is poured into water (50 mL) and the precipitate is collected by filtration. The solid is purified via column chromatography using CH.sub.2Cl.sub.2 as eluent. Further purification is carried out by recrystallization from CH.sub.2Cl.sub.2/methanol to obtain the compound as a red powder.

(38) The compounds given in the following table can be made according to the general procedure out of the chloro-bridged-dimers (Ir(L1).sub.2Cl).sub.2 to (Ir(L44).sub.2Cl).sub.2 and the third ligands ligand (fppz, fptz, mppz, bppz, hppz, hptz, pptz, mptz, tptz, or ftmpi). The over-all yield for each reaction is between 43% and 78%.

(39) ##STR00263## ##STR00264## ##STR00265## ##STR00266## ##STR00267## ##STR00268## ##STR00269## ##STR00270## ##STR00271## ##STR00272## ##STR00273## ##STR00274## ##STR00275## ##STR00276## ##STR00277## ##STR00278## ##STR00279## ##STR00280## ##STR00281## ##STR00282## ##STR00283## ##STR00284## ##STR00285## ##STR00286## ##STR00287## ##STR00288## ##STR00289## ##STR00290## ##STR00291## ##STR00292## ##STR00293## ##STR00294## ##STR00295## ##STR00296## ##STR00297## ##STR00298## ##STR00299## ##STR00300## ##STR00301## ##STR00302## ##STR00303## ##STR00304## ##STR00305## ##STR00306## ##STR00307## ##STR00308## ##STR00309## ##STR00310## ##STR00311## ##STR00312## ##STR00313## ##STR00314## ##STR00315## ##STR00316## ##STR00317## ##STR00318## ##STR00319## ##STR00320## ##STR00321## ##STR00322## ##STR00323## ##STR00324## ##STR00325## ##STR00326## ##STR00327## ##STR00328## ##STR00329## ##STR00330## ##STR00331## ##STR00332## ##STR00333## ##STR00334## ##STR00335## ##STR00336## ##STR00337## ##STR00338## ##STR00339## ##STR00340## ##STR00341## ##STR00342## ##STR00343## ##STR00344## ##STR00345## ##STR00346## ##STR00347## ##STR00348## ##STR00349## ##STR00350## ##STR00351## ##STR00352## ##STR00353## ##STR00354## ##STR00355## ##STR00356## ##STR00357## ##STR00358## ##STR00359## ##STR00360## ##STR00361## ##STR00362## ##STR00363## ##STR00364## ##STR00365## ##STR00366## ##STR00367## ##STR00368## ##STR00369## ##STR00370## ##STR00371## ##STR00372## ##STR00373## ##STR00374## ##STR00375## ##STR00376## ##STR00377## ##STR00378## ##STR00379## ##STR00380## ##STR00381## ##STR00382## ##STR00383## ##STR00384## ##STR00385## ##STR00386## ##STR00387## ##STR00388## ##STR00389## ##STR00390## ##STR00391## ##STR00392## ##STR00393##

Example 12

Synthesis of compound (XIV) [(dbfq)2Ir(ftmpp)]

(40) ##STR00394##

(41) Compound (XIII) (500 mg, 0.46 mmol) is dissolved in a mixture of CH.sub.2Cl.sub.2 and MeOH (2:1, 30 mL) and KPF.sub.6 in MeOH (5 mL) is added. After stirring for 12 h at room temperature, the solvent is removed in vacuu and the residue is washed with de-ionized water (50 mL), Recrystallization yields in a red powder of compound (XIV) (395 mg, 0,36 mmol, 78% yield).

Example 13

Preparation of further complexes

(42) In analogy to the preparation according to Example 12 further complexes can be produced. The general preparation method is as follows:

(43) Compound (Ir(Lxx)ftmpi) (0.5 mmol) is dissolved in a mixture of CH.sub.2Cl.sub.2 and MeOH (2:1, 30 mL) and KPF.sub.6 in MeOH (5 mL) is added, wherein Lxx is defined as being one of the ligands L1 to L44. After stirring for 12 h at room temperature, the solvent is removed in vacuu and the residue is washed with de-ionized water (50 mL). Recrystallization yields in a powder of the hexafluorophosphate compound (Ir(Lxx)ftmpp).

(44) The following table shows all ftmpi-based emitter compounds which can be converted to the ftmpp compounds according to this procedure with yields between 67% to 83%.

(45) ##STR00395## ##STR00396## ##STR00397## ##STR00398## ##STR00399## ##STR00400## ##STR00401## ##STR00402## ##STR00403## ##STR00404## ##STR00405## ##STR00406##

Example 14

Electroluminescent Devices

(46) Organic light emitting diodes (OLEDs) comprising materials according to this invention are made according to processes that are well known to one skilled in the art and that have been described in the literature many times (for example in WO 2004/037887 A2 for OLEDs made from solution, and WO 2004/058911 for OLEDs made by thermal evaporation).

(47) Emitters from the present invention are particularly well suited for OLEDs made from solution. A typical OLED device has the following layered structure: Ba/Al cathode (3 nm/100 nm)/EML (80 nm; 6-7 wt.-% emitter)/Interlayer (20 nm; HIL-012)/PEDOT (80 nm; Clevios P 4083 Al)/ITO, wherein EML represents the emissive layer. ITO-coated glass substrates are purchased from Technoprint, the cathode is deposited by vapour-deposition through an evaporation mask.

(48) The substrates are cleaned with de-ionised water and a detergent (Deconex 15 PF) in a clean room and then activated by UV/ozone plasma treatment. An 80 nm PEDOT layer (PEDOT is a polythiophene derivative (Clevios P 4083 Al) from H. C. Starck, Goslar, which is supplied as an aqueous dispersion) is then applied by spin coating, likewise in a clean room. The required spin rate depends on the degree of dilution and the specific spin-coater geometry (typical for 80 nm: 4500 rpm). In order to remove residual water from the layer, the substrates are dried by heating on a hotplate at 180 C. for 10 minutes. The substrates are transferred into a glove box and all subsequent coating and annealing steps are carried out in an inert-gas atmosphere (nitrogen or argon). A 20 nm film of an interlayer (typically a hole-dominated polymer, here HIL-012 from Merck) is spin-coated onto the substrate from a 5 g/L toluene solution and heated for 60 min. at 180 C. A particular advantage of some of the devices shown here is that even the interlayer can be omitted and thus very simple devices can be made. In the device setup 80 nm of an EML are applied from toluene solution. The concentrations depend on the specific composition of the EML: For EMLs that contain polymeric host materials, the concentration is 10 g/L, for EMLs based on soluble small molecules 18 to 20 g/L. The solvent for spin-coating is toluene. After the film is applied, the layers are annealed at 180 C. for 10 minutes. The Ba/Al cathode is then vapour-deposited, (high-purity metals from Aldrich, particularly barium 99.99% (Order No. 474711); typical vacuum level 510.sup.6 mbar). Alternatively, an organic electron transport layer (ETL) may be vapour-deposited between the solution processed EML and the cathode which then typically does not contain a Ba-layer. Finally, the device is encapsulated in order to protect the layers from air and atmospheric moisture.

(49) Devices are characterized in holders manufactured specifically for the substrate size. Electrical contact is made with spring contacts. A photodiode with eye response filter is placed directly on the measurement holder in order to exclude influences from extraneous light. Voltages are typically increased from 0 to max. 12 V in 0.2 V steps and reduced again. For each voltage, the current through the device and the photocurrent through the photodiode are measured. This way, the IUL data of the test devices are obtained. Important parameters are the efficiency and required voltage for 1000 cd/m.sup.2 as well as the external quantum efficiency (EQE, in %). To determine the colour and the precise electroluminescence spectrum of the test devices, the voltage required for 1000 cd/m.sup.2 is applied again and the photodiode is replaced by a cover that connects the sample holder with an Ocean Optics spectrometer via an optical fibre. The colour coordinates (CIE: Commission Internationale de l'Eclairage, standard observer from 1931) can be derived from the measured spectrum.

(50) Device lifetimes are measured in a separate setup, but in a very similar way. Based on the characterization data, voltage and current are provided to reach an initial luminance of 2000 to 6000 cd/m.sup.2 (chosen based on the initial efficiency of the specific device). Then the current is kept constant, which typically leads to an increase in voltage while the device is driven. Here, the lifetimes are determined as T50, the time when the initial luminance has degraded to 50% of the initial value. In order to compare lifetimes for devices with different starting brightnesses, the lifetimes are extrapolated to a starting brightness of 1000 cd/m.sup.2 with an extrapolation factor of 1.9 for devices with interlayer and 1.625 for devices without.

(51) The examples of solution processed devices with polymer matrices are mainly intended for cheap monochrome applications. They need sufficient lifetime, but mainly good efficiency and unusual (not display-type) colour. Solution processed devices with soluble small molecules can still be used for these applications, but are a little more demanding in terms of processing. They will therefore more likely be used in high-end applications where lifetime is also very important.

(52) Simplified Devices without Interlayer (Devices 1-17):

(53) 80 nm of the EML are spin-coated directly onto PEDOT. The concentration of the emitters is 7% by weight based on the polymer matrix P1. The overall concentration is 10 g/L, i.e. 9.3 g/L P1 and 0.7 g/L emitter, the spin-rate is 1200 rpm. The matrix of choice for these simple devices is P1, the polymerization of the monomers is carried out according to WO 2005/040302:

(54) ##STR00407##
(monomer concentrations in the matrix polymer are given in mol-% with respect to the polymer)

(55) The results are summarized in Table 1. The new emitters have a reasonable lifetime even in these simple and, thus, cheap devices. The colour is more orange, as intended, the efficiencies are very high for such a simple setup.

(56) TABLE-US-00003 TABLE 1 ETL/ Eff.*/ Device Emitter Host Cathode (cd/A) EQE* U*/V CIE* LT50*/h 1 V1 P1 Ba/Al 10.4 6.4% 4.2 0.63/0.37 840 2 (Ir(L1)fppz) P1 Ba/Al 11.4 6.0% 5.1 0.61/0.39 460 3 (Ir(L1)fptz) P1 Ba/Al 10.8 5.2% 4.9 0.59/0.41 320 4 (Ir(L3)tptz) P1 Ba/Al 10.1 6.1 4.9 0.59/0.38 530 5 (Ir(L5)bppz) P1 Ba/Al 10.5 5.9 5.0 0.58/0.39 350 6 (Ir(L6)hppz) P1 Ba/Al 10.9 5.7 4.5 0.62/0.35 480 7 (Ir(L9)pptz) P1 Ba/Al 10.8 6.2 4.8 0.61/0.37 340 8 (Ir(L11)fptz) P1 Ba/Al 11.0 6.1 4.7 0.59/0.39 510 9 (Ir(L14)mptz) P1 Ba/Al 11.3 5.9 5.1 0.61/0.38 490 10 (Ir(L16)pptz) P1 Ba/Al 10.6 5.6 4.3 0.61/0.36 400 11 (Ir(L19)pptz) P1 Ba/Al 10.3 5.2 4.4 0.60/0.37 420 12 (Ir(L22)hppz) P1 Ba/Al 11.1 5.3 5.1 0.58/0.37 500 13 (Ir(L26)mptz) P1 Ba/Al 9.8 5.9 5.3 0.59/0.35 390 14 (Ir(L35)bppz) P1 Ba/Al 10.7 5.7 4.8 0.56/0.40 450 16 (Ir(L41)pptz) P1 Ba/Al 11.2 6.0 5.1 0.60/0.39 380 17 (Ir(L44)mppz) P1 Ba/Al 10.7 5.7 5.0 0.61/0.36 430 *all values at 1000 cd/m.sup.2
Devices with Interlayer and a Polymer Matrix (Devices 18-6):

(57) 80 nm of the EML are spin-coated onto HIL-012. The concentration of the emitters is 7% by weight based on the polymer matrix P2. The overall concentration is 10 g/L, i.e. 9.3 g/L P2 and 0.7 g/L emitter, the spin-rate is 1200 rpm. The matrix of choice for these devices is P2, the polymerization of the monomers is carried out according to WO 2005/040302:

(58) ##STR00408##
(monomer concentrations in the matrix polymer are given in mol-% with respect to the polymer.)

(59) The results are summarized in Table 2.

(60) TABLE-US-00004 TABLE 2 Inter- ETL/ Eff.*/ Device layer Emitter Host Cathode (cd/A) EQE* U*/V CIE* LT50*/h 18 HIL-012 V2 P2 Ba/Al 0.70 0.4% 10.1 0.57/0.41 NA 19 HIL-012 (Ir(L1)fppz) P2 Ba/Al 9.3 4.7% 6.0 0.60/0.39 550 20 HIL-012 (Ir(L1)fptz) P2 Ba/Al 7.3 3.4% 6.2 0.58/0.41 450 21 HIL-012 (Ir(L3)tptz) P2 Ba/Al 7.1 4.0 5.9 0.58/0.38 737 22 HIL-012 (Ir(L5)bppz) P2 Ba/Al 7.8 4.4 6.3 0.57/0.39 473 23 HIL-012 (Ir(L6)hppz) P2 Ba/Al 8.6 4.2 5.4 0.61/0.35 667 24 HIL-012 (Ir(L9)pptz) P2 Ba/Al 8.3 4.8 5.7 0.60/0.37 425 25 HIL-012 (Ir(L11)fptz) P2 Ba/Al 7.7 4.3 5.6 0.58/0.39 658 26 HIL-012 (Ir(L14)mptz) P2 Ba/Al 7.4 4.5 6.4 0.60/0.38 686 27 HIL-012 (Ir(L16)pptz) P2 Ba/Al 7.9 3.9 5.3 0.60/0.36 520 28 HIL-012 (Ir(L19)pptz) P2 Ba/Al 7.9 3.1 5.5 0.59/0.37 512 29 HIL-012 (Ir(L22)hppz) P2 Ba/Al 7.4 3.6 6.2 0.57/0.37 625 30 HIL-012 (Ir(L26)mptz) P2 Ba/Al 7.4 4.2 6.4 0.58/0.35 534 31 HIL-012 (Ir(L35)bppz) P2 Ba/Al 9.3 3.8 5.7 0.55/0.40 599 33 HIL-012 (Ir(L41)pptz) P2 Ba/Al 7.9 4.4 6.3 0.59/0.39 532 34 HIL-012 (Ir(L44)mppz) P2 Ba/Al 7.1 4.3 6.1 0.60/0.36 563 *all values at 1000 cd/m.sup.2
Devices with Interlayer and Soluble Small Molecule Matrix 1 (Comp. 1) (Devices 35 to 58):

(61) 80 nm of the EML are spin-coated onto HIL-012. The soluble small molecule matrix consists of 30 wt.-% SSM1, 42 wt.-% SSM2 and 22 wt.-% SSM3 (=composition 1). The emitter concentration is 6 wt.-%. The overall concentration is 18 g/L, the spin-rates are between 650 and 1300 rpm. The results are summarized in Table 3.

(62) TABLE-US-00005 TABLE 3 Inter- ETL/ Eff.*/ Device layer Emitter Host Cathode (cd/A) EQE* U*/V CIE* LT50*/h 35 HIL-012 V1 Comp. 1 Ba/Al 11.0 7.5% 7.3 0.63/0.37 8000 36 HIL-012 V2 Comp. 1 Ba/Al 7.3 3.9% 10.1 0.58/0.41 330 37 HIL-012 V3 Comp. 1 Ba/Al 15.6 7.9% 7.4 0.59/0.41 3900 38 HIL-012 V4 Comp. 1 Ba/Al 13.9 9.5% 6.7 0.64/0.36 21000 39 HIL-012 (Ir(L1)fppz) Comp. 1 Ba/Al 24.2 11.5% 6.7 0.59/0.41 31000 40 HIL-012 (Ir(L1)fptz) Comp. 1 Ba/Al 25.3 11.1% 6.6 0.57/0.42 12000 41 HIL-012 (Ir(L1)hptz) Comp. 1 Ba/Al 15.3 7.9% 7.1 0.58/0.42 12000 42 HIL-012 (Ir(L1)mptz) Comp. 1 Ba/Al 13.0 7.0% 7.5 0.58/0.42 8000 43 HIL-012 (Ir(L2)fppz) Comp. 1 Ba/Al 23.7 9.9% 6.5 0.60/0.40 12000 44 HIL-012 (Ir(L2)fptz) Comp. 1 Ba/Al 17.4 7.2% 7.1 0.55/0.45 8000 45 HIL-012 (Ir(L3)tptz) Comp. 1 Ba/Al 20.1 11.4% 6.5 0.57/0.39 32000 46 HIL-012 (Ir(L5)bppz) Comp. 1 Ba/Al 24.1 12.5% 6.8 0.56/0.38 16000 47 HIL-012 (Ir(L6)hppz) Comp. 1 Ba/Al 28.0 12.6% 5.8 0.60/0.34 29000 48 HIL-012 (Ir(L9)pptz) Comp. 1 Ba/Al 26.0 15.3% 6.4 0.59/0.36 13000 49 HIL-012 (Ir(L11)fptz) Comp. 1 Ba/Al 26.3 11.0% 6.1 0.57/0.38 19000 50 HIL-012 (Ir(L14)mptz) Comp. 1 Ba/Al 22.6 13.3% 6.9 0.59/0.37 25000 51 HIL-012 (Ir(L16)pptz) Comp. 1 Ba/Al 21.9 11.4% 5.7 0.59/0.35 22000 52 HIL-012 (Ir(L19)pptz) Comp. 1 Ba/Al 22.9 10.0% 6.0 0.58/0.36 15000 53 HIL-012 (Ir(L22)hppz) Comp. 1 Ba/Al 22.7 11.0% 6.8 0.56/0.36 23000 54 HIL-012 (Ir(L26)mptz) Comp. 1 Ba/Al 24.4 13.7% 7.1 0.57/0.34 29000 55 HIL-012 (Ir(L35)bppz) Comp. 1 Ba/Al 28.3 12.1% 6.3 0.54/0.39 23000 57 HIL-012 (Ir(L41)pptz) Comp. 1 Ba/Al 24.2 12.6% 6.9 0.58/0.38 15000 58 HIL-012 (Ir(L44)mppz) Comp. 1 Ba/Al 21.9 10.9% 6.8 0.59/0.35 26000 *all values at 1000 cd/m.sup.2

(63) Compared to the two standard emitters V1 and V2, the emitters according to the invention show an overall much improved set of device characteristics. The co-ligand in V3 shortens the lifetime significantly. V4 is deep-red, the co-ligand thus introduces a strong batho-chromic shift. It is also worse in all parameters than the 1:1 comparison (Ir(L1)fppz).

(64) Devices with Interlayer, Soluble Small Molecule Matrix 1 (Comp. 1) and Additional Evaporated ETL:

(65) (Devices 59 to 75):

(66) 60 nm of the EML in composition 1 are spin-coated onto HIL-012. The emitter concentration is 6 wt.-%. The overall concentration is 18 g/L, the spin-rate is increased to 1900 rpm (due to the thinner EML-layer). A 50 nm ETL consisting of 50 wt.-% ET1 and 50 wt.-% ET2 is vapour-deposited on top of the spin-coated layer and capped with 100 nm of Al. The results are summarized in Table 4.

(67) TABLE-US-00006 TABLE 4 Inter- ETL/ Eff.*/ Device layer Emitter Host Cathode (cd/A) EQE* U*/V CIE* LT50*/h 59 HIL-012 V1 Comp. 1 ET1:ET2/Al 19.5 11.7 6.4 0.63/0.37 11500 60 HIL-012 (Ir(L1)fppz) Comp. 1 ET1:ET2/Al 23.1 12.4 7.0 0.60/0.40 18000 61 HIL-012 (Ir(L1)fptz) Comp. 1 ET1:ET2/Al 24.9 12.7 6.6 0.59/0.41 18000 62 HIL-012 (Ir(L3)tptz) Comp. 1 ET1:ET2/Al 20.1 11.4% 6.5 0.58/0.40 41000 63 HIL-012 (Ir(L5)bppz) Comp. 1 ET1:ET2/Al 24.1 12.5% 6.8 0.57/0.39 19000 64 HIL-012 (Ir(L6)hppz) Comp. 1 ET1:ET2/Al 28.0 12.6% 5.8 0.61/0.35 18000 65 HIL-012 (Ir(L9)pptz) Comp. 1 ET1:ET2/Al 26.0 15.3% 6.4 0.60/0.35 19000 66 HIL-012 (Ir(L11)fptz) Comp. 1 ET1:ET2/Al 26.3 11.0% 6.1 0.58/0.37 22000 67 HIL-012 (Ir(L14)mptz) Comp. 1 ET1:ET2/Al 22.6 13.3% 6.9 0.60/0.36 30000 68 HIL-012 (Ir(L16)pptz) Comp. 1 ET1:ET2/Al 21.9 11.4% 5.7 0.60/0.34 23000 69 HIL-012 (Ir(L19)pptz) Comp. 1 ET1:ET2/Al 22.9 10.0% 6.0 0.59/0.35 9000 70 HIL-012 (Ir(L22)hppz) Comp. 1 ET1:ET2/Al 22.7 11.0% 6.8 0.57/0.35 33000 71 HIL-012 (Ir(L26)mptz) Comp. 1 ET1:ET2/Al 24.4 13.7% 7.1 0.58/0.35 28780 72 HIL-012 (Ir(L35)bppz) Comp. 1 ET1:ET2/Al 28.3 12.1% 6.3 0.55/0.40 33437 74 HIL-012 (Ir(L41)pptz) Comp. 1 ET1:ET2/Al 24.2 12.6% 6.9 0.59/0.39 17234 75 HIL-012 (Ir(L44)mppz) Comp. 1 ET1:ET2/Al 21.9 10.9% 6.8 0.60/0.34 25384

(68) Again the new materials result in much improved devices, especially in terms of efficiency, lifetime and color.