Metal complexes, comprising carbene ligands having an O-substituted non-cyclometallated aryl group and their use in organic light emitting diodes

Abstract

Cyclometallated Ir complex comprising three N,N diaryl substituted carbene ligands, bearing substituents in the 2 position of the non-cyclometallated aryl ring; an organic electronic device, preferably an organic light-emitting diode (OLED), comprising at least one cyclometallated Ir complex as described above, a light-emitting layer comprising said cyclometallated Ir complex preferably as emitter material, preferably in combination with at least one host material, use of said cyclometallated Ir complex in an OLED and an apparatus selected from the group consisting of stationary visual display units, mobile visual display units, illumination units, units in items of clothing, units in handbags, units in accessories, units in furniture and units in wallpaper comprising said organic electronic device, preferably said OLED, or said light-emitting layer. The present invention further relates to a process for the preparation of said cyclometallated Ir complex.

Claims

1. A cyclometallated Ir complex of formula (I) ##STR00194## wherein A.sup.1 is CH or N; A.sup.2 is CR.sup.1 or N; A.sup.3 is CR.sup.2 or N; wherein in the case that A.sup.1 and/or A.sup.3 are N, A.sup.2 is CR.sup.1; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.6 and R.sup.7 are each independently hydrogen; deuterium; a linear or branched, substituted or unsubstituted alkyl radical having from 1 to 20 carbon atoms, optionally interrupted by at least one heteroatom, selected from O, S and N; a substituted or unsubstituted cycloalkyl radical having a total of from 3 to 30 carbon atoms; a substituted or unsubstituted heterocyclo alkyl radical, interrupted by at least one heteroatom selected from O, S and N and having a total of from 3 to 30 carbon atoms and/or heteroatoms; a substituted or unsubstituted aryl radical, having a total of from 6 to 30 carbon atoms; a substituted or unsubstituted heteroaryl radical, having a total of from 5 to 30 carbon atoms and/or heteroatoms, selected from O, S and N; or a group with donor or acceptor action; or R.sup.1 and R.sup.2, R.sup.3 and R.sup.4 and/or R.sup.6 and R.sup.7 may form, independently of each other, together with the carbon atoms to which they are bonded, a saturated or unsaturated or aromatic, optionally substituted ring, which is optionally interrupted by at least one heteroatom, selected from O, S and N, has a total of from 5 to 18 carbon atoms and/or heteroatoms, and may optionally be fused to at least one further optionally substituted saturated or unsaturated or aromatic ring, optionally interrupted by at least one heteroatom, selected from O, S and N, and having a total of from 5 to 18 carbon atoms and/or heteroatoms; R.sup.5 is a linear or branched, substituted or unsubstituted alkyl radical having from 1 to 20 carbon atoms, optionally interrupted by at least one heteroatom, selected from O, S and N; a substituted or unsubstituted cycloalkyl radical having a total of from 3 to 30 carbon atoms; a substituted or unsubstituted heterocyclo alkyl radical, interrupted by at least one heteroatom selected from O, S and N and having a total of from 3 to 30 carbon atoms and/or heteroatoms; a substituted or unsubstituted aryl radical, having a total of from 6 to 30 carbon atoms; a substituted or unsubstituted heteroaryl radical, having a total of from 5 to 30 carbon atoms and/or heteroatoms, selected from O, S and N; or a group with donor or acceptor action; X is CH, CD or N; Y is CR.sup.8 or N; R.sup.8 is hydrogen; deuterium; a linear or branched, substituted or unsubstituted alkyl radical having from 1 to 20 carbon atoms, optionally interrupted by at least one heteroatom, selected from O, S and N; a substituted or unsubstituted cycloalkyl radical having a total of from 3 to 30 carbon atoms; a substituted or unsubstituted heterocyclo alkyl radical, interrupted by at least one heteroatom selected from O, S and N and having a total of from 3 to 30 carbon atoms and/or heteroatoms; a substituted or unsubstituted aryl radical, having a total of from 6 to 30 carbon atoms; a substituted or unsubstituted heteroaryl radical, having a total of from 5 to 30 carbon atoms and/or heteroatoms, selected from O, S and N; or a group with donor or acceptor action, with the proviso that cyclometallated Ir complex of formula (I) is not ##STR00195##

2. The cyclometallated Ir complex according to claim 1, wherein the cyclometallated Ir complex of formula (I) is a cyclometallated Ir complex of the formula ##STR00196## wherein A.sup.1 is CH or N; A.sup.2 is CR.sup.1 or N; A.sup.3 is CR.sup.2 or N; wherein in the case that A.sup.1 and/or A.sup.3 are N, A.sup.2 is CR.sup.1; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.6 and R.sup.7 are each independently hydrogen; deuterium; a linear or branched, substituted or unsubstituted alkyl radical having from 1 to 20 carbon atoms, optionally interrupted by at least one heteroatom, selected from O, S and N; a substituted or unsubstituted cycloalkyl radical having a total of from 3 to 30 carbon atoms; a substituted or unsubstituted heterocyclo alkyl radical, interrupted by at least one heteroatom selected from O, S and N and having a total of from 3 to 30 carbon atoms and/or heteroatoms; a substituted or unsubstituted aryl radical, having a total of from 6 to 30 carbon atoms; a substituted or unsubstituted heteroaryl radical, having a total of from 5 to 30 carbon atoms and/or heteroatoms, selected from O, S and N; or a group with donor or acceptor action; or R.sup.1 and R.sup.2, R.sup.3 and R.sup.4 and/or R.sup.6 and R.sup.7 may form, independently of each other, together with the carbon atoms to which they are bonded, a saturated or unsaturated or aromatic, optionally substituted ring, which is optionally interrupted by at least one heteroatom, selected from O, S and N, has a total of from 5 to 18 carbon atoms and/or heteroatoms, and may optionally be fused to at least one further optionally substituted saturated or unsaturated or aromatic ring, optionally interrupted by at least one heteroatom, selected from O, S and N, and having a total of from 5 to 18 carbon atoms and/or heteroatoms; R.sup.5 is a linear or branched, substituted or unsubstituted alkyl radical having from 1 to 20 carbon atoms, optionally interrupted by at least one heteroatom, selected from O, S and N; a substituted or unsubstituted cycloalkyl radical having a total of from 3 to 30 carbon atoms; a substituted or unsubstituted heterocyclo alkyl radical, interrupted by at least one heteroatom selected from O, S and N and having a total of from 3 to 30 carbon atoms and/or heteroatoms; a substituted or unsubstituted aryl radical, having a total of from 6 to 30 carbon atoms; a substituted or unsubstituted heteroaryl radical, having a total of from 5 to 30 carbon atoms and/or heteroatoms, selected from O, S and N; or a group with donor or acceptor action; X is CH, CD or N and Y is CR.sup.8; or Y is N or CR.sup.8 and X is CH or CD; R.sup.8 is hydrogen; deuterium; a linear or branched, substituted or unsubstituted alkyl radical having from 1 to 20 carbon atoms, optionally interrupted by at least one heteroatom, selected from O, S and N; a substituted or unsubstituted cycloalkyl radical having a total of from 3 to 30 carbon atoms; a substituted or unsubstituted heterocyclo alkyl radical, interrupted by at least one heteroatom selected from O, S and N and having a total of from 3 to 30 carbon atoms and/or heteroatoms; a substituted or unsubstituted aryl radical, having a total of from 6 to 30 carbon atoms; a substituted or unsubstituted heteroaryl radical, having a total of from 5 to 30 carbon atoms and/or heteroatoms, selected from O, S and N; or a group with donor or acceptor action.

3. The cyclometallated Ir complex according to claim 1, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.6 and R.sup.7 are each independently hydrogen; deuterium; methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, iso-butyl, cyclopentyl, cyclohexyl, OCH.sub.3, OCF.sub.3; phenyl, pyridyl, pyrimidyl, pyrazinyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, benzofuranyl and benzothiophenyl wherein the aforementioned radicals may be unsubstituted or substituted by methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, iso-butyl, methoxy, CF.sub.3 or phenyl; or a group with donor or acceptor action, selected from F, CF.sub.3, CN and SiPh.sub.3; and R.sup.5 is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, iso-butyl, cyclopentyl, cyclohexyl, OCH.sub.3, OCF.sub.3; phenyl, pyridyl, pyrimidyl, pyrazinyl, wherein the aforementioned radicals may be substituted by methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, iso-butyl, methoxy or phenyl or unsubstituted; or a group with donor or acceptor action, selected from CF.sub.3 and CN.

4. The cyclometallated Ir complex according to claim 1, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.6 and R.sup.7 are each independently hydrogen; deuterium; methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, iso-butyl; phenyl, pyridyl, pyrimidyl, pyrazinyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, wherein the aforementioned radicals may be unsubstituted or substituted by methyl, ethyl, iso-propyl, tert-butyl, iso-butyl or methoxy; CF.sub.3 or CN; and R.sup.5 is methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl; phenyl, tolyl or pyridyl.

5. A cyclometallated Ir complex selected from the group consisting of: ##STR00197## ##STR00198## ##STR00199## ##STR00200## ##STR00201## ##STR00202## ##STR00203## ##STR00204## ##STR00205## ##STR00206## ##STR00207## ##STR00208## ##STR00209## ##STR00210## ##STR00211##

6. An organic electronic device comprising at least one cyclometallated Ir complex according to claim 1.

7. The organic electronic device according to claim 6, wherein the organic electronic device is selected from an organic light-emitting diode (OLED), a light-emitting electrochemical cell (LEEC), an organic photovoltaic cell (OPV) and an organic field-effect transistor (OFET).

8. The organic electronic device according to claim 6, wherein the cyclometallated Ir complex of formula (I) is employed in OLEDs or LEECs or in OPVs.

9. The organic electronic device according to claim 8, wherein the OLED comprises (a) an anode, (b) a cathode, (c) a light-emitting layer between the anode and the cathode, (d) optionally a hole transport layer between the light-emitting layer and the anode, wherein the cyclometallated Ir complex of formula (I) is present in the light-emitting layer and/orif presentin the hole transport layer of the OLED.

10. The organic electronic device according to claim 6, wherein the cyclometallated Ir complex of formula (I) is employed in combination with at least one host material.

11. A light-emitting layer comprising at least one cyclometallated Ir complex of formula (I) as defined in claim 1 as emitter material.

12. An organic light-emitting diode (OLED) comprising the cyclometallated Ir complex of formula (I) as defined in claim 1.

13. An apparatus comprising the organic electronic device according to claim 6, wherein the apparatus is selected from the group consisting of a stationary visual display unit; a mobile visual display unit; an illumination unit; a unit in items of clothing; a unit in handbags, a unit in accessories, a unit in furniture and a unit in wallpaper.

14. A process for preparing a cyclometallated Ir complex of formula (I) as defined in claim 1, by contacting suitable compounds comprising Ir with appropriate ligands or ligand precursors.

15. An organic electronic device comprising at least one cyclometallated Ir complex according to claim 5.

16. The organic electronic device according to claim 5, wherein the cyclometallated Ir complex is employed in OLEDs or LEECs or in OPVs.

17. The organic electronic device according to claim 15, wherein the OLED comprises (a) an anode, (b) a cathode, (c) a light-emitting layer between the anode and the cathode, (d) optionally a hole transport layer between the light-emitting layer and the anode, wherein the cyclometallated Ir complex is present in the light-emitting layer and/orif presentin the hole transport layer of the OLED.

18. A light-emitting layer comprising at least one cyclometallated Ir complex as defined in claim 5 as emitter material.

19. An apparatus comprising the organic electronic device according to claim 15, wherein the apparatus is selected from the group consisting of a stationary visual display unit; a mobile visual display unit; an illumination unit; a unit in items of clothing; a unit in handbags, a unit in accessories, a unit in furniture and a unit in wallpaper.

20. A process for preparing a cyclometallated Ir complex as defined in claim 5, by contacting suitable compounds comprising Ir with appropriate ligands or ligand precursors.

Description

EXAMPLES

(1) The examples which follow, more particularly the methods, materials, conditions, process parameters, apparatus and the like detailed in the examples, are intended to support the present invention, but not to restrict the scope of the present invention.

(2) All experiments are carried out in protective gas atmosphere.

(3) The percentages and ratios mentioned in the examples belowunless stated otherwiseare % by weight and weight ratios.

(4) A Synthesis of the Inventive Ir Complexes

(5) 1 Synthesis of

(6) ##STR00137##
1.1 Intermediate 1

(7) ##STR00138##

(8) 1-Phenylamino-2-chloropyrazine (the synthesis is described in the not yet published European patent application EP13178675.8) (11.8 g, 57.4 mmol) is dissolved in anhydrous THF (300 mL). o-Toluidine (7.39 g, 68.9 mmol), 2-(dicyclohexylphosphino)-3,6-dimethoxy-2,4,6-tri-Isopropyl-1,1-biphenyl (BrettPhos) (0.31 g, 0.57 mmol) and chloro[2-(dicyclohexylphosphino)-3,6-dimethoxy-2,4,6-tri-i-propyl-1,1-biphenyl][2-(2-aminoethyl)phenyl]palladium(I) (0.47 g, 0.57 mmol) are added. To the solution cesium carbonate (22.7 g, 68.9 mmol) is added. The suspension is stirred at 80 C. for 24 h. After cooling to room temperature, the suspension is filtered. The filtrate is reduced under vacuum and the residue is dissolved in 200 mL of hot acetonitrile. The hot solution is cooled to 20 C. and 200 mL of n-pentane is added. Then the mixture is cooled to 15 C. After 5 minutes stirring at this temperature the precipitate is filtered off and washed with cold n-pentane. The solid is dried at 30 C. under vacuum to give 11.0 g of the desired product. The acetonitrile/n-pentane filtrate is evaporated and the residue is dissolved in 100 mL of hot acetonitrile. The hot solution is cooled to 20 C. and 100 mL of n-pentane are added. Then the mixture is cooled to 15 C. After 5 minutes stirring at this temperature the precipitate is filtered off and washed with cold n-pentane to give 2.80 g of the desired product. The collected solids give 13.8 g of the desired product in 87% yield. .sup.1H-NMR (CD.sub.2Cl.sub.2): =2.17 (s, 3H), 6.03 (s, 1H), 6.32 (s, 1H), 6.99-7.07 (m, 2H), 7.17 (t, 1H), 7.22 (d, 1H), 7.31 (d, 4H), 7.35 (d, 1H), 7.74 (d, 2H).

(9) 1.2 Intermediate 2

(10) ##STR00139##

(11) Intermediate 1 (1.52 g, 5.50 mmol) is dissolved in 27.5 mL of hydrochloric acid in methanol (c=1 mol/L). The reaction is stirred at room temperature overnight. The resulting suspension is cooled to 0-5 C. and then it is filtered and washed first with the filtrate, then with petrol ether. The solid is dried at 60 C. under vacuum to give 1.49 g of the desired product (87% yield). .sup.1H-NMR (CD.sub.2Cl.sub.2): =2.25 (s, 3H), 7.08 (t, 1H), 7.25-7.32 (m, 3H), 7.35-7.39 (m, 4H), 7.52 (s, 1H), 7.87 (d, 2H), 9.9 (br. s, 1H), 10.3 (br. s, 1H).

(12) 1.3 Intermediate 3

(13) ##STR00140##

(14) Intermediate 2 (1.33 g, 4.26 mol) and molecular sieves (5 and 3 , 3 g each) are added in a flask. Then 28 mL of trimethylorthoformate are added. The mixture is purged with argon and then heated to reflux for 1.5 h. After cooling to room temperature, the mixture is evaporated under vacuum. Then the residue is dissolved in dichloromethane and evaporated again (3). The residue is directly used in the next step. .sup.1H-NMR (CD.sub.2Cl.sub.2): =2.27 (s, 3H), 3.20 (s, 3H), 7.13 (s, 1H), 7.18 (t, 1H), 7.30-7.40 (m, 5H), 7.41-7.47 (m, 3H), 8.03 (d, 2H).

(15) 1.4 Complex 1 (Fac Und Mer)

(16) ##STR00141##

(17) Intermediate 3 (1.36 g, 4.26 mmol) is dissolved in 40 mL of anhydrous o-xylene under argon. Then di--chloro-bis[(cycloocta-1,5-dien)iridium(I)] (0.29 g, 0.43 mmol) is added to the solution.

(18) After degassing the solution with argon flux, the reaction is heated up to 140 C. overnight. The solvent of the reaction mixture is removed and the residue is purified by column chromatography (silica). One fraction yields 140 mg of the fac isomer (15%). The solid obtained from another fraction is stirred in a solution of acetone/acetonitrile and precipitated by addition of acetone to yield 295 mg of the mer isomer (33%).

(19) fac isomer: .sup.1H-NMR (CD.sub.2Cl.sub.2): =0.68 (s, 9H), 6.49-6.55 (m, 6H), 6.66 (t, 3H), 6.77 (t, 3H), 6.87 (d, 3H), 7.05 (t, 3H), 7.84 (d, 3H), 8.07 (d, 3H), 8.24 (d, 3H), 8.44 (d, 3H).

(20) Photoluminescence (2% film in PMMA): .sub.max=475 nm; .sub.0=3.0 s; PLQY=93%.

(21) mer isomer: MALDI-MS: m/z=1047.228.

(22) Photoluminescence (2% film in PMMA): .sub.max=521 nm; .sub.0=1.2 s; PLQY=75%.

(23) 2 Synthesis of

(24) ##STR00142##
(Complex 2; Mer Complex)
2.1 Intermediate 1

(25) ##STR00143##

(26) 5,6-dichloropyridine-3-carboxylic acid (33 g, 0.17 mol) is dissolved in 310 mL of THF. To this solution thionyl chloride (26.2 mL, 0.22 mol) is added. Then 0.17 mL of DMF is added. The reaction mixture is stirred for 2.5 h at 50 C. After cooling to room temperature, the reaction mixture is poured into 390 mL of a concentrated ammonia solution (25%) and 500 mL of water. The mixture is cooled to 0 C. and stirred overnight to room temperature. The THF is reduced under vacuum, the aqueous solution is extracted with ethyl acetate. The organic layer is washed with water, followed by a sodium hydroxide solution (10%). After drying over anhydrous sodium sulfate the solvent is reduced. The residue is dried under vacuum to give 30.9 g of the desired product in 95% yield. .sup.1H-NMR (DMSO): =7.83 (s, 1H), 8.28 (s, 1H), 8.49 (s, 1H), 8.81 (s, 1H).

(27) 2.2 Intermediate 2

(28) ##STR00144##

(29) Intermediate 1 (8.4 g, 44 mmol) is suspended in 76 mL of thionyl chloride. The reaction mixture is stirred under reflux for 72 h. The solvent is reduced under vacuum and the residue is dissolved in chloroform. The organic layer is washed with water and dried over anhydrous sodium sulfate. After reducing the solvent under vacuum, the solid is first purified via column chromatography (reversed phase, eluent: acetonitrile/dichloromethane) and then crystallized in ethyl acetate to give the title product in 78% yield (5.95 g). .sup.1H-NMR (CDCl.sub.3): =8.05 (s, 1H), 8.60 (s, 1H).

(30) 2.3 Intermediate 3

(31) ##STR00145##

(32) Intermediate 2 (10.0 g, 58 mmol), 4-tert-butylphenylamine (9.5 g, 64 mmol) and 30 mL of diisopropylethylamine are suspended in 200 mL of dimethylacetamide under argon atmosphere. The suspension is heated to 120 C. and stirred overnight. After cooling to room temperature, the remaining liquid is removed and the residue is taken up in methylene chloride. The organic phase is sequentially washed with hydrochloric acid (5%), a saturated sodium hydrogen carbonate solution and finally with water. The organic layer is dried over anhydrous sodium sulfate. The remaining solution is filtered over silica, then the solvent is removed and the solid dried at 40 C. under vacuum. The yellow product is crystallized in ethyl acetate to give the title product as a white powder (15.5 g) in 93% yield. .sup.1H-NMR (400 MHz, CDCl.sub.3): =1.33 (s, 9H), 7.28 (br. s, 1H), 7.41 (d, 2H), 7.50 (d, 2H), 7.75 (d, 1H), 8.38 (d, 1H).

(33) 2.4 Intermediate 4

(34) ##STR00146##

(35) Intermediate 3 (13.2 g, 46.2 mmol) is suspended in 150 mL of THF. Then 8.94 g (64.7 mmol) potassium carbonate, 248 mg (1.16 mmol) 2-(dicyclohexylphosphino)-3,6-dimethoxy-2,4,6-tri-Isopropyl-1,1-biphenyl, 369 mg (1.16 mmol) chloro-[2-(dicyclohexylphosphino)-3,6-dimethoxy-2,4,6-tri-Isopropyl-1,1-biphenyl]-[2-(2-aminoethyl)phenyl]palladium(II) and 4.95 g (46.2 mmol) o-toluidine are added under argon atmosphere. The mixture is stirred for 48 h at 66 C. After cooling to room temperature, the reaction is diluted with 500 mL of methylene chloride. The organic phase is washed with water, then dried over anhydrous sodium sulfate and the solvents are removed. The residue is dissolved in methylene chloride and filtered over silica. After removing the solvent the brown oil is purified via column chromatography (silica, cyclohexane/ethyl acetate) and the desired product is obtained in 46% yield (7.52 g).

(36) 1H-NMR (400 MHz, CDCl.sub.3): =1.31 (s, 9H), 2.27 (s, 3H), 5.00 (s, 1H), 6.67 (d, 1H), 6.98 (t, 1H), 7.14 (t, 1H), 7.23 (d, 2H), 7.31 (s, 1H), 7.36 (d, 2H), 7.43 (d, 2H), 8.29 (d, 1H).

(37) 2.5 Intermediate 5

(38) ##STR00147##

(39) Intermediate 4 (3.15 g, 8.84 mmol) is dissolved in 107 mL of acetonitrile under argon atmosphere. The mixture is degassed with argon for 5 minutes and then cooled to 0 C. (Chlormethylene)dimethylammonium chloride (3.4 g, 26.5 mmol) is added. The mixture is stirred at 0-15 C. for 24 h. Then 3.98 g (26.5 mmol) sodium iodide is added at 0 C. to the reaction. The mixture is stirred at 0-12 C. overnight. The suspension is filtered and the residue is washed with cold acetonitrile. The filtrate is evaporated and dissolved in acetonitrile. This solution is washed with petrol ether. The acetonitrile phase is evaporated again to give an oily residue. The oil is mixed with a mixture of methyl tert-butyl ether and methylene chloride (3:1). A yellow precipitate is falling out. The suspension is stirred overnight, then filtered and washed with a mixture of methyl tert-butyl ether and methylene chloride (3:2). The residue is dried at 40 C. under vacuum to give 5.69 g of the desired product. .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2): =1.42 (s, 9H), 2.33 (s, 3H), 7.54-7.59 (m, 2H), 7.68 (t, 1H), 7.75 (d, 2H), 8.13 (d, 1H), 8.20 (t, 3H), 8.40 (s, 1H), 9.09 (s, 1H), 10.91 (s, 1H).

(40) 2.6 Intermediate 6

(41) ##STR00148##

(42) Intermediate 5 (2.8 g, 6.0 mmol) is dissolved in 60 mL of methanol under argon atmosphere. The mixture is cooled to 0 C. Sodium methanolate (325 mg, 6.0 mmol) is added to the solution. The mixture is stirred at 0 C. up to room temperature overnight. The resulting suspension is filtered and washed with cold methanol. The residue is dried at 40 C. under vacuum. The desired product is obtained as a solid in 55% yield (1.04 g). .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2): =1.35 (s, 9H), 2.25 (s, 3H), 3.19 (s, 3H), 6.42 (s, 1H), 7.08 (s, 1H), 7.33-7.41 (m, 4H), 7.48 (d, 2H), 7.84 (d, 2H), 7.93 (d, 1H).

(43) 2.7 Complex 2 (Mer Complex)

(44) ##STR00149##

(45) Intermediate 6 (0.97 g, 2.43 mmol) is added to a mixture of 58 mL of o-xylene and 163 mg (0.243 mmol) di--chloro-bis[(cycloocta-1,5-dien)iridium(I)]. After degassing the mixture with argon for 5 minutes, the reaction is heated up to 140 C. overnight. After cooling to room temperature, the reaction mixture is filtered and the residue is washed with o-xylene. The filtrate is evaporated under vacuum and the obtained residue is purified via column chromatography (silica, cyclohexane/ethyl acetate) to give 863 mg of the desired product. The solid is stirred in a solution of acetone/acetonitrile (1:1; 8 mL) overnight, filtered and washed with clean acetone/acetonitrile mixture (1:1) to give 495 mg of the desired product (79%). MALDI-MS: m/z=1289.501.

(46) Photoluminescence (2% film in PMMA): .sub.max=512 nm; .sub.0=0.9 s; PLQY=80%.

(47) 3 Synthesis of

(48) ##STR00150##
(Complex 3; Mer Complex)
3.1 Intermediate 1

(49) ##STR00151##

(50) 40.0 g (0.19 mol) 5-(trifluoromethyl)-2,3-dichloropyridine, 19.0 g (0.20 mol) aniline and 91.8 g (0.71 mol) diisopropylethylamine are dissolved in 200 mL of DMA. The mixture is purged with argon for 10 minutes and then heated to 110 C. overnight. The orange solution is evaporated under vacuum and the residue is dried in vacuum at 80 C. for 1.5 h. The residue is heated in 250 mL of toluene and activated char coal. After filtration and evaporating the solvent, the residue is dissolved again in toluene and filtered over silica. The filtrate is again evaporated under vacuum, then dissolved in dichloromethane and filtered. The yellow solution is concentrated and dried to give 13.1 g of the desired product in 26% yield. .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2): =7.13 (t, 1H), 7.29 (br. s, 1H), 7.36 (t, 2H), 7.64 (d, 2H), 7.80 (d, 1H), 8.36 (d, 1H).

(51) 3.2 Intermediate 2

(52) ##STR00152##

(53) 8.80 g (63.7 mmol) potassium carbonate, 5.45 g (50.9 mmol) o-toluidine, 0.61 g (1.14 mmol) 2-(dicyclohexylphosphino)-3,6-dimethoxy-2,4,6-triisopropyl-1,1-biphenyl and 0.91 g (1.14 mmol) chloro[2-(dicyclohexylphosphino)-3,6-dimethoxy-2,4,6-tri-i-propyl-1,1-biphenyl][2-(2-aminoethyl)phenyl]palladium(II) are added to a solution of intermediate 1 (13.0 g, 47.7 mmol) in 500 mL of THF. The reaction mixture is degassed with argon and then heated to reflux overnight. After cooling to room temperature, the suspension is filtered and washed with dichloromethane. The filtrate is concentrated. The residue is dissolved in toluene and filtered over 7 cm silica column to give 13.7 g of the product in 83% yield. .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2): =2.29 (s, 3H), 5.10 (s, 1H), 6.64-6.69 (m, 1H), 6.91-7.42 (m, 8H), 7.54-7.59 (m, 2H), 8.29 (s, 1H).

(54) 3.3 Intermediate 3

(55) ##STR00153##

(56) Intermediate 2 (13.7 g, 39.8 mmol) is suspended in 50 mL of toluene. To this mixture 20 mL of hydrochloric acid (32%) are added. After 10 minutes the suspension is diluted with 50 mL of toluene and the reaction is stirred overnight at room temperature. The suspension is filtered and washed with toluene. The residue is dried at 50 C. under vacuum to give 12.4 g of the desired product in 82% yield. .sup.1H-NMR (400 MHz, DMSO): =2.19 (s, 3H), 6.81 (s, 1H), 6.99-7.09 (m, 3H), 7.21 (t, 1H), 7.29 (d, 1H), 7.35 (t, 2H), 7.75 (d, 2H), 8.00 (s, 1H), 9.02 (br. s, 1H).

(57) 3.4 Intermediate 4

(58) ##STR00154##

(59) Intermediate 3 (12.0 g, 31.6 mmol) is suspended in 120 mL of trimethylorthoformate. The suspension is degassed with argon and then heated to 120 C. overnight. The orange solution is concentrated under vacuum to give 12.2 g of a brown oil which is used without further purification. .sup.1H-NMR (400 MHz, DMSO): =2.26 (s, 3H), 3.10 (s, 3H), 6.40 (s, 1H), 7.22 (t, 1H), 7.35-7.61 (m, 7H), 7.93 (s, 1H), 8.04 (d, 2H).

(60) 3.5 Complex 3 (Mer Complex)

(61) ##STR00155##

(62) Intermediate 4 (2.48 g, 6.44 mmol) is dissolved in 60 ml xylene. Molecular sieve (3 , 2.5 g) and then di--chloro-bis[(cycloocta-1,5-dien)iridium(I)] (432 mg, 0.643 mmol) are added to the solution. After degassing the solution with argon for 30 minutes, the reaction is stirred overnight at 120 C. After cooling to room temperature, the solid residues are removed by filtration and washed with dichloromethane. The solvent is removed and the residue is dissolved in toluene. The solution is stirred overnight. The precipitate is filtered off and the filtrate is concentrated under vacuum. The residue is purified via column chromatography (silica, cyclohexane/ethyl acetate). The resulting product is stirred in MTBE overnight, then filtered and dried. The product is obtained as a yellow solid in 49% yield (780 mg).

(63) Photoluminescence (2% film in PMMA): .sub.max=488 nm; .sub.0=0.9 s; PLQY=91%.

(64) 4 Synthesis of

(65) ##STR00156##
(Complex 4, Mer Complex)
4.1 Intermediate 1

(66) ##STR00157##

(67) 2-Chloro-3-iodopyridine (4.22 g, 17.6 mmol) is dissolved in toluene (50 mL) and degassed under argon flux. Then palladium(II)acetate (117 mg, 0.52 mmol), (R)-BINAP (333 mg, 0.53 mmol), cesium carbonate (5.38 g, 16.5 mmol) and o-toluidine (1.90 g, 17.7 mmol) are added. The mixture is heated to reflux and stirred for 72 h. After cooling to room temperature, the reaction mixture is filtered and the filtrate is concentrated under vacuum. The residue is purified by column chromatography (silica, eluent: toluene). The product is obtained in 73% yield (2.81 g). .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2): =2.24 (s, 3H), 5.94 (s, 1H), 7.05 (d, 2H), 7.12 (m, 1H), 7.22 (d, 2H), 7.29 (d, 1H), 7.78 (t, 1H).

(68) 4.2 Intermediate 2

(69) ##STR00158##

(70) Intermediate 1 (1.80 g, 8.23 mmol) is dissolved in toluene (42 mL) and degassed with an argon flux. Then tris(dibenzylidenacetone)dipalladium(0) (113 mg, 0.12 mmol), (R)-BINAP (234 mg, 0.38 mmol), sodium tert-butoxide (1.15 g, 12.0 mmol) and aniline (0.92 g, 9.88 mmol) are added. The suspension is heated to reflux and stirred for 3 d. After cooling to room temperature, the reaction mixture is filtered and the residue is washed with dichloromethane. The filtrate is concentrated under vacuum. Then the residue is dissolved in dichloromethane and silica is added to the solution, till the color of the overlaying solvent is orange. The mixture is filtered with dichloromethane over a layer of silica and the product is obtained in 92% yield (2.08 g). .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2): =2.29 (s, 3H), 5.07 (s, 1H), 6.61 (d, 1H), 6.78 (q, 1H), 6.85 (t, 1H), 6.91 (s, 1H), 6.96 (t, 1H), 7.05 (t, 1H), 7.19 (d, 1H), 7.27 (t, 3H), 7.53 (d, 2H), 8.05 (d, 1H).

(71) 4.3 Intermediate 3

(72) ##STR00159##

(73) Intermediate 2 (1.41 g, 5.12 mmol) and ammonium iodide (0.78 g, 5.38 mmol) are suspended in triethylorthoformate (8.5 mL) under argon. The mixture is heated to 80 C. and stirred for 3 d. The formed suspension is filtered and the product is obtained in 52% yield (1.11 g). .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2): =2.31 (s, 3H), 7.58 (m, 2H), 7.71 (m, 5H), 7.89 (d, 1H), 7.96 (d, 1H), 8.32 (d, 2H), 8.89 (d, 1H), 11.15 (s, 1H).

(74) 4.4 Complex 4 (Mer Complex)

(75) ##STR00160##

(76) Intermediate 3 (300 mg, 0.93 mmol) and molecular sieve 3 (4 g) are suspended in anhydrous 1,4-dioxane (20 mL). The suspension is degassed with argon flux and then silver oxide (163 mg, 0.70 mmol) is added. The reaction is stirred in the dark at room temperature for 20 h. Then a degassed solution of di--chloro-bis[(cycloocta-1,5-dien)iridium(I)] (63 mg, 0.09 mmol) in anhydrous o-xylene (20 mL) is added to the suspension. The mixture is heated to 150 C. and the 1,4-dioxane is distilled off. The resulting suspension is stirred at reflux over the weekend. The reaction mixture is filtered over a thin layer of silica and the residue is washed with o-xylene. The received filtrate is concentrated under vacuum and purified by column chromatography (silica, eluent:cyclohexane/ethyl acetate). The product is obtained in 26% yield (52 mg). MALDI-MS: m/z=1043,588.

(77) Photoluminescence (2% film in PMMA): .sub.max=453 nm; .sub.0=0.9 s; PLQY=72%.

(78) Synthesis of

(79) ##STR00161##
(Complex 5)
5.1 Intermediate 1

(80) ##STR00162##
4-Bromo-2-methylaniline (20.0 g, 0.11 mol), phenylboronic acid (19.8 g, 0.16 mol) and Pd(dppf)Cl.sub.2*CH.sub.2Cl.sub.2 (4.4 g, 5.4 mmol) are suspended in toluene (1000 mL) under argon atmosphere. Then a 3 M sodium hydroxide solution (108 mL) is added dropwise to the suspension.

(81) The mixture is heated to 90 C. and stirred overnight. After cooling to room temperature the reaction mixture is filtered over a layer of celite and the filtrate is concentrated under vacuum. The residue is dissolved in dichloromethane and extracted with water and a saturated sodium hydrogen carbonate solution. The organic layer is dried over sodium sulfate and the solvent is removed. The remaining brown oil is purified by column chromatography (silica, eluent:cyclohexane/ethyl acetate) to obtain the product in 66% yield (13.1 g). .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2): =2.21 (s, 3H), 3.70 (s, 2H), 6.72 (d, 1H), 7.25 (m, 2H), 7.31 (s, 1H), 7.37 (t, 2H), 7.53 (q, 2H).

(82) 5.2 Intermediate 2

(83) ##STR00163##

(84) 1-Phenylamino-2-chloropyrazine (14.6 g, 0.071 mol) is suspended in tetrahydrofuran (300 mL) under argon atmosphere. Then 2-(dicyclohexylphosphino)-3,6-dimethoxy-2,4,6-tri-Isopropyl-1,1-biphenyl (BrettPhos) (389 mg, 0.71 mmol) is added and stirred until it is solved. The same procedure is done with chloro[2-(dicyclohexylphosphino)-3,6-dimethoxy-2,4,6-tri-i-propyl-1,1-biphenyl][2-(2-aminoethyl)phenyl]palladium(II) (579 mg, 0.71 mmol). Then cesium carbonate (27.8 g, 0.085 mol) and intermediate 1 (13.0 g, 0.071 mol) are added to the solution. The suspension is heated to 78 C. and stirred for 22 h. After cooling to room temperature the mixture is filtered under vacuum and the residue washed with tetrahydrofuran. The concentrated filtrate yields 26.1 g product which is used for the next step without further purification. .sup.1H-NMR (400 MHz, DMSO): =2.24 (s, 3H), 6.99 (t, 1H), 7.33 (q, 3H), 7.47 (m, 5H), 7.54 (d, 1H), 7.56 (s, 1H), 7.68 (d, 2H), 7.72 (d, 2H), 8.074 (s, 1H), 8.513 (s, 1H).

(85) 5.3 Intermediate 3

(86) ##STR00164##

(87) Intermediate 2 (1.5 g, 4.25 mmol) is suspended in 32% hydrochloric acid (40 mL) and stirred at room temperature overnight. Then water (40 mL) is added and the mixture is stirred at room temperature for 2 d. The suspension is filtered and the solid is washed with diethyl ether and dried in vacuum. The filtrate is concentrated under vacuum, dissolved in methanol and precipitated with water. The precipitate is filtered, washed with diethyl ether and also dried in a vacuum oven. The combined residues give 1.63 g product in 98% yield. .sup.1H-NMR (400 MHz, DMSO): =2.26 (s, 3H), 7.02 (t, 1H), 7.35 (q, 3H), 7.45 (m, 4H), 7.53 (q, 2H), 7.59 (d, 1H), 7.69 (d, 2H), 7.76 (d, 2H), 8.63 (s, 1H), 8.87 (d, 2H).

(88) 5.4 Intermediate 4

(89) ##STR00165##

(90) Intermediate 3 (1.97 g, 5.1 mmol) is dissolved in triethyl orthoformate (50 mL) under argon atmosphere. The mixture is heated to 100 C. and stirred for 1 h. The solution is diluted with dichloromethane and the solvent is evaporated under vacuum. The resulting solid (1.97 g) is used for the next step without further purification. .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2): =1.09 (t, 3H), 2.34 (s, 3H), 3.37-3.44 (m, 1H), 3.53-3.62 (m, 1H), 7.15 (s, 1H), 7.18 (t, 1H), 7.35-7.40 (m, 2H), 7.41-7.49 (m, 6H), 7.56 (dd, 1H), 7.61 (s, 1H), 7.64 (d, 2H), 8.05 (d, 2H).

(91) 5.5 Complex 5 (Fac Und Mer)

(92) ##STR00166##

(93) Intermediate 4 (1.97 g, 4.8 mmol) and di--chloro-bis[(cycloocta-1,5-dien)iridium(I)] (324 mg, 0.48 mmol) are suspended in anhydrous o-xylene (138 mL) and the suspension is degassed under argon flux. The mixture is heated to 140 C. and stirred overnight. The suspension is cooled to room temperature and the solid is filtered off. The filtrate is concentrated and the residue is purified by column chromatography (eluent:cyclohexane/dichloromethane). The solid of one fraction is stirred in a mixture of acetone/acetonitrile 1:1 to yield 99 mg of the fac isomer (8%). Another fraction is purified further by stirring in a mixture of acetone/acetonitrile 1:1 to yield 410 mg of the mer isomer (33%).

(94) fac isomer: .sup.1H-NMR (CD.sub.2Cl.sub.2): =0.77 (s, 9H), 6.48 (dd, 3H), 6.65 (dt, 3H), 7.06 (dt, 3H), 7.22-7.38 (m, 21H), 7.70 (d, 3H), 7.80 (d, 3H), 8.10 (d, 3H), 8.50 (d, 3H).

(95) Photoluminescence (2% film in PMMA): .sub.max=471 nm; .sub.0=3.7 s; PLQY=90%.

(96) mer isomer: Photoluminescence (2% film in PMMA): .sub.max=521 nm; .sub.0=1.1 s; PLQY=70%.

(97) 6 Synthesis of

(98) ##STR00167##
(Complex 6; Mer Complex)
6.1 Intermediate 1

(99) ##STR00168##

(100) 4-bromo-2-fluoronitrobenzene (1.0 g, 4.3 mmol) and aniline (490 mg, 5.2 mmol) are suspended in 1-methyl-2-pyrrolidon (2 mL). The mixture is purged with argon, then heated to 50 C. for 15 h. Additional aniline (350 mg, 3.7 mmol) is added to the reaction. The mixture is stirred at 50 C. for 15 h. After cooling to room temperature the mixture is diluted with 2 mL of methanol and 15 mL of water. The obtained precipitate is filtered and washed twice with methanol/water-solution (2:1). The solid is dried at 60 C. under vacuum. The desired product is obtained in 88% yield (1.1 g). .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2): =6.89 (d, 1H), 7.32-7.26 (m, 3H), 7.33 (s, 1H), 7.46 (t, 2H), 8.05 (d, 1H), 9.47 (s, 1H).

(101) 6.2 Intermediate 2

(102) ##STR00169##

(103) Intermediate 1 (1.0 g, 4.3 mmol) is suspended in 10 mL of dioxane and 2.5 mL of 5N NaOH solution. The mixture is purged with argon. Then 2-methylphenylboronic acid (1.09 g, 7.86 mmol) and Pd[P(tBu).sub.3].sub.2 (75 mg, 0.14 mmol) are added under argon atmosphere. The reaction mixture is heated to 85 C. and stirred for 15 h. After cooling to room temperature the reaction mixture is filtered over celite and washed with dichloromethane. The combined organic layers are washed with water, dried over anhydrous sodium sulphate and concentrated under vacuum. The residue is purified via column chromatography (silica, eluent: n-hexane/THF) and the desired product is obtained in 93% yield (1.2 g). .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2): =2.24 (s, 3H), 6.76 (d, 1H), 7.13 (s, 1H), 7.15 (d, 1H), 7.18-7.26 (m, 4H), 7.31 (d, 2H), 7.40 (t, 2H), 8.22 (d, 1H), 9.54 (s, 1H).

(104) 6.3 Intermediate 3

(105) ##STR00170##

(106) Intermediate 2 (736 mg, 2.42 mmol) is suspended in 30 mL of methanol. After adding 10 mL of THF the solid is solved in an ultrasonic bath. Saturated ammonia chloride solution (4 mL) is added and zinc powder (380 mg, 5.8 mmol) is added at room temperature. The yellow reaction mixture is stirred at room temperature for 18 h. Then 20 mL of THF and additional zinc powder (380 mg, 5.8 mmol) are added. After keeping the reaction mixture in an ultrasonic bath, the mixture is stirred at room temperature overnight. The solvent is evaporated and the residue is diluted in dichloromethane (50 mL). The suspension is filtered over celite and washed with dichloromethane. The filtrate is washed with water and then dried over Na.sub.2SO.sub.4. The desired product is obtained as a yellow solid (97%, 640 mg). .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2): =2.28 (s, 3H), 3.84 (s, 2H), 5.26 (s, 1H), 6.79 (m, 3H), 6.85 (d, 1H), 6.96 (d, 1H), 7.10 (s, 1H), 7.15-7.25 (m, 6H).

(107) 6.4 Intermediate 4

(108) ##STR00171##

(109) Intermediate 3 (0.27 g, 1.0 mmol), 2-bromotoluene (0.17 g, 1.0 mmol) and potassium carbonate (0.19 g, 1.4 mmol) in t-butanol (10 mL) is added 2-(Dicyclohexylphosphino)-3,6-dimethoxy-2,4,6-tri-Isopropyl-1,1-biphenyl (0.027 g, 0.05 mmol) and 2-Chloro-[2-(Dicyclohexylphosphino)-3,6-dimethoxy-2,4,6-tri-Isopropyl-1,1-biphenyl]-[2-(2-aminoethyl)phenyl]palladium(II) (0.040 g, 0.05 mmol) under argon atmosphere. The reaction mixture is stirred at 40 C. for 30 minutes, then heated to 80 C. and stirred overnight. After cooling to room temperature the reaction mixture is diluted with dichloromethane and water. After separation of the layers, the organic layer is washed several times with water and then dried with anhydrous sodium sulphate. The organic layers are concentrated and the residue is purified via column chromatography (silica, eluent: cyclohexane/ethyl acetate). The desired product is obtained in 97% yield (0.35 g).

(110) 6.5 Intermediate 5

(111) ##STR00172##

(112) Intermediate 4 (2.0 g, 5.5 mmol) is suspended in 70 mL of acetonitrile and purged with argon. Then the mixture is cooled to 0 C. (Chlormethyl)-dimethylammonium chloride (2.11 g, 16.5 mmol) is added. The resulting solution is allowed to reach room temperature overnight while stirring. The mixture is cooled again to 0 C. and sodium iodide (2.47 g, 16.5 mmol), suspended in 10 mL of acetonitrile, is added. A yellow precipitate is forming. After stirring at 0 C. for 5 h the suspension is filtered and the solid is washed with acetonitrile. The filtrate is diluted with dichloromethane. The combined organic layers are washed several times with water, then dried over Na.sub.2SO.sub.4 and concentrated under vacuum. The desired product is obtained as a yellow solid in 95% yield (2.6 g). .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2): =2.26 (s, 3H), 2.35 (s, 3H), 7.21-7.32 (m, 4H), 7.49 (d, 1H), 7.52-7.61 (m, 2H), 7.62-7.77 (m, 6H), 7.93 (d, 1H), 8.10 (d, 2H), 10.84 (s, 1H).

(113) 6.6 Intermediate 6

(114) ##STR00173##

(115) Intermediate 5 (1.0 g, 2.0 mmol) is solved in 60 mL of methanol and cooled to 0 C. Sodium methanolate (0.44 g, 2.4 mmol) in methanol is added dropwise. The mixture is stirred and allowed to reach room temperature overnight. The obtained suspension is cooled to 0 C. and filtered. The solid is washed two times with cold methanol and is then dried at 40 C. overnight. The desired product is obtained as a colorless solid (0.63 g, 64%). .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2): =2.29 (s, 3H), 2.33 (s, 3H), 3.23 (s, 3H), 6.38 (d, 1H), 6.68 (d, 1H), 6.81 (s, 1H), 7.06-7.49 (m, 11H), 7.56 (d, 2H).

(116) 6.7 Complex 6 (Mer Isomer)

(117) ##STR00174##

(118) Intermediate 6 (0.61 g, 1.5 mmol) is solved in o-xylene (78 mL). Molecular sieves (5 and 3 , 0.5 g each), chloro([1,5]cyclooctadien)Iridium(I)-dimer (0.17 g, 0.25 mmol) and DMF (13 mL) are added to the solution. After purging with an argon flux for 5 minutes, the reaction is heated at 140 C. for 15 h. After cooling to room temperature, the solids are removed by filtration and washed with o-xylene. The filtrate is concentrated under vacuum and then purified several times via column chromatography (silica, eluent: 1 cyclohexane/dichloromethane; 2 toluene). The desired product is obtained in 4 isomers. MALDI-MS 1312

(119) Photoluminescence (2% film in PMMA): .sub.max=428 nm; .sub.0=3.8 s; PLQY=42%.

(120) 7 Synthesis of

(121) ##STR00175##
(Complex 7; Mer Complex)
7.1 Intermediate 1

(122) ##STR00176##

(123) Under argon atmosphere N-phenyl-o-diaminobenzene (23.0 g, 122 mmol) and 2-brombiphenyl (29.1 g, 122 mmol) are suspended in toluene (275 mL). To this mixture xantphos (97%, 4.38 g, 7.34 mmol), Pd.sub.2(dba).sub.3 (2.24 g, 2.45 mmol), NaOzBu (11.8 g, 122 mmol) and water (1.5 mL) are added. The reaction is stirred at reflux overnight. The reaction is cooled to room temperature and purged with argon for 10 minutes. Then additional xantphos (2.18 g, 3.67 mmol) and Pd.sub.2(dba).sub.3 (1.11 g, 1.22 mmol) are added. The reaction is heated to reflux and stirred overnight. Then the reaction is again cooled to room temperature and purged with argon for 10 minutes. Then additional xantphos (2.18 g, 3.67 mmol) and Pd.sub.2(dba).sub.3 (1.11 g, 1.22 mmol) are added for the third time. The reaction is heated to reflux and stirred overnight. After cooling to room temperature the suspension is filtered under vacuum and washed with toluene. The filtrate is concentrated under vacuum. The residue is purified via column chromatography (silica, cyclohexane/dichloromethane) and the desired product is obtained in 94% yield (39 g). .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2): =5.68 (d, 2H), 6.81-6.90 (m, 3H), 7.00 (m, 3H), 7.02 (d, 1H), 7.13-7.25 (q, 6H), 7.27-7.44 (m, 5H).

(124) 7.2 Intermediate 2

(125) ##STR00177##

(126) Intermediate 1 (600 mg, 1.8 mmol) is suspended in 5 mL of triethylorthoformiate under argon atmosphere. To this mixture NH.sub.4BF.sub.4 (190 mg, 1.8 mmol) is added. The reaction is kept under reflux for 15 h. After cooling to room temperature the reaction mixture is diluted with CH.sub.2Cl.sub.2 and evaporated under vacuum. The brown residue is suspended in MeO tBu and ethyl acetate (10 mL, each) and is filtered and washed with MeO tBu. The product is dried at 45 C. for 15 h to give a solid (93%, 720 g). .sup.1H-NMR (400 MHz, DMSO): =7.16-7.32 (m, 5H), 7.44 (d, 1H), 7.56 (t, 1H), 7.65 (t, 1H), 7.70-7.94 (m, 9H), 7.99 (d, 1H), 10.51 (s, 1H).

(127) 7.3 Complex 7 (Mer Isomer)

(128) ##STR00178##

(129) Tetrafluoroborate salt B (2.00 g, 4.61 mmol) is suspended in toluene (30 mL) and potassium hexamethyldisilizan (KHMDS, 0.5 M in toluene, 9.2 mL, 4.6 mmol) added dropwise over 25 min. The reaction mixture is stirred for 30 minutes at room temperature and then transferred dropwise within 20 minutes to a mixture of di--chloro-bis[(cycloocta-1,5-dien)-iridium(I)] (310 mg, 0.46 mmol) in toluene (30 mL). The reaction mixture is heated reflux for 18 h. After cooling to room temperature the suspension is filtered and the residue is washed with toluene. The combined organic layers are concentrated. The formed solid is dissolved in dichloromethane (20 mL) and ethanol (40 ml). Solvent is removed until a precipitate is formed, which is filtered and washed with ethanol. This procedure is repeated for a second time. Then the solid is suspended in THF (30 mL), the residue filtered and the filtrate is slightly concentrated to yield a second portion of solid, which both contain the meridional isomer of the complex (21%).

(130) Photoluminescence (2% film in PMMA): .sub.max=434 nm; .sub.0=17 s; PLQY=27%.

(131) 8 Synthesis of

(132) ##STR00179##
(Complex 8; Mer Complex)
8.1 Intermediate 1

(133) ##STR00180##

(134) In 36 mL of toluene 2-chloro-3-iodpyridine (1.4 g, 6.0 mmol) and (1.0 g, 5.7 mmol) 2-aminobiphenyl are added under argon atmosphere. The suspension is degassed 10 min with argon flux, then BINAP (112 mg, 0.18 mmol) and Pd(OAc).sub.2 (40 mg, 0.18 mmol) are added. The suspension is stirred a few minutes then cesium carbonate (9.7 g, 30 mmol) and triethyl amine (550 mg, 5.4 mmol) are added. The suspension is stirred for 5 minutes at room temperature and is then heated to reflux. The reaction is stirred for 4 h, then BINAP (112 mg, 0.18 mmol) and Pd(OAc).sub.2 (40 mg, 0.18 mmol) are added. After stirring over night at reflux, again BINAP (112 mg, 0.18 mmol) and Pd(OAc).sub.2 (40 mg, 0.18 mmol) are added. The reaction is stirred at reflux for 15 h. After cooling to room temperature, the suspension is filtered under vacuum and washed with toluene. The filtrate is concentrated to 3 mL. The residue is diluted with methanol. A brown precipitate is formed. After filtration the filtrate is concentrated. The residue is purified via column chromatography (silica, eluent:cyclohexane/dichloromethane) and the desired product is obtained in 77% yield (1.24 g). .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2): =6.10 (s, 1H), 7.03-7.10 (m, 1H), 7.15-7.24 (m, 1H), 7.32-7.48 (m, 9H), 7.79 (d, 1H).

(135) 8.2 Intermediate 2

(136) ##STR00181##

(137) Intermediate 1 (14.3 g, 50.8 mmol) and aniline (5.06 g, 54.3 mmol) are suspended in 175 mL of toluene. The mixture is degassed for 10 minutes with argon. Then BINAP (1.42 g, 2.28 mmol) and Pd.sub.2(dba).sub.3 (697 mg, 0.761 mmol) are added. The mixture is stirred a 5 minutes at room temperature. Then sodium tert-butylat (7.04 g, 71.1 mmol) is added. After stirring for 5 min at room temperature, the mixture is heated to reflux for 15 h. After cooling to room temperature the suspension is filtered and washed with toluene. The filtrate is concentrated. The residue is charged on celite and purified via column chromatography (silica, eluent toluene/ethyl acetate).

(138) The obtained product fractions are concentrated under reduced pressure. The solid is solved in dichloromethane and diluted with the same amount of methanol. After removing a part of the solvent a white precipitate is formed. The solid is filtered and washed with methanol. The desired product is obtained in 45% yield (7.76 g). .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2): =5.29 (s, 1H), 6.71 (d, 1H), 6.73-6.79 (m, 1H), 6.91-7.00 (m, 3H), 7.18 (t, 1H), 7.21-7.30 (q, 3H), 7.34-7.42 (m, 2H), 7.44-7.57 (m, 6H), 8.05 (d, 1H).

(139) 8.3 Intermediate 3

(140) ##STR00182##

(141) Intermediate 2 (7.70 g, 22.8 mmol) is suspended in 180 mL of hydrochloric acid (32%) at room temperature. The suspension is stirred at room temperature for 15 h. After treatment in an ultrasonic bath the mixture is stirred at 30 C. for 15 h. The suspension is filtered and the residue is washed with water. After drying at 45 C. the desired product is obtained in 96% yield (8.22 g). .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2): =4.38 (s, 1H), 6.69 (t, 1H), 6.96 (d, 1H), 7.20-7.35 (m, 7H), 7.35-7.44 (m, 4H), 7.45-7.56 (m, 4H), 8.08 (s, 1H), 10.09 (s, 1H),

(142) 8.4 Intermediate 4

(143) ##STR00183##

(144) Intermediate 3 (300 mg, 0.80 mmol) is suspended in 5 mL of triethyl ortho formiate. The reaction is heated to reflux and stirred for 15 h. After cooling to room temperature the suspension is filtered and washed a few times with ethyl acetate. The solid is dried at 45 C. under vacuum. The desired product is obtained in 84% yield (260 mg). .sup.1H-NMR (400 MHz, DMSO): =7.20-7.30 (m, 3H), 7.36 (d, 2H), 7.58-7.65 (q, 1H), 7.69-7.87 (m, 5H), 7.91 (t, 1H), 7.97 (t, 3H), 8.05 (d, 1H), 8.73 (d, 1H), 10.90 (s, 1H).

(145) 8.5 Complex 8 (Mer Isomer)

(146) ##STR00184##

(147) Intermediate 4 (3.38 g, 8.81 mmol) is suspended in 100 mL of anhydrous acetonitrile. The suspension is sparkled with argon flux for 10 minutes. Then silver oxide (1.03 g, 4.40 mmol) is added to the suspension and the reaction is stirred at room temperature for 18 h. The suspension is evaporated under reduced pressure. The solid is diluted with anhydrous o-xylene, then [Ir(COD)Cl].sub.2 (600 mg, 0.88 mmol) is added. Under an argon flux the reaction is heated to reflux for 18 h. After cooling to room temperature the brown reaction mixture is filtered under vacuum. The filtrate is evaporated and the residue is solved in a few mL of dichloromethane. This solution is diluted with 100 mL of ethanol, while a solid is formed. The precipitate is filtered and dried at 40 C. The mixture is purified via column chromatography (silica, eluent:cyclohexane/ethyl acetate) to yield the product as light yellow solid (0.53 g, 25%).

(148) Photoluminescence (2% film in PMMA): .sub.max=455 nm; .sub.0=1.3 s; PLQY=79%.

(149) 9 Synthesis of

(150) ##STR00185##
(Complex 9; Mer Complex)
9.1 Intermediate 1

(151) ##STR00186##

(152) 1-Amino-2-chloropyrazine (4.64 g, 22.6 mmol), 2-aminobiphenyl (4.72 g, 22.1 mmol) and cesium carbonate (8.82 g, 27.1 mmol) are suspended in 125 mL of THF under argon atmosphere. The suspension is degassed 10 minutes under argon flux. Then BrettPhos (250 mg, 0.45 mmol) and BrettPhos Palladacycle (370 mg, 0.45 mmol) are added. The suspension is stirred a few minutes at room temperature and is then heated to reflux for 18 h. After cooling to room temperature the reaction mixture is filtered over silica gel and washed with THF. The filtrate is evaporated under vacuum. The residue is stirred in 50 mL of acetonitrile. The suspension is filtered and the residue is washed twice with a few mL of acetonitrile. The solid is dried at 45 C. under reduced pressure. The solid is recrystallized (100 mL of acetonitrile, drying at 45 C.) to yield the product in 58% yield (4.48 g). .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2): =6.09 (s, 1H), 6.28 (s, 1H), 7.00 (t, 1H), 7.12 (t, 1H), 7.17 (d, 2H), 7.26 (t, 3H), 7.30-7.44 (m, 6H), 7.73 (d, 2H), 7.83 (d, 1H).

(153) 9.2 Intermediate 2

(154) ##STR00187##

(155) Intermediate 1 (1.00 g, 2.96 mmol) is suspended in 65 mL of hydrochloric acid (32%) at room temperature under nitrogen atmosphere. The mixture is stirred for 2 h at room temperature.

(156) Then the mixture is poured into 200 mL of water. The yellow precipitate is filtered and washed with water. After drying at 45 C. the desired product is obtained in 81% yield (0.81 g). .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2): =7.05-7.10 (m, 2H), 7.22-7.28 (m, 1H), 7.30-7.36 (m, 4H), 7.40 (d, 1H), 7.45-7.53 (m, 6H), 7.75 (d, 2H), 9.60 (br.s, 1H), 10.50 (br.s, 1H).

(157) 9.3 Intermediate 3

(158) ##STR00188##

(159) Intermediate 2 (975 mg, 2.27 mmol) is suspended in 42 mL of triethylorthoformate. The reaction is stirred for 1 h at room temperature, then 2 h at 50 C. and then 2 h at 70 C. Then the reaction is stirred at room temperature overnight. The reaction is concentrated under vacuum. The yellow residue is suspended in ethanol and sonificated. The solid is filtered and washed with anhydrous ethanol. After drying at 40 C. the desired product is obtained in 77% yield (0.8 g). .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2): =0.87 (t, 3H), 3.10-3.29 (m, 2H), 6.27 (s, 1H), 7.10 (t, 1H), 7.24-7.38 (m, 8H), 7.41 (d, 1H), 7.45-7.55 (m, 3H), 7.57-7.69 (d, 2H).

(160) 9.4 Complex 9 (Mer Isomer)

(161) ##STR00189##

(162) Intermediate 3 (660 mg, 1.67 mmol) and [Ir(COD)Cl].sub.2 (112.38 mg, 0.167 mmol) are suspended in 10 mL of anhydrous o-xylene. The reaction is sparkled with argon for 10 minutes and then heated to reflux for 18 h. After cooling to room temperature, the suspension is filtered and the filtrate is evaporated under vacuum. The brown residue is suspended in 10 mL of ethanol. The solid is filtered and washed with a few mL of ethanol. The solid is solved in dichloromethane and diluted with ethanol. The solution is evaporated under vacuum until a yellow precipitate is formed. This mixture is stirred at room temperature for 18 h. After filtering the suspension, the solid is washed with a few mL of ethanol. Then the product is purified via column chromatography (silica, eluent:cyclohexane/ethyl acetate). The product is isolated in 17% yield (69 mg).

(163) Maldi-MS 1235 (M+H)

(164) Photoluminescence (2% film in PMMA): .sub.max=521 nm; .sub.0=1.3 s; PLQY=63%.

(165) B Device Examples

(166) Device Examples: All Initial Performance Given at 1000 cd/m.sup.2

(167) 1 OLED Comprising Complex 1 as Emitter (E-X)

(168) 40 nm HIL Plexcore AJ20-1000-10 nm Ir(DPBIC).sub.3:MoO.sub.3 (50:50)10 nm Ir(DPBIC).sub.340 nm E-X/Ir(DPBIC).sub.3/SH-2 (10:10:80)5 nm SH-2-25 nm ETM-2:Liq (50:50)4 nm KF100 nm Al

(169) TABLE-US-00002 LT.sub.50 Voltage CurrEff LumEff EQE CIE [relative Example E-X [V] [cd/A] [lm/W] [%] x, y value].sup.1) Device Complex 5.3 44.7 26.4 13.9 0.34; 2500% 1.1 1 0.56 .sup.1)in view of the OLED in example 3 with complex 3 V as E-X
2 OLED Comprising Complex 1 or 2 as Emitter (E-X)

(170) 40 nm HIL Plexcore AJ20-1000-10 nm Ir(DPBIC).sub.3:MoO.sub.3 (90:10)10 nm Ir(DPBIC).sub.340 nm E-X/Ir(DPBIC).sub.3/SH-2 (10:10:80)5 nm SH-2-20 nm ETM-2:Liq (50:50)4 nm KF100 nm Al

(171) TABLE-US-00003 LT.sub.50 CurrEff LumEff EQE [relative Example E-X Voltage [V] [cd/A] [lm/W] [%] CIE x, y value].sup.1) Device 2.1 Complex 2 5.9 43.6 23.4 13.9 0.32;0.55 1500% Device 2.2 Complex 1 5.1 45.1 27.8 14.1 0.35;0.56 2200% .sup.1)in view of the OLED in example 3 with complex 3 V as E-X
3 OLED Comprising Complex 3 or 3V (Comparative Example) as Emitter (E-X)

(172) 40 nm HIL Plexcore AJ20-1000-10 nm Ir(DPBIC).sub.3:NDP-9 (99:1)10 nm Ir(DPBIC).sub.340 nm O18742/Ir(DPBIC).sub.3/SH-2 (10:10:80)5 nm SH-2-25 nm ETM-2:Liq (50:50)4 nm KF100 nm Al

(173) TABLE-US-00004 LT.sub.50 Voltage CurrEff LumEff EQE [relative Example E-X [V] [cd/A] [lm/W] [%] CIE x, y value] Device 3.1 Complex 3 V 4.8 41.3 27.1 17.2 0.21;0.38 100% (comp. (example) Device 3.2 Complex 3 4.5 42.1 29.1 15.8 0.23;0.44 490%
Comparative Complex 3V:

(174) ##STR00190##
(described in WO 2012/172482)
4 OLED Comprising Complexes 5 or 9 as Emitter (E-X)

(175) 40 nm HIL Plexcore AJ20-1000-10 nm Ir(DPBIC).sub.3:MoO.sub.3 (90:10)10 nm Ir(DPBIC).sub.340 nm E-X/Ir(DPBIC).sub.3/SH-2 (10:10:80)5 nm SH-2-20 nm ETM-2:Liq (50:50)4 nm KF100 nm Al

(176) Device 4.1: E-X: Complex 5

(177) Device 4.2: E-X: Complex 9

(178) Luminescent OLEDs with long lifetimes are obtained in examples 4.1 and 4.2.

(179) 5 OLED Comprising Complexes 4 or 8 as Emitter (E-X)

(180) 40 nm HIL Plexcore AJ20-1000-10 nm Ir(DPBIC).sub.3:MoO.sub.3 (90:10)10 nm Ir(DPBIC).sub.340 nm E-X/Ir(DPBIC).sub.3/SH-2 (10:10:80)5 nm Host-X20 nm ETM-2:Liq (50:50)4 nm KF100 nm Al

(181) Device 5.1: E-X: Complex 4

(182) Device 5.2: E-X: Complex 8

(183) Luminescent OLEDs with long lifetimes are obtained in examples 5.1 and 5.2.

(184) 6 OLED Comprising Complex 4 (Mer) or 4V (Comparative Example) as Emitter (E-X)

(185) ITO 120 nmIr(DPBIC).sub.3:MoO.sub.3 (90:10) 90 nmIr(DPBIC).sub.3 10 nmEmitter:Host-X (% Host-X=100%-% Emitter) 40 nmHost-X 5 nmETM-2:Liq (50:50) 25 nmKF 4 nmAlu

(186) TABLE-US-00005 LT.sub.50 % Voltage CurrEff LumEff EQE [relative Emitter Emitter [V] [cd/A] [lm/W] [%] CIEx CIEy value] 4 V 30 5.22 16.46 9.91 12.65 0.152 0.167 100% 4 30 5.35 12.86 7.55 8.72 0.161 0.190 367% 4 V 40 4.72 18.73 12.46 13.23 0.152 0.188 100% 4 40 5.25 12.68 7.58 7.65 0.167 0.229 300%

(187) Diaryl substituted, yet meridional, emitters show better lifetime in OLEDs than those with monoaryl-monoalkyl substituted meridional emitters.

(188) Comparative Complex 4V:

(189) ##STR00191##

(190) (mer Em-2, described in WO 2012/172482)

(191) Host-X in devices 5.1 and 5.2 and 6 has the following formula:

(192) ##STR00192##
(published in WO2009/003898, compound 4g),

(193) SH-2 and ETM-2 employed in the devices mentioned above have the following formulae:

(194) ##STR00193##