Organoiridium complex for organic electroluminescent elements

Abstract

The present invention provides an organometallic complex having a high quantum efficiency even in a polymer thin film as a emitting material for organic electroluminescent (EL) element. The present invention relates to an organoiridium complex for an organic electroluminescent element represented by the following Formula; wherein a CN ligand including two atomic groups (A.sup.1, A.sup.2), and a -diketone ligand in line symmetry having two tert-butyl-substituted phenyl groups are coordinated with an iridium atom. The organoiridium complex of the present invention has a high quantum efficiency even in a polymer thin film with respect to green to yellow electroluminescence. ##STR00001##
(In the aforementioned Formula, R.sup.1, R.sup.2, and R.sup.3 are each a tert-butyl group or a hydrogen atom, and have at least one tert-butyl group; they may bond each other to thereby form a saturated hydrocarbon ring, when having two tert-butyl groups; A.sup.1, A.sup.2 are each an unsaturated hydrocarbon ring, at least one is a single ring, and at least one is a heterocyclic ring).

Claims

1. An organoiridium complex for an organic electroluminescent element represented by Chemical Formula 1, wherein a CN ligand comprising two atomic groups (A.sup.1, A.sup.2), and a -diketone ligand in line symmetry having two tert-butyl-substituted phenyl groups are coordinated with an iridium atom, ##STR00051## wherein R.sup.1, R.sup.2, and R.sup.3 are each a tert-butyl group or a hydrogen atom, and two of R.sup.1, R.sup.2, and R.sup.3 are a tert-butyl group, and each phenyl ring of the -diketone is substituted with the two tert-butyl groups, wherein the two tert-butyl groups may bond each other to thereby form a saturated hydrocarbon ring, and wherein the -diketone ligand is represented by any of the formula in Chemical Formula 2; ##STR00052## wherein A.sup.1 is an unsubstituted or substituted benzene ring or an unsubstituted or substituted 6-membered heteroaryl ring, wherein the 6-membered heteroaryl ring contains one N as a heteroatom, and A.sup.2 is an unsubstituted or substituted 6-membered heteroaryl ring which contains one N as a heteroatom.

2. The organoiridium complex according to claim 1, wherein the A.sup.1 is substituted with a fluorine atom (F), a trifluoro (CF.sub.3) group, or a cyano (CN) group.

3. The organoiridium complex according to claim 1, wherein the A.sup.2 is substituted with a fluorine atom (F), a trifluoro (CF.sub.3) group, an alkyl group (R), or an alkoxy group (OR).

4. The organoiridium complex according to claim 1, wherein a PL quantum yield .sub.PL when 0.05 mmol/g doping is performed in a polymer thin film is 0.45 or more.

5. The organoiridium complex according to claim 1, wherein the light emission wavelength (.sub.PL) in the polymer thin film is 510 nm or more and 580 nm or less.

6. An organic electroluminescent element having an emission layer including the organoiridium complex according to claim 1.

7. The organoiridium complex according to claim 2, wherein the A.sup.2 is substituted with a fluorine atom (F), a trifluoro (CF.sub.3) group, an alkyl group (R), or an alkoxy group (OR).

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 shows the results of the light emission property of the organoiridium complex according to the embodiment.

(2) FIG. 2 is a cross-sectional schematic view of the organic EL element produced in the embodiment.

(3) FIG. 3A and FIG. 3B shows the results of the light emission property of the organic EL element according to the embodiment.

DESCRIPTION OF EMBODIMENTS

(4) Hereinafter, there will be explained the preferred embodiments according to the present invention.

(5) The following organoiridium complexes having the respective ligands were synthesized, and the emission spectrum of the obtained complexes was measured and the photoluminescence quantum yield was evaluated. X is a -diketone ligand in the conventional example. Each iridium complex was synthesized by reacting an iridium salt and a nitrogen-containing compound to obtain a precursor, and then reacting the precursor and the -diketone compound.

(6) ##STR00026##

(7) First, summary of the synthetic method of each of the aforementioned iridium complexes is explained. Firstly, each of the -diketone compounds and each of the CN ligands (1: 2,6-difluoro-2,3-bipyridine), (2: 2-(3,5-bis(trifluoromethyl)phenyl)pyridine), (3: 2-(2,4-bis(trifluoromethyl)phenyl)pyridine) was synthesized. Then, each of the CN ligands was reacted respectively with iridium chloride to synthesize precursors (1), (2) and (3). Each iridium complex described above was obtained by reacting each precursor with the -diketone compound.

(8) All of the starting materials, the reagents and solvents used for the synthesis were those having commercially available reagent grades without purification. Also with respect to dibenzoylmethane (-diketone (X)), the commercially available compound was used as it was for the complex synthesis. The commercially available dehydrated THF was used as the dry THF as it was. In addition, a spherical silica gel (neutral) manufactured by KANTO CHEMICAL CO., INC. was used as a filler to be used for a column chromatography.

(9) A proton nuclear magnetic resonance (.sup.1H NMR) spectrum and a mass analysis (mass (MS) spectrum) were used for identification of the synthesized complexes. Jeol JNM-ECX400 spectrophotometer (400 MHz) or Jeol JNM-ECS400 spectrophotometer (400 MHz) was used for measurement of the .sup.1H NMR spectrum. The MS spectrum was measured by subjecting a sample ionized by an electro-spray ionization method (ESI method), or a matrix-assisted laser desorption ionization method (MALDI method) to the time-of-flight (TOF) type mass spectrometry (ESI-TOF-MS and MALDI-TOF-MS spectrum). Note that, in the MALDI-TOF-MS spectrum, -cyano-4-hydroxycinnamic acid (CHCA) was used as a matrix. For the ESI-TOF-MS measurement, Jeol JML-T100LP mass spectrometry analyzer was used, and for the MALDI-TOF-MS measurement, Shimadzu-Kratos AXIMA-CFR PLUS TOF Mass mass spectrometry analyzer was used. Elemental analysis was performed by J-Science MICRO CORDER JM10 analysis machine by using acetanilide as a standard substance.

Synthesis of -Diketone Compound (A)

(10) After methyl 3,5-di(tert-butyl)benzoate and 3,5-di(tert-butyl)acetophenone were synthesized from 3,5-di(tert-butyl)benzoic acid, the -diketone compound (A) was obtained by the synthetic reaction using these two compounds.

Synthesis of methyl 3,5-di(tert-butyl)benzoate

(11) A concentrated sulfuric acid (0.9 mL) was dropped onto a mixture of 3,5-di(tert-butyl)benzoic acid (3.00 g, 12.8 mmol) and methanol (9 mL) under a nitrogen atmosphere at 0 C., followed by heating and refluxing the resulting substance for 1 hour with stirring. After being allowed to cool, chloroform (100 mL) was added, and further water (100 mL) was added, with the result that an organic layer was separated by shaking in a separating funnel. After repeating this procedure again, the separated organic layers were combined into one. After further washing the organic layer with a saturated aqueous sodium bicarbonate solution (50 mL) and a saturated saline (50 mL), the organic layer was then dried by addition of an appropriate amount of anhydrous magnesium sulfate. After removal of the magnesium sulfate by filtration, methyl 3,5-di(tert-butyl)benzoate was obtained by distilling the solvent with an evaporator, and by drying the residue in a desiccator under a reduced pressure. The obtained compound was a white solid, and a yield was 92% (2.92 g, 11.8 mmol). The properties (.sup.1H NMR, TOF MS) of the compound thus synthesized were as follows.

(12) .sup.1H NMR (CDCl.sub.3): 1.35 (s, 18H), 3.91 (s, 3H), 7.62 (t, J=2.0 Hz, 1H), 7.89 (d, J=2.0 Hz, 2H)

(13) MALDI-TOF MS: m/z 249 ([M+H].sup.+)

(14) ##STR00027##

Synthesis of 3,5-di(tert-butyl)acetophenone

(15) 3,5-di(tert-t-butyl)benzoic acid (3.00 g, 12.8 mmol) was added to a dry tetrahydrofuran (120 mL), and was cooled to 0 C. or less with stirring under a nitrogen atmosphere. 3.0 M methyl lithium solution in diethoxymethane (15 mL) was dropped onto the mixture, and after raising the temperature to a room temperature, was stirred for 2 hours. After adding a 6 M hydrochloric acid to the reaction mixture to be acidic, extraction with chloroform (100 mL2) was carried out. The obtained organic layers were combined into one, and after washing with water (50 mL2), a saturated aqueous sodium bicarbonate solution (50 mL) and a saturated saline (50 mL), an appropriate amount of anhydrous magnesium sulfate was added for drying. After removal of the magnesium sulfate by filtration, 3,5-di(tert-butyl)acetophenone was obtained by distilling the solvent with an evaporator, and by purifying the residue with a silica gel column chromatography (development solvent; chloroform). The obtained compound was a colorless liquid, and a yield was 75% (2.23 g, 9.60 mmol). The properties of the thus obtained compound were as follows.

(16) .sup.1H NMR (CDCl.sub.3) 1.37 (s, 18H), 2.60 (s, 3H), 7.64 (t, J=1.6 Hz, 1H), 7.80 (d, J=1.6 Hz, 2H)

(17) MALDI-TOF MS: m/z 232 (M.sup.+)

(18) ##STR00028##

Synthesis of -Diketone Compound (A)

(19) Methyl 3,5-di(tert-butyl)bezoate (2.92 g, 11.8 mmol) and sodium hydride (60% oil dispersion; 1.27 g, 31.8 mmol) were added to a dry THF (23 mL), and were stirred at a room temperature under a nitrogen atmosphere. Then, a solution obtained by dissolving the 3,5-di(tert-butyl)acetophenone (2.23 g, 9.60 mmol) in a dry THF (23 mL) was dropped onto the resultant substance for 30 minutes. Subsequently, the obtained reaction mixture was stirred for 24 hours at 60 C. After being allowed to cool, and after adding a 1 M hydrochloric acid to be acidic, extraction with chloroform (100 mL2) was carried out. The obtained organic layers were combined into one, and after washing with water (50 mL2), a saturated aqueous sodium bicarbonate solution (50 mL) and a saturated saline (50 mL), an appropriate amount of anhydrous magnesium sulfate was added for drying. After removal of the magnesium sulfate by filtration, 1,3-bis(3,5-di-(tert-butyl)phenyl) propane-1,3-dion(-diketone A) was obtained by distilling the solvent with an evaporator, and by purifying the residue with a silica gel column chromatography (development solvent; chloroform). The obtained compound was an amber syrup substance, and a yield was 49% (2.12 g, 4.73 mmol). The properties of the thus obtained compound were as follows.

(20) .sup.1H NMR (CDCl.sub.3) 1.38 (s, 36H), 6.78 (s, 1H), 7.63 (t, J=2.0 Hz, 2H), 7.78 (d, J=2.0 Hz, 4H), 16.9 (brs, 1H)

(21) MALDI-TOF MS: m/z 449 ([M+H].sup.+)

(22) ##STR00029##

Synthesis of -Diketone Compound (B)

(23) The -diketone compound (B) was obtained by the synthetic reaction of 1,2,3,4-tetrahydro-1,1,4,4-tetramethylnaphthalene and malonyl chloride.

Synthesis of -Diketone Compound (B)

(24) 1,2,3,4-tetrahydro-1,1,4,4-tetramethylnaphthalene (5.00 g, 26.6 mmol), malonyl chloride (1.35 g, 9.58 mmol) and aluminum chloride (5.51 g, 41.3 mmol) were added to carbon disulfide (27 mL), and were heated and stirred at 50 C. Next, a cooled 2 mol/L hydrochloric acid (27 mL) was added, and after transferring to a separating funnel, extraction was carried out with chloroform. The organic layer was further washed with water, and after distilling the solvent with an evaporator, a concentrated hydrochloric acid (3.5 mL) and chloroform (35 mL) were added, and were then heated and refluxed for 9 hours. After being allowed to cool, the mixture was transferred to a separatory funnel, and was washed with water and a saturated saline. The solvent was distilled off with a rotary evaporator after drying the organic layer by using an anhydrous magnesium sulfate. The -diketone (B) was obtained in a yield of 39% (1.66 g, 3.74 mmol) by purifying the residue with a silica gel column chromatography (development solvent; ethyl acetate:hexane=1:2 (v/v)). The properties of the thus obtained compound were as follows.

(25) .sup.1H NMR (CDCl.sub.3): 1.30 (s, 12H), 1.34 (s, 12H), 1.71 (m, 8H), 6.76 (s, 1H), 7.40 (d, J=8.0 Hz, 2H), 7.68 (dd, J=8.0 and 2.0 Hz, 2H), 7.94 (d, J=2.0 Hz, 2H), 16.96 (brs, 1H)

(26) MALDI-TOF MS: m/z 445 ([M+H].sup.+)

(27) ##STR00030##

(28) Next, the CN ligands (1) to (4) were synthesized according to the following manner.

Synthesis of CN Ligand (1)

(29) In accordance with the following formula, a CN ligand (1) was obtained by reacting 2,6-difluoropyridineboronic acid with 2-bromopyridine. A mixture of 2,6-difluoropyridineboronic acid (2.08 g, 13.1 mmol), 2-bromopyridine (1.34 g, 8.48 mmol), THF (65 mL), water (26 mL), K.sub.2CO.sub.3 (1.51 g, 10.9 mmol) and Pd(PPh.sub.3).sub.4 (0.67 g, 0.580 mmol) was heated and refluxed for 16 hours under a nitrogen atmosphere. After being allowed to coot, the mixture was concentrated to approximately in solution volume by a rotary evaporator, and then the obtained mixture was transferred to a separating funnel. After diluting with an appropriate amount of chloroform, the mixture was washed with water and a saturated saline, and the organic layer was dried on anhydrous magnesium sulfate. After removal of the magnesium sulfate by filtration, the solvent of the filtrate was distilled off with a rotary evaporator. The CN ligand (1) was obtained in a yield of 93% (1.51 g, 7.86 mmol) by purifying the residue with a silica gel chromatography (development solvent; ethyl acetate:hexane=1:3 (v/v)). The .sup.1H NMR property of the thus synthesized compound was as follows.

(30) .sup.1H NMR (CDCl.sub.3): 6.93 (dd, J=3.2, and 8.4 Hz, 1H), 7.20-7.32 (m, 1H), 7.68-7.86 (m, 2H), 8.56-8.73 (m, 2H)

(31) ##STR00031##

Synthesis of CN Ligand (2)

(32) In accordance with the following formula, a CN ligand (2) was obtained by reacting 3,5-bis(trifluoromethyl)phenylboronic acid with 2-iodopyridine. A mixture of 3,5-bis(trifluoromethyl)phenylboronic acid (2.00 g, 7.75 mmol), 2-iodopyridine (1.17 g, 5.71 mmol), THF (30 mL), water (10 mL), K.sub.2CO.sub.3 (4.50 g, 32.6 mmol) and Pd(PPh.sub.3).sub.4 (0.261 g, 0.226 mmol) was heated and refluxed for 48 hours under a nitrogen atmosphere. After being allowed to cool, the mixture was concentrated to approximately in solution volume by a rotary evaporator, and then the obtained mixture was transferred to a separating funnel. After diluting with an appropriate amount of chloroform, the mixture was washed with water and a saturated saline, and the organic layer was dried on anhydrous magnesium sulfate. After removal of the magnesium sulfate by filtration, the solvent of the filtrate was distilled off with a rotary evaporator. The CN ligand (2) was obtained in a yield of 51% (0.850 g, 2.92 mmol) by purifying the residue with a silica gel chromatography (development solvent; chloroform). The .sup.1H NMR property of the thus synthesized compound was as follows.

(33) .sup.1H NMR (CDCl.sub.3): 7.34-7.38 (m, 1H), 7.81-7.87 (m, 2H), 7.92 (s, 1H), 8.49 (s, 2H), 8.76 (dt, J=2.2 and 5.0 Hz, 1H)

(34) ##STR00032##

Synthesis of CN Ligand (3)

(35) In accordance with the following formula, a CN ligand (3) was obtained by reacting 2,4-bis(trifluoromethyl)phenylboronic acid with 2-iodopyridine. A mixture of 2,4-bis(trifluoromethyl)phenylboronic acid (2.31 g, 8.96 mmol), 2-iodopyridine (1.16 g, 5.66 mmol), benzene (25 mL), ethanol (10 mL), K.sub.2CO.sub.3 (7.31 g, 52.9 mmol) and PdCl.sub.2(PPh.sub.3).sub.2 (0.383 g, 0.546 mmol) was heated and refluxed for 16 hours under a nitrogen atmosphere. After being allowed to cool, the reaction mixture was transferred to a separating funnel. After diluting with an appropriate amount of chloroform, the mixture was washed with water and a saturated saline, and the organic layer was dried on anhydrous magnesium sulfate. After removal of the magnesium sulfate by filtration, the solvent was distilled off with a rotary evaporator. The CN ligand (3) was obtained in a yield of 59% (0.978 g, 3.36 mmol) by purifying the residue with a silica gel chromatography (development solvent; chloroform). The .sup.1H NMR property of the thus synthesized compound was as follows.

(36) .sup.1H NMR (CDCl.sub.3): 7.33 (ddd, J=7.8, 7.7 and 1.1 Hz, 1H), 7.42 (d, J=7.8 Hz, 1H), 7.64 (d, J=7.7 Hz, 1H), 7.76 (ddd, J=7.7, 7.7 and 1.9 Hz, 1H), 7.86 (d, J=8.3 Hz, 1H), 8.01 (s, 1H)

(37) ##STR00033##

Synthesis of CN Ligand (4)

(38) In accordance with the following formula, a CN ligand (4) was obtained by reacting 2,4-difluoro-3-cyanophenylboronic acid with 2-iodopyridine. A mixture of 2,4-difluoropyridineboronic acid (0.976 g, 5.34 mmol), 2-iodopyridine (0.733 g, 3.58 mmol), benzene (15 mL), ethanol (6 mL), water (15 mL), K.sub.2CO.sub.3 (4.56 g, 33.0 mmol) and Pd(PPh.sub.3).sub.2 Cl.sub.2 (0.215 g, 0.306 mmol) was heated and refluxed for 18 hours under a nitrogen atmosphere. After being allowed to cool, the mixture was concentrated to approximately in solution volume by a rotary evaporator, and then the obtained mixture was transferred to a separating funnel. After diluting with an appropriate amount of chloroform, the mixture was washed with water and a saturated saline, and the organic layer was dried on anhydrous magnesium sulfate. After removal of the magnesium sulfate by filtration, the solvent of the filtrate was distilled off with a rotary evaporator. The CN ligand (4) was obtained in a yield of 80% (0.620 g, 2.87 mmol) by purifying the residue with a silica gel chromatography (development solvent; chloroform). The .sup.1H NMR property of the thus synthesized compound was as follows.

(39) .sup.1H NMR (CDCl.sub.3): 7.18 (ddd, J=1.4, 7.8 and 9.2 Hz, 1H), 7.33 (ddd, J=1.4, 5.0 and 7.3 Hz, 1H), 7.76-7.84 (m, 2H), 7.86 (td, J=6.4 and 8.7 Hz, 1H), 8.72 (m, 1H)

(40) ##STR00034##

(41) Precursor (1) to (3) were obtained by casing each of the thus synthesized CN ligands and iridium chloride to react with each other.

Synthesis of Precursor (1)

(42) In accordance with the following formula, a precursor (1) was obtained by casing the CN ligand (1) and iridium chloride to react with each other. A mixture of 2,6-difluoro-2,3-bipyridine (0.500 g, 2.60 mmol), iridium chloride trihydrate (0.442 g, 1.25 mmol), water (17 mL) and 2-ethoxyethanol (48 mL) was stirred for 12 hours at 100 C. After being allowed to cool, the mixture was concentrated by a rotary evaporator, water (50 mL) was added to the mixture. The resulting precipitant was recovered by suction filtration, and then the precursor (1) was obtained in a yield of 73% (0.580 g, 0.475 mmol) by washing with an appropriate amount of methanol. The thus obtained compound was an insoluble solid. Without further purification, the compound was used for the following synthesis of an iridium complex.

(43) ##STR00035##

Synthesis of Precursor (2)

(44) In accordance with the following formula, a precursor (2) was obtained by casing the CN ligand (2) and iridium chloride to react with each other. A mixture of 2-(3,5-bis(trifluoromethyl)phenyl)pyridine (0.850 g, 2.92 mmol), iridium chloride trihydrate (0.430 g, 1.22 mmol), water (20 mL) and 2-ethoxyethanol (48 mL) was stirred for 12 hours at 100 C. After being allowed to cool, the mixture was concentrated by a rotary evaporator, water (50 mL) was added to the mixture. The resulting precipitant was recovered by suction filtration, and then the precursor (2) was obtained in a yield of 79% (0.930 g, 0.575 mmol) by washing with an appropriate amount of methanol. The thus obtained compound was an insoluble solid. Without further purification, the compound was used for the following synthesis of an iridium complex.

(45) ##STR00036##

Synthesis of Precursor (3)

(46) In accordance with the following formula, a precursor (3) was obtained by casing the CN ligand (3) and iridium chloride to react with each other. A mixture of 2-(2,4-bis(trifluoromethyl)phenyl)pyridine (0.431 g, 1.48 mmol), iridium chloride trihydrate (0.264 g, 0.749 mmol), water (10 mL) and 2-ethoxyethanol (28 mL) was stirred for 12 hours at 100 C. After being allowed to cool, the mixture was concentrated by a rotary evaporator, water (30 mL) was added to the mixture. The resulting precipitant was recovered by suction filtration, and then the precursor (3) was obtained in a yield of 55% (0.329 g, 0.204 mmol) by washing with an appropriate amount of methanol. The thus obtained compound was an insoluble solid. Without further purification, the compound was used for the following synthesis of an iridium complex.

(47) ##STR00037##

Synthesis of Precursor (4)

(48) In accordance with the following formula, a precursor (4) was obtained by casing the CN ligand (4) and iridium chloride to react with each other. A mixture of 2,6-difluoro-3-(pyridine-2-yl)benzonitrile (0.612 g, 2.83 mmol), iridium chloride trihydrate (0.492 g, 1.40 mmol), water (21 mL) and 2-ethoxyethanol (64 mL) was stirred for 25 hours at 100 C. After being allowed to cool, the mixture was concentrated by a rotary evaporator, water (50 mL) was added to the mixture. The resulting precipitant was recovered by suction filtration, and then the precursor (4) was obtained in a yield of 83% (0.762 g, 0.579 mmol) by washing with an appropriate amount of methanol. The thus obtained compound was an insoluble solid. Without further purification, the compound was used for the following synthesis of an iridium complex.

(49) ##STR00038##

(50) The thus synthesized precursors (1) to (4) and -diketones (A), (B), and (X) were reacted with each other respectively to give respective iridium complexes.

Synthesis of Iridium Complex (1-A)

(51) In accordance with the following formula, the iridium complex 1-A was obtained by reacting the precursor (1) and the -diketone (A) with each other.

(52) ##STR00039##

Synthesis of Iridium Complex (1-A)

(53) The precursor (1) (0.244 g, 0.200 mmol), 1,3-bis(3,5-di(tert-butyl)phenyl)propane-1,3-dione (-diketone (A)), (0.131 g, 0.292 mmol) and sodium carbonate (1.90 g, 17.9 mmol) was added to 2-ethoxyethanol (50 mL), and the resulting mixture was stirred for 30 minutes at 80 C. under a nitrogen atmosphere. After being allowed to cool, the solvent was distilled off by a rotary evaporator, and then chloroform was added to the residue. The obtained mixed solution was washed with water and a saturated saline, and was then dried by adding an appropriate amount of anhydrous sodium sulfate. After removal of the sodium sulfate by filtration, the solvent of the filtrate was distilled off with a rotary evaporator. The iridium complex 1-A was obtained in a yield of 25% (73.5 mg, 0.0719 mmol) by purifying the obtained residue with a silica gel column chromatography (development solvent; methylene chloride), and by further performing recrystallization using acetonitrile. The properties of the thus synthesized compound were as follows.

(54) .sup.1H NMR (CDCl.sub.3): 1.26 (s, 36H), 5.81 (t, J=1.8 Hz, 2H), 6.58 (s, 1H), 7.19-7.22 (m, 2H), 7.53 (m, 6H), 7.85-7.89 (m, 2H), 8.29 (d, J=7.6 Hz, 2H), 8.57 (dd, J=0.80 and 6.0 Hz, 2H)

(55) ESI-TOF MS: m/z 1045 ([M+Na].sup.+)

(56) Anal. Calcd for C.sub.51H.sub.53F.sub.4IrN.sub.4O.sub.2: C, 59.92; H, 5.23; 5.48. Found: C, 60.10; H, 5.03; 5.50.

Synthesis of Iridium Complex (1-B)

(57) In accordance with the following formula, the iridium complex 1-B was obtained by reacting the precursor (1) and the -diketone (B) with each other.

(58) ##STR00040##

Synthesis of Iridium Complex (1-B)

(59) The precursor (1) (0.246 g, 0.201 mmol), -diketone (B), (0.129 g, 0.290 mmol) and sodium carbonate (1.90 g, 17.9 mmol) was added to 2-ethoxyethanol (50 mL), and the resulting mixture was stirred for 30 minutes at 80 C. under a nitrogen atmosphere. After being allowed to cool, the solvent was distilled off by a rotary evaporator, and then chloroform was added to the residue. The obtained mixed solution was washed with water and a saturated saline, and was then dried by adding an appropriate amount of anhydrous sodium sulfate. After removal of the sodium sulfate by filtration, the solvent of the filtrate was distilled off with a rotary evaporator. The iridium complex 1-B was obtained in a yield of 25% (75.1 mg, 0.0738 mmol) by purifying the obtained residue with a silica gel column chromatography (development solvent; methylene chloride), and by further performing recrystallization using methanol. The properties of the thus synthesized compound were as follows.

(60) .sup.1H NMR (CDCl.sub.3): 1.23 (s, 12H), 1.25 (s, 12H), 1.66 (s, 8H), 5.76 (s, 2H), 6.58 (s, 1H), 7.17-7.21 (m, 2H), 7.29 (d, J=8.0 Hz, 2H), 7.49-7.52 (m, 2H), 7.71 (d, J=2.0 Hz, 2H), 7.83-7.87 (m, 2H), 8.27 (d, J=8.8 Hz, 2H), 8.53 (d, J=6.0 Hz, 2H)

(61) ESI-TOF MS: m/z 1041 ([M+Na].sup.+)

(62) Anal. Calcd for C.sub.51H.sub.49F.sub.4IrN.sub.4O.sub.2: C, 60.16; H, 4.85; 5.50. Found: C, 60.12; H, 4.61; 5.45.

Synthesis of Iridium Complex (1-X)

(63) In accordance with the following formula, the iridium complex 1-X was obtained by reacting the precursor (1) and the -diketone (X) with each other.

(64) ##STR00041##

Synthesis of Iridium Complex (1-X)

(65) The precursor (1) (0.500 g, 0.410 mmol), -diketone (X), (0.435 g, 1.94 mmol) and sodium carbonate (0.389 g, 3.67 mmol) was added to 2-ethoxyethanol (77 mL), and the resulting mixture was stirred for 2 hours at 105 C. under a nitrogen atmosphere. After being allowed to cool, the solvent was distilled off by a rotary evaporator, and then chloroform was added to the residue. The obtained mixed solution was washed with water and a saturated saline, and was then dried by adding an appropriate amount of anhydrous sodium sulfate. After removal of the sodium sulfate by filtration, the solvent of the filtrate was distilled off with a rotary evaporator. The iridium complex 1-X was obtained in a yield of 38% (250 mg, 0.313 mmol) by purifying the obtained residue with a silica gel column chromatography (development solvent; methylene chloride), and by further performing recrystallization using methanol. The properties of the thus synthesized compound were as follows.

(66) .sup.1H NMR (CDCl.sub.3): 5.75 (s, 2H), 6.66 (s, 1H), 7.23-7.25 (m, 2H), 7.35 (t, J=7.8 Hz, 4H), 7.45-7.47 (m, 2H), 7.77 (dd, J=1.2 and 7.8 Hz, 4H), 7.88 (t, J=7.8 Hz, 2H), 8.29 (d, J=8.0 Hz, 2H), 8.52 (d, J=6.0 Hz, 2H)

(67) ESI-TOF MS: m/z 821 ([M+Na].sup.+)

(68) Anal. Calcd for C.sub.35H.sub.21F.sub.4IrN.sub.4O.sub.2: C, 52.69; H, 2.65; 7.02. Found: C, 52.92; H, 2.73; 7.01.

Synthesis of Iridium Complex (2-A)

(69) In accordance with the following formula, the iridium complex 2-A was obtained by reacting the precursor (2) and the -diketone (A) with each other.

(70) ##STR00042##

Synthesis of Iridium Complex (2-A)

(71) The precursor (2) (0.245 g, 0.152 mmol), 1,3-bis(3,5-di(tert-butyl)phenyl)propane-1,3-dione (-diketone (A)), (0.129 g, 0.288 mmol) and sodium carbonate (1.90 g, 17.9 mmol) was added to 2-ethoxyethanol (50 mL), and the resulting mixture was stirred for 2 hours at 100 C. under a nitrogen atmosphere. After being allowed to cool, the solvent was distilled off by a rotary evaporator, and then chloroform was added to the residue. The obtained mixed solution was washed with water and a saturated saline, and was then dried by adding an appropriate amount of anhydrous sodium sulfate. After removal of the sodium sulfate by filtration, the solvent of the filtrate was distilled off with a rotary evaporator. The iridium complex 2-A was obtained in a yield of 5.8% (20.3 mg, 0.0166 mmol) by purifying the obtained residue with a silica gel column chromatography (development solvent; chloroform:hexane=1:1 (v/v)), and by further performing recrystallization using methanol. The properties of the thus synthesized compound were as follows.

(72) .sup.1H NMR (CDCl.sub.3): 1.24 (s, 36H), 6.34 (s, 1H), 6.94-6.97 (m, 2H), 7.30 (d, J=1.6 Hz, 4H), 7.48 (t, J=1.6 Hz, 2H), 7.55 (brs, 2H), 7.78 (dt, J=1.6 and 7.8 Hz, 2H), 8.05 (d, J=7.6 Hz, 2H), 8.16 (brs, 2H), 8.27 (d, J=6.0 Hz, 2H)

(73) ESI-TOF MS: m/z 1243 ([M+Na].sup.+)

(74) Anal. Calcd for C.sub.57H.sub.55F.sub.12IrN.sub.2O.sub.2: C, 56.10; H, 4.54; 2.30. Found: C, 55.93; H, 4.49; 2.26.

Synthesis of Iridium Complex (2-B)

(75) In accordance with the following formula, the iridium complex 2-B was obtained by reacting the precursor (2) and the -diketone (B) with each other.

(76) ##STR00043##

Synthesis of Iridium Complex (2-B)

(77) The precursor (2) (0.154 g, 0.0953 mmol), -diketone (B), (0.200 g, 0.450 mmol) and sodium carbonate (0.0900 g, 0.849 mop was added to 2-ethoxyethanol (18 mL), and the resulting mixture was stirred for 3 hours at 105 C. under a nitrogen atmosphere. After being allowed to cool, the solvent was distilled off by a rotary evaporator, and then chloroform was added to the residue. The obtained mixed solution was washed with water and a saturated saline, and was then dried by adding an appropriate amount of anhydrous sodium sulfate. After removal of the sodium sulfate by filtration, the solvent of the filtrate was distilled off with a rotary evaporator. The iridium complex 2-B was obtained in a yield of 39% (90.0 mg, 0.0740 mmol) by purifying the obtained residue with a silica gel column chromatography (development solvent; chloroform), and by further performing recrystallization using methanol. The properties of the thus synthesized compound were as follows.

(78) .sup.1H NMR (CDCl.sub.3): 1.16 (s, 12H), 1.23 (s, 12H), 1.64 (s, 8H), 6.32 (s, 1H), 6.91-6.95 (m, 2H), 7.22 (d, J=7.8 Hz, 2H), 7.30 (dd, J=2.0 and 7.8 Hz, 2H), 7.43 (d, J=2.0 Hz, 2H), 7.55 (s, 2H), 7.73-7.78 (m, 2H), 8.01 (d, J=8.0 Hz, 2H), 8.16 (s, 2H), 8.22 (d, J=6.0 Hz, 2H)

(79) ESI-TOF MS: m/z 1239 ([M+Na].sup.+)

(80) Anal. Calcd for C.sub.57H.sub.51F.sub.12IrN.sub.2O.sub.2: C, 56.29; H, 4.23; 2.30. Found: C, 56.60; H, 4.40; 2.26.

Synthesis of Iridium Complex (2-X)

(81) In accordance with the following formula, the iridium complex 2-X was obtained by reacting the precursor (2) and the -diketone (X) with each other.

(82) ##STR00044##

Synthesis of Iridium Complex (2-X)

(83) The precursor (2) (0.331 g, 0.205 mmol), -diketone (X), (0.220 g, 0.981 mmol) and sodium carbonate (0.195 g, 1.84 mmol) was added to 2-ethoxyethanol (39 mL), and the resulting mixture was stirred for 3 hours at 105 C. under a nitrogen atmosphere. After being allowed to cool, the solvent was distilled off by a rotary evaporator, and then chloroform was added to the residue. The obtained mixed solution was washed with water and a saturated saline, and was then dried by adding an appropriate amount of anhydrous sodium sulfate. After removal of the sodium sulfate by filtration, the solvent of the filtrate was distilled off with a rotary evaporator. The iridium complex 2-X was obtained in a yield of 30% (120 mg, 0.121 mmol) by purifying the obtained residue with a silica gel column chromatography (development solvent; chloroform), and by further performing recrystallization using methanol. The properties of the thus synthesized compound were as follows.

(84) .sup.1H NMR (CDCl.sub.3): 6.43 (s, 1H), 6.94-6.98 (m, 2H), 7.29 (t, J=7.8 Hz, 4H), 7.41 (t, J=7.8 Hz, 2H), 7.55-7.57 (m, 6H), 7.74-7.78 (m, 2H), 8.00 (d, J=8.4 Hz, 2H), 8.13 (s, 2H), 8.21 (d, J=6.0 Hz, 2H)

(85) ESI-TOF MS: m/z 1019 ([M+Na].sup.+)

(86) Anal. Calcd for C.sub.41H.sub.23F.sub.12IrN.sub.2O.sub.2.H.sub.2O: C, 48.57; H, 2.49; 2.76. Found: C, 48.76; H, 2.60; 2.67.

Synthesis of Iridium Complex (3-A)

(87) In accordance with the following formula, the iridium complex 3-A was obtained by reacting the precursor (3) and the -diketone (A) with each other.

(88) ##STR00045##

Synthesis of Iridium Complex (3-A)

(89) The precursor (3) (0.240 g, 0.149 mmol), 1,3-bis(3,5-di(tert-butyl)phenyl)propane-1,3-dione (-diketone (A)), (0.129 g, 0.288 mmol) and sodium carbonate (1.91 g, 18.1 mmol) was added to 2-ethoxyethanol (50 mL), and the resulting mixture was stirred for 2 hours at 100 C. under a nitrogen atmosphere. After being allowed to cool, the solvent was distilled off by a rotary evaporator, and then chloroform was added to the residue. The obtained mixed solution was washed with water and a saturated saline, and was then dried by adding an appropriate amount of anhydrous sodium sulfate. After removal of the sodium sulfate by filtration, the solvent of the filtrate was distilled off with a rotary evaporator. The iridium complex 3-A was obtained in a yield of 44% (154 mg, 0.126 mmol) by purifying the obtained residue with a silica gel column chromatography (development solvent; chloroform:hexane=1:1 (v/v)), and by further performing recrystallization using methanol. The properties of the thus synthesized compound were as follows.

(90) .sup.1H NMR (CDCl.sub.3): 1.25 (s, 36H), 6.53 (s, 1H), 6.70 (s, 2H), 7.20-7.24 (m, 2H), 7.44 (d, J=2.0 Hz, 4H), 7.50 (t, J=2.0 Hz, 2H), 7.54 (s, 2H), 7.86-7.91 (m, 2H), 8.44 (d, J=8.0 Hz, 2H), 8.67 (dd, J=1.4 and 5.8 Hz, 2H)

(91) ESI-TOF MS: m/z 1243 ([M+Na].sup.+)

(92) Anal. Calcd for C.sub.57H.sub.55F.sub.12IrN.sub.2O.sub.2: C, 56.10; H, 4.54; 2.30. Found: C, 56.27; H, 4.74; 2.41.

Synthesis of Iridium Complex (3-B)

(93) In accordance with the following formula, the iridium complex 3-B was obtained by reacting the precursor (3) and the -diketone (B) with each other.

(94) ##STR00046##

Synthesis of Iridium Complex (3-B)

(95) The precursor (3) (0.241 g, 0.149 mmol), -diketone (B), (0.129 g, 0.290 mmol) and sodium carbonate (1.90 g, 18.0 mmol) was added to 2-ethoxyethanol (50 mL), and the resulting mixture was stirred for 2 hours at 100 C. under a nitrogen atmosphere. After being allowed to cool, the solvent was distilled off by a rotary evaporator, and then chloroform was added to the residue. The obtained mixed solution was washed with water and a saturated saline, and was then dried by adding an appropriate amount of anhydrous sodium sulfate. After removal of the sodium sulfate by filtration, the solvent of the filtrate was distilled off with a rotary evaporator. The iridium complex 2-B was obtained in a yield of 17% (59.7 mg, 0.0491 mmol) by purifying the obtained residue with a silica gel column chromatography (development solvent; chloroform:hexane=1:1 (v/v)), and by further performing recrystallization using methanol. The properties of the thus synthesized compound were as follows.

(96) .sup.1H NMR (CDCl.sub.3): 1.16 (s, 6H), 1.18 (s, 6H), 1.22 (s, 6H), 1.23 (s, 6H), 1.64 (s, 8H), 6.52 (s, 1H), 6.64 (s, 2H), 7.20 (t, J=6.0 Hz, 2H), 7.27 (d, J=7.8 Hz, 2H), 7.43 (dd, J=2.0 and 7.8 Hz, 2H), 7.53 (s, 2H), 7.61 (d, J=2.0 Hz, 2H), 7.83-7.88 (m, 2H), 8.41 (d, J=8.0 Hz, 2H), 8.63 (d, J=6.0 Hz, 2H)

(97) ESI-TOF MS: m/z 1239 ([M+Na].sup.+)

(98) Anal. Calcd for C.sub.57H.sub.51F.sub.12IrN.sub.2O.sub.2: C, 56.29; H, 4.23; 2.30. Found: C, 56.30; H, 4.05; 2.28.

Synthesis of Iridium Complex (3-X)

(99) In accordance with the following formula, the iridium complex 3-X was obtained by reacting the precursor (3) and the -diketone (X) with each other.

(100) ##STR00047##

Synthesis of Iridium Complex (3-X)

(101) The precursor (3) (0.200 g, 0.124 mmol), -diketone (X), (0.128 g, 0.571 mmol) and sodium carbonate (0.115 g, 1.09 mmol) was added to 2-ethoxyethanol (23 mL), and the resulting mixture was stirred for 3 hours at 105 C. under a nitrogen atmosphere. After being allowed to cool, the solvent was distilled off by a rotary evaporator, and then chloroform was added to the residue. The obtained mixed solution was washed with water and a saturated saline, and was then dried by adding an appropriate amount of anhydrous sodium sulfate. After removal of the sodium sulfate by filtration, the solvent of the filtrate was distilled off with a rotary evaporator. The iridium complex 3-X was obtained in a yield of 10% (25.0 mg, 0.0251 mmol) by purifying the obtained residue with a silica gel column chromatography (development solvent; chloroform), and by further performing recrystallization using methanol. The properties of the thus synthesized compound were as follows.

(102) .sup.1H NMR (CDCl.sub.3): 6.60 (s, 2H), 6.61 (s, 1H), 7.21-7.24 (m, 2H), 7.32 (t, J=7.4 Hz, 4H), 7.44 (t, J=7.4 Hz, 2H), 7.54 (s, 2H), 7.72 (d, J=7.4 Hz, 4H), 7.85-7.90 (m, 2H), 8.41 (d, J=8.8 Hz, 2H), 8.64 (dd, J=0.8 and 5.8 Hz, 2H)

(103) ESI-TOF MS: m/z 1019 ([M+Na].sup.+)

(104) Anal. Calcd for C.sub.41H.sub.23F.sub.12IrN.sub.2O.sub.2: C, 49.45; H, 2.33; 2.81. Found: C, 49.60; H, 2.70; 2.70.

Synthesis of Iridium Complex (4-A)

(105) In accordance with the following formula, the iridium complex 4-A was obtained by reacting the precursor (4) and the -diketone (A) with each other.

(106) ##STR00048##

Synthesis of Iridium Complex (4-A)

(107) The precursor (4) (0.243 g, 0.185 mmol), 1,3-bis(3,5-di(tert-butyl)phenyl)propane-1,3-dione (-diketone (A)), (0.133 g, 0.296 mmol) and sodium carbonate (1.90 g, 17.9 mmol) was added to 2-ethoxyethanol (50 mL), and the resulting mixture was stirred for 2 hours at 100 C. under a nitrogen atmosphere. After being allowed to cool, the solvent was distilled off by a rotary evaporator, and then ethyl acetate was added to the residue. The obtained mixed solution was washed with water and a saturated saline, and was then dried by adding an appropriate amount of anhydrous magnesium sulfate. After removal of the magnesium sulfate by filtration, the solvent of the filtrate was distilled off with a rotary evaporator. The iridium complex 4-A was obtained in a yield of 12% (0.0459 g, 0.0429 mmol) by purifying the obtained residue with a silica gel column chromatography (development solvent; chloroform), and by further performing recrystallization using methanol. The properties of the thus synthesized compound were as follows.

(108) .sup.1H NMR (CDCl.sub.3): 1.26 (s, 36H), 5.98 (d, J=8.6 Hz, 2H), 6.56 (s, 1H), 7.22 (td, J=1.4 and 5.9 Hz, 2H), 7.49 (d, J=1.8 Hz, 4H), 7.54 (t, J=1.8 Hz, 2H), 7.90 (td, J=1.4 and 8.2 Hz, 2H), 8.32 (d, J=8.2 Hz, 2H), 8.55 (dd, J=1.4 and 5.9 Hz, 2H)

(109) ESI-TOF MS: m/z 1093 ([M+Na].sup.+)

(110) Anal. Calcd for C.sub.55H.sub.53F.sub.4IrN.sub.4O.sub.2: C, 61.72; H, 4.99; N, 5.23. Found: C, 61.72; H, 5.03; N, 5.23.

Synthesis of Iridium Complex (4-B)

(111) In accordance with the following formula, the iridium complex 4-B was obtained by reacting the precursor (4) and the -diketone (B) with each other.

(112) ##STR00049##

Synthesis of Iridium Complex (4-B)

(113) The precursor (4) (0.106 g, 0.0805 mmol), -diketone (B), (0.0884 g, 0.199 mmol) and sodium carbonate (0.0531 g, 0.501 mmol) was added to 2-ethoxyethanol (25 mL), and the resulting mixture was stirred for 1 hour and 30 minutes at 40 C. under a nitrogen atmosphere. After being allowed to cool, the solvent was distilled off by a rotary evaporator, and then methylene chloride was added to the residue. The obtained mixed solution was washed with water and a saturated saline, and was then dried by adding an appropriate amount of anhydrous magnesium sulfate. After removal of the magnesium sulfate by filtration, the solvent of the filtrate was distilled off with a rotary evaporator. The iridium complex 4-B was obtained in a yield of 22% (0.0378 g, 0.0355 mmol) by purifying the obtained residue with a silica gel column chromatography (development solvent; methylene chloride), and by further performing recrystallization using methanol. The properties of the thus synthesized compound were as follows.

(114) .sup.1H NMR (CDCl.sub.3): 1.24 (m, 24H), 1.66 (m, 8H), 5.92 (d, J=8.6 Hz, 2H), 6.58 (s, 1H), 7.21-7.24 (m, 2H), 7.29 (d, J=8.6 Hz, 2H), 7.48 (dd, J=1.8 and 8.6 Hz, 2H), 7.69 (d, J=1.8 Hz, 2H), 7.86-7.90 (m, 2H), 8.30 (d, J=8.6 Hz, 2H), 8.50 (dd, J=1.4 and 5.9 Hz, 2H)

(115) ESI-TOF MS: m/z 1089 ([M+Na].sup.+)

(116) Anal. Calcd for C.sub.55H.sub.49F.sub.4IrN.sub.4O.sub.2: C, 61.96; H, 4.63; N, 5.25. Found: C, 61.94; H, 4.59; N, 5.25.

Synthesis of Iridium Complex (4-X)

(117) In accordance with the following formula, the iridium complex 4-X was obtained by reacting the precursor (4) and the -diketone (X) with each other.

(118) ##STR00050##

Synthesis of Iridium Complex (4-X)>

(119) The precursor (4) (0.0980 g, 0.0745 mmol), -diketone (X), (0.0496 g, 0.221 mmol) and sodium carbonate (0.0650 g, 0.613 mmol) was added to 2-ethoxyethanol (7 mL), and the resulting mixture was stirred for 30 minutes at 40 C. under a nitrogen atmosphere. After being allowed to cool, the solvent was distilled off by a rotary evaporator, and then methylene chloride was added to the residue. The obtained mixed solution was washed with water and a saturated saline, and was then dried by adding an appropriate amount of anhydrous magnesium sulfate. After removal of the magnesium sulfate by filtration, the solvent of the filtrate was distilled off with a rotary evaporator. The iridium complex 4-X was obtained in a yield of 21% (0.0254 g, 0.0300 mmol) by purifying the obtained residue with a silica gel column chromatography (development solvent; methylene chloride), and by further performing recrystallization using methanol. The properties of the thus synthesized compound were as follows.

(120) .sup.1H NMR (CDCl.sub.3): 5.91 (d, J=8.8 Hz, 2H), 6.65 (s, 1H), 7.26-7.28 (m, 2H), 7.35 (t, J=7.7 Hz, 4H), 7.45-7.49 (m, 2H), 7.75-7.77 (m, 4H), 7.90 (td, J=1.4 and 8.4 Hz, 2H), 8.32 (d, J=8.4 Hz, 2H), 8.49 (dd, J=1.4 and 5.6 Hz, 2H)

(121) ESI-TOF MS: m/z 869 ([M+Na].sup.+)

(122) Anal. Calcd for C.sub.39H.sub.21F.sub.4IrN.sub.4O.sub.2: C, 55.38; H, 2.50; N, 6.62. Found: C, 55.38; H, 2.74; N, 6.74.

(123) [Evaluation of Photoluminescence (PL) Spectrum and PL Quantum Yield]

(124) The photoluminescence (PL) spectrum and the PL quantum yield .sub.PL of each iridium complex obtained above were measured. Fluorolog-3 spectrometer manufactured by HORIBA, Ltd. was used for measuring the PL spectrum. C9920-12 Quantum yield measuring machine manufactured by HAMAMATSU Photonics K.K. was used for measuring the PL quantum yield. The evaluation of these PL spectrum and PL quantum yield were conducted in a polymer thin film (polymethyl methacrylate, PMMA), as medium. Note that the solution sample sealed with argon gas was measured as a deoxidized solution, and the polymer thin film sample was measured under a nitrogen atmosphere. The polymer thin film sample was measured by 0.05 mmol/g (4 wt %) doping of each iridium complex into PMMA. The results are shown in the following Table.

(125) TABLE-US-00001 TABLE 1 Wavelength PL .sub.PL Quantum yield (nm) .sub.PL 1-A 537 0.58 2-A 545 0.52 3-A 545 0.49 4-A 543 0.45 1-B 537 0.62 2-B 548 0.47 3-B 548 0.68 4-B 537 0.53 1-X 550 0.23 2-X 561 0.17

(126) From the above Table, the iridium complexes having the tert-butyl-substituted phenyl group as the -diketone (1-A, 2-A, 3-A, 4-A, 1-B, 2-B, 3-B, 4-B) showed photoluminescence quantum yields higher than 0.45 in the polymer thin film.

(127) Next, with respect to the iridium complexes 1-A, 2-A, 1-B, 2-B, the PL spectrum and PL quantum yield were evaluated in an organic solvent (dichloromethane (CH.sub.2Cl.sub.2)), as medium. The results are shown in the following Table and in FIG. 1. In the following Table, the results in the polymer thin film are shown together, and also calculated values of difference (wavelength shift .sub.PL) between the position of wavelength peak in the organic solvent and the position of wavelength peak in the polymer thin film are shown.

(128) TABLE-US-00002 TABLE 2 In organic solvent In polymer thin film .sub.PL .sub.PL Wavelength shift (nm) .sub.PL (nm) .sub.PL .sub.PL 1-A 573 0.19 537 0.58 36 2-A 595 0.11 545 0.52 50 1-B 567 0.28 537 0.62 30 2-B 596 0.18 548 0.47 48

(129) From the above Table and FIG. 1, with respect to the iridium complexes having the tert-butyl-substituted phenyl group as the -diketone (1-A, 2-A, 1-B, 2-B), the rigidchromism was observed where the position of the wavelength peak in the polymer thin film shifted to the short wavelength side relative to the wavelength peak in an organic solvent. In the viewpoint of luminescent color, the light emission wavelength of yellowish green to orange in the organic solvent changed to the light emission wavelength of green to yellow in the polymer thin film.

(130) From the aforementioned results, it has been found that the iridium complexes having the tert-butyl-substituted phenyl group as the -diketone had the PL quantum yield .sub.PL of 0.45 or more when doping to the polymer thin film at a dose of 0.05 mmol, and showed the rigidchromism where the light emission wavelength in the polymer thin film shifted to the short wavelength side relative to the light emission wavelength in an organic solvent.

(131) [Production and Property Evaluation of Organic EL Element]

(132) The iridium complexes were used to produce the organic EL element (1) shown in FIG. 2 in the following procedures, and its properties were evaluated.

(133) <Production of Organic EL Element>

(134) (a) Formation of Hole Injection Layer (5)

(135) An anode (2) was prepared by subjecting an ITO-glass substrate (manufactured by SANYO Vacuum Industries Co., Ltd., ITO, film thickness 150 nm) to patterning treatment and then by performing washing. Next, the ITO thin film was surface-treated by ozone. After the surface treatment, a hole injection layer (5) having a thickness of 40 nm was formed by rapid film formation of a hole injection material on the ITO film through the use of the spin coating method, and by baking at 120 C. for 1 hour. An electrically conductive polymer (P VP CH8000 manufactured by Heraeus Clevios) containing PEDOT and PSS was used as the hole injection material.

(136) (b) Formation of Emission Layer (4)

(137) An ink Ink (1-A) for the emission layer was prepared by dissolution of poly(9-vinylcarbasol) (PVCz, manufactured by Sigma-Aldrich, Number average molecular weight Mn, 25000-50000, purified by re-precipitating from THF-methanol), 2-(4-biphenilyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD) and the iridium complex 1-A in a dehydrated toluene, and by filtration with a membrane filter (0.2 m Millex-FG manufactured by Merck Millipore Corporation). The concentrations of the PBD and the iridium complex to be doped to 1 g of PVCz were 850 mol and 98 mol, respectively, and 0.7 ml of the toluene was used to 10 mg of PVCz as a solvent for the ink. Through the use of the obtained ink (1-A) for the emission layer, a emission layer 4 having a thickness of 80 nm was formed on the hole injection layer (5) by film formation using the spin coating method, and then by baking at 120 C. for 1 hour.

(138) (c) Formation of Electron Injection Layer (6) and Cathode (3)

(139) A thin film of cesium fluoride (electron injection layer (6), thickness 1 nm) as the electron-injecting material was formed by the vacuum deposition, through the use of a shadow mask, and then, a thin film of aluminum (cathode (3), thickness 250 nm) was produced. At this time, the electron injection layer (6) and the cathode (3) were produced so that the area of the light-emitting portion was 10 mm.sup.2 (2 mm5 mm). In this way, the organic EL element EL(1-A) was completed.

(140) <Production of Organic EL Element Used Each Iridium Complex as Emitting Material>

(141) An ink Ink (2-A) for the emission layer was prepared by using the iridium complex 2-A instead of the iridium complex 1-A. An organic EL element EL(2-A) was obtained in the similar way to the above procedures except that the ink Ink (2-A) was used for the emission layer. The organic EL elements EL(3-A), EL(4-A), EL(1-B), EL(2-B), EL(3-B), EL(4-B), EL(1-X), EL(2-X), EL(3-X), EL(4-X) were also produced by using the complexes 3-A, 4-A, 1-B, 2-B, 3-B, 4-B, 1-X, 2-X, 3-X, 4-X instead of the complex 1-A.

(142) <Evaluation of Organic EL Element Properties>

(143) Samples for evaluating the organic EL properties were produced with the organic EL element obtained by the above steps sealed into a cavity glass by using an ultraviolet curable resin.

(144) The organic EL element properties such as EL spectrum, maximum luminance L.sub.max (cd/m.sup.2), maximum external quantum efficiency .sub.ext.max (%), and CIE standard colorimetric system (x,y) were measured by a luminance goniophotometer (C-9920-11, manufactured by HAMAMATSU Photonics K.K.).

(145) Table 2 shows the results of the peak wavelength .sub.EL (nm), the maximum luminance L.sub.max (cd/m.sup.2), the maximum external quantum efficiency .sub.ext.max (%), the maximum current efficiency .sub.j,max (cd/A), the maximum power efficiency .sub.p,max (Im/W), and CIE standard colorimetric system (x,y). The L.sub.max and .sub.ext,max are shown along with the applied voltage (V) at the time of measurement in brackets. Note that the luminescence starting voltage V.sub.turn-on represents the voltage at which the luminance reaches 1 cd/m.sup.2.

(146) Furthermore, FIG. 3A and FIG. 3B shows the electroluminescent (EL) spectrum of the organic EL element EL(1-A), EL(2-A), EL(3-A), EL(4-A), EL(1-B), EL(2-B), EL(3-B), EL(4-B), EL(1-X), EL(2-X), EL(3-X), EL(4-X). The EL spectrum was measured at the maximum luminance L.sub.max.

(147) TABLE-US-00003 TABLE 3 Maximum Maximum Maximum Maximum external current power Luminescence luminance quantum efficiency efficiency starting L.sub.max/ efficiency .sub.j, max/ .sub.p, max/ voltage cd m.sup.2 .sub.ext. max/% cd A.sup.1 lm W.sup.1 .sub.EL/ CIE Element V.sub.turn-on/V (@V) (@V) (@V) (@V) nm (x, y) EL (1-A) 4.0 6200 (14.0) 3.0 (8.5) 9.5 (8.5) 4.1 (7.0) 550 (0.43, 0.54) EL (1-B) 4.5 4500 (15.0) 1.8 (8.0) 5.8 (6.5) 3.8 (4.5) 539 (0.42, 0.54) EL (1-X) 5.0 2900 (15.0) 1.3 (9.5) 4.0 (9.5) 1.2 (7.0) 564 (0.45, 0.53) EL (2-A) 4.0 4900 (14.0) 1.7 (9.5) 5.1 (9.5) 1.8 (8.0) 555 (0.44, 0.52) EL (2-B) 4.5 3200 (15.5) 1.5 (9.5) 4.3 (11.0) 1.4 (9.5) 555 (0.44, 0.52) EL (2-X) 5.5 1500 (15.0) 0.51 (9.0) 1.4 (8.5) 0.58 (7.0) 568 (0.48, 0.50) EL (3-A) 6.0 2700 (17.0) 1.1 (11.5) 3.7 (11.5) 1.1 (10.0) 545 (0.46, 0.53) EL (3-B) 5.0 3700 (15.5) 1.2 (10.0) 4.1 (11.0) 1.2 (10.0) 543 (0.46, 0.53) EL (3-X) 8.5 1000 (18.0) 0.37 (12.5) 1.3 (12.5) 0.31 (12.5) 545 (0.46, 0.53) EL (4-A) 4.0 8300 (15.5) 2.9 (10.5) 9.4 (9.5) 3.1 (9.5) 549 (0.42, 0.54) EL (4-B) 4.0 11000 (15.0) 2.9 (10.0) 9.0 (10.0) 2.8 (10.0) 551 (0.41, 0.54) EL (4-X) 3.5 4400 (15.5) 1.1 (11.0) 3.1 (11.0) 0.98 (9.0) 569 (0.45, 0.52)

(148) From the above results, the organic EL elements produced by using complexes 1-A, 2-A, 3-A, 4-A, 1-B, 2-B, 3-B, and 4-B exhibit improved organic EL properties in comparison with the organic EL elements produced by using the complexes 1-X, 2-X, 3-X, and 4-X.

INDUSTRIAL APPLICABILITY

(149) The organoiridium complex of the present invention is suitable as a emitting material of the organic EL element because of high photoluminescence quantum yield in the polymer thin film. Particularly, the present invention is suitable as a yellow to green emitting material.