CN113214325A - Organic iridium metal complex and preparation method and application thereof - Google Patents
Organic iridium metal complex and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an organic iridium metal complex, which has a structural general formula shown in chemical formula 1:
Description
Technical Field
The invention belongs to the technical field of organic light-emitting devices, and particularly relates to an organic iridium metal complex, a preparation method thereof and application thereof in preparation of organic electroluminescent devices.
Background
In 1987, doctor dung Qing cloud reported an electroluminescent diode technology based on organic luminescent material, which mainly adopts a vacuum evaporation way to prepare a double-layer device with a transmission layer and a luminescent layer, improves the quantum efficiency to 1 percent and can reach 1000cd/m under the working voltage lower than 10V2The brightness of the organic electroluminescence device promotes the organic electroluminescence technology to move to the practical stage. Electroluminescent devices have an all-solid-state structure, and organic electroluminescent materials are the core and foundation of the device. The development of new materials is a source for promoting the continuous progress of the electroluminescent technology. The preparation of the original material and the optimization of the device are also the research hotspots of the organic electroluminescent industry at present.
The phenomenon of phosphorescence has been pursued since the discovery, and since the luminous efficiency of phosphorescence materials is obviously higher than that of fluorescence, theoretically 100%, many research and development institutions are increasing the research and development efforts of phosphor materials, and trying to accelerate the industrialization development through phosphorescence materials. However, the development of the market is greatly hindered due to the high synthesis price of the phosphorescent material, the complex synthesis process, the environmental pollution during the synthesis process, the low synthesis purity, the low efficiency and the like.
Therefore, it is an urgent need to solve the technical problems of the art to provide a phosphorescent material for an organic light emitting device, which has low synthesis cost, simple synthesis process, no pollution, and high synthesis purity and efficiency.
Disclosure of Invention
The invention provides an organic iridium metal complex, a preparation method thereof and application thereof in preparing organic electroluminescent devices.
In order to achieve the purpose, the invention adopts the following technical scheme:
an organic iridium metal complex, the structural general formula of which is shown in chemical formula 1:
the left side of the transition metal Ir is an auxiliary ligand A
The right side is a main ligand C
Wherein: r1, R2, R3, R4, R5, R6, R7 each independently represent hydrogen, deuterium, amino, hydroxyl, halogen, cyano, alkyl, alkoxy, aryl or an aromatic heterocyclic group.
Further, the halogen is specifically one or more of F, Cl, Br and I, and is preferably F.
Further, the alkyl is one of C1-C8 alkyl;
the above-mentioned C1-C8 alkyl group is selected from a substituted or unsubstituted straight-chain alkyl group, a substituted or unsubstituted branched-chain alkyl group, a substituted or unsubstituted cycloalkyl group; and the substituents are independently selected from deuterium, amino, hydroxy, halogen, cyano;
further, the alkoxy is one of C1-C8 alkoxy;
the alkylene is one of C2-C6 alkylene;
the alkynyl is one of C2-C6 alkynyl;
the aryl is one of C6-C18 aryl;
the above aryl group is selected from an unsubstituted aryl group or an aryl group having at least one substituent;
further, the aromatic heterocyclic group is one of C4-C12 aromatic heterocyclic groups;
the above aromatic heterocyclic groups are independently selected from unsubstituted aromatic heterocyclic groups or aromatic heterocyclic groups having at least one substituent; and the substituent is independently selected from one or more of deuterium, amino, hydroxyl, halogen and cyano.
Preferably, the primary ligand C is selected from any one of the following structural formulas:
more preferably, the structural formula of the organic iridium metal complex is any one of the following structural formulas:
the invention also provides a preparation method of the organic iridium metal complex, which comprises the following steps:
(1) under the protection of nitrogen, mixing the compound A and iridium trichloride trihydrate, adding the mixture into a solvent I for heating reaction, performing suction filtration after the reaction is finished, leaching with water, absolute ethyl alcohol and petroleum ether in sequence, and drying to obtain a bridging ligand B;
(2) under the protection of nitrogen, mixing the bridged ligand B obtained in the step (1) with a compound C, adding the mixture into a solvent II for heating reaction, after the reaction is finished, sequentially performing suction filtration, alcohol washing, drying and silica gel column chromatography, and concentrating the filtrate to obtain the organic iridium metal complex shown in the chemical formula 1;
the synthetic route of the organic iridium metal complex shown in chemical formula 1 is as follows:
further, in the step (1), the molar ratio of the compound A to the iridium trichloride trihydrate is (2.5-4) to 1;
the solvent I is ethylene glycol ethyl ether aqueous solution, and the volume ratio of the ethylene glycol ethyl ether to the water is (2.5-4) to 1; the molar ratio of the ethylene glycol ethyl ether to the compound A is 73: 1;
further, in step (2), the molar ratio of compound C to bridging ligand B is (2.5-4): 1;
the solvent II is a mixed solution of ethylene glycol ethyl ether and anhydrous potassium carbonate; the molar ratio of the ethylene glycol ethyl ether to the anhydrous potassium carbonate is 35: 1;
the molar ratio of ethylene glycol ethyl ether to compound C is 350: 1;
further, in the step (1), the reaction temperature is 100-130 ℃, and the reaction time is 20-24 h.
Furthermore, in the step (2), the reaction temperature is 100-130 ℃, and the reaction time is 20-24 h.
The invention also provides application of the organic iridium metal complex in preparing organic electroluminescent devices.
Preferably, the organic electroluminescent device comprises: the organic electroluminescent device comprises a first electrode, an organic electroluminescent material layer and a second electrode; wherein the organic electroluminescent material layer includes the organic iridium metal complex of claim 1.
More preferably, the organic electroluminescent material layer comprises, in order by evaporation: one or more layers of a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron blocking layer, an electron transport layer, and an electron injection layer, and at least one of them comprises the organic iridium metal complex according to claim 1.
The invention has the beneficial effects that: the invention provides an organic iridium metal complex phosphor luminescent material and a preparation method thereof, the phosphor luminescent material is used as a complex with a novel structure, an organic metal compound is obtained by combining metal iridium with a specific heterocyclic ligand, and the phosphor luminescent material can obviously improve the luminous efficiency of an organic electroluminescent device after being applied to the organic electroluminescent device. The preparation method of the phosphor luminescent material provided by the invention has the characteristics of simple synthesis steps, mild condition requirements and high yield of target products, and solves the problems of high synthesis price and higher synthesis process requirements of the existing phosphor luminescent material.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Compound L001 was prepared by the following specific steps:
(1) a-001(85.2mmol, 21.73g) and IrCl were charged into a nitrogen-substituted reactor under a nitrogen atmosphere3·3H2O (28.4mmo1, 10g), 600mL of ethylene glycol ethyl ether and 200mL of purified water are refluxed at 120 ℃ for 24 hours under the nitrogen atmosphere, then the mixture is cooled to room temperature, precipitates are separated out, solid is obtained by suction filtration, and is sequentially leached by 50mL of water, 50mL of absolute ethyl alcohol and 50mL of petroleum ether and dried to obtain red powdery bridging ligand B-001(13.26g, the yield is 61%);
(2) adopting a nitrogen replacement reactor, adding B-001(8mmol, 11.78g) and C-001(24mmol, 2.37g) into the reactor under the nitrogen atmosphere, adding 270mL of ethylene glycol ethyl ether and 11.04g of potassium carbonate into the system, stirring for 24 hours at 120 ℃ under the nitrogen atmosphere, carrying out suction filtration, washing with alcohol, drying, using dichloromethane as an eluent, carrying out silica gel column chromatography, concentrating the filtrate, precipitating a solid, and carrying out suction filtration to finally obtain a red compound L001(6.33g, the yield is 49.5%).
Specifically, the reaction formulae of steps (1) to (2) are as follows:
the compound L001 was analyzed, and the specific results were as follows:
HPLC purity: greater than 99%.
Mass spectrum: calculated value 799.95; the test value was 800.23.
Elemental analysis:
the calculated values are: 64.56 percent of C; 3.91 percent of H; 3.50 percent of N; 4.00 percent of O; 24.03 percent of Ir;
the test values are: 64.55 percent of C; 3.90 percent of H; 3.51 percent of N; 4.01 percent of O; 24.04 percent of Ir.
The comparison of the calculated value and the test value proves that the measured value is basically consistent with the theoretical value, so that the organic iridium metal complex can be successfully synthesized by the technical scheme disclosed by the invention.
Example 2
The method for preparing the organic iridium metal complex phosphor luminescent material L015 comprises the following specific steps:
(1) a-015(85.2mmol, 24.81g) is added into a nitrogen displacement reactor in the nitrogen atmosphere,IrCl3·3H2O (28.4mmo1, 10g), 600mL of ethylene glycol ethyl ether and 200mL of purified water are refluxed at 120 ℃ for 24 hours under the atmosphere of nitrogen, then the mixture is cooled to room temperature, precipitates are separated out, solid is obtained by suction filtration, and is sequentially leached by 50mL of water, 50mL of absolute ethyl alcohol and 50mL of petroleum ether and dried to obtain red powdery bridging ligand B-015(14.46g, the yield is 63%);
(2) adopting a nitrogen replacement reactor, adding B-015(8mmol, 12.93g) and C-015(24mmol, 2.37g) into the reactor in a nitrogen atmosphere, adding 270mL of ethylene glycol ethyl ether and 11.04g of potassium carbonate into the system, stirring for 24 hours at 120 ℃ in the nitrogen atmosphere, carrying out suction filtration, washing with alcohol, drying, using dichloromethane as an eluent, carrying out silica gel column chromatography, concentrating the filtrate, precipitating a solid, and carrying out suction filtration to finally obtain a red compound L015(6.76g, the yield is 48.5%).
Specifically, the reaction formulae of steps (1) to (2) are as follows:
the compound L015 is subjected to detection analysis, and specific results are as follows:
HPLC purity: greater than 99%.
Mass spectrum: calculated value 871.91; the test value was 872.72.
Elemental analysis:
the calculated values are: 59.23 percent of C; 3.12 percent of H; 3.21 percent of N; 3.67 percent of O; 22.05 percent of Ir; 8.72 percent of F;
the test values are: 59.22 percent of C; 3.13 percent of H; 3.22 percent of N; 3.68 percent of O; 22.04 percent of Ir; f, 8.73 percent.
The comparison of the calculated value and the test value proves that the measured value is basically consistent with the theoretical value, so that the organic iridium metal complex can be successfully synthesized by the technical scheme disclosed by the invention.
Example 3
The compound with the number of L016 is prepared by the following specific synthetic steps:
(1) replacing the reactor with nitrogen, and adding into the reactor under nitrogen atmosphereA-016(85.2mmol, 21.73g), IrCl3·3H2O (28.4mmo1, 10g), 600mL of ethylene glycol ethyl ether and 200mL of purified water are refluxed at 120 ℃ for 24 hours under the nitrogen atmosphere, then the mixture is cooled to room temperature, precipitates are separated out, solid is obtained by suction filtration, and is sequentially leached by 50mL of water, 50mL of absolute ethyl alcohol and 50mL of petroleum ether and dried to obtain red powdery bridging ligand B-016(12.7g, the yield is 61%);
2) adopting a nitrogen replacement reactor, adding B-016(8mmol, 11.78g) and C-016(24mmol, 3.72g) into the reactor under the nitrogen atmosphere, adding 270mL of ethylene glycol ethyl ether and 11.04g of potassium carbonate into the system, stirring at 120 ℃ for 24 hours under the nitrogen atmosphere, carrying out suction filtration, washing with alcohol, drying, using dichloromethane as an eluent, carrying out silica gel column chromatography, concentrating the filtrate, precipitating a solid, and carrying out suction filtration to finally obtain a red compound L016(6.5g, the yield is 47.5%).
Specifically, the reaction formulae of steps (1) to (2) are as follows:
the compound L016 was analyzed and the specific results are as follows:
HPLC purity: greater than 99%.
Mass spectrum: calculated value 856.06; the test value was 857.17.
Elemental analysis:
the calculated values are: 65.94 percent of C; 4.59 percent of H; 3.27 percent of N; 3.74 percent of O; 22.45 percent of Ir;
the test values are: c, 65.95 percent; 4.58 percent of H; 3.26 percent of N; 3.75 percent of O; 22.44 percent of Ir.
The comparison of the calculated value and the test value proves that the measured value is basically consistent with the theoretical value, so that the organic iridium metal complex can be successfully synthesized by the technical scheme disclosed by the invention.
Example 4
The compound with the number L025 is prepared by the following specific synthetic steps:
(1) replacing the reactor with nitrogen gas, and introducing into the reactor under nitrogen gas atmosphereAdding A-025(85.2mmol, 26.53g) and IrCl3·3H2O (28.4mmo1, 10g), 600mL of ethylene glycol ethyl ether and 200mL of purified water are refluxed at 120 ℃ for 24 hours under the nitrogen atmosphere, then the mixture is cooled to room temperature, precipitates are separated out, solid is obtained by suction filtration, and is sequentially leached by 50mL of water, 50mL of absolute ethyl alcohol and 50mL of petroleum ether and dried to obtain red powdery bridging ligand B-025(14.21g, the yield is 59%);
(2) adopting a nitrogen replacement reactor, adding B-025(8mmol, 13.57g) and C-025(24mmol, 3.72g) into the reactor under the nitrogen atmosphere, adding 270mL of ethylene glycol ethyl ether and potassium carbonate (11.04g) into the system, stirring for 24 hours at 120 ℃ under the nitrogen atmosphere, carrying out suction filtration, washing with alcohol, drying, using dichloromethane as an eluent, carrying out silica gel column chromatography, concentrating the filtrate, precipitating a solid, and carrying out suction filtration to finally obtain a red compound L025(7.6g, yield 50%).
Specifically, the reaction formulae of steps (1) to (2) are as follows:
the compound L025 was subjected to detection analysis, and the specific results were as follows:
HPLC purity: greater than 99%.
Mass spectrum: calculated value 968.27; the test value was 969.34.
Elemental analysis:
the calculated values are: 68.23 percent of C; 5.73 percent of H; 2.89 percent of N; 3.30 percent of O; 19.85 percent of Ir;
the test values are: 68.24 percent of C; 5.72 percent of H; 2.88 percent of N; 3.31 percent of O; 19.84 percent of Ir.
The comparison of the calculated value and the test value proves that the measured value is basically consistent with the theoretical value, so that the organic iridium metal complex can be successfully synthesized by the technical scheme disclosed by the invention.
Example 5
The compound with the number of L035 was prepared by the following specific synthetic steps:
(1) replacing the reactor with nitrogen gas, and introducing into the reactor under nitrogen gas atmosphereAdding A-035(85.2mmol, 25.67g) and IrCl3·3H2O (28.4mmo1, 10g), 600mL of ethylene glycol ethyl ether and 200mL of purified water are refluxed at 120 ℃ for 24 hours under the nitrogen atmosphere, then the mixture is cooled to room temperature, precipitates are separated out, solid is obtained by suction filtration, and is sequentially leached by 50mL of water, 50mL of absolute ethyl alcohol and 50mL of petroleum ether and dried to obtain red powdery bridging ligand B-035(14.58g, the yield is 62%);
(2) by adopting a nitrogen replacement reactor, adding B-035(8mmol, 13.25g) and C-035(24mmol, 4.06g) into the reactor under the nitrogen atmosphere, adding 270mL of ethylene glycol ethyl ether and potassium carbonate (11.04g) into the system, stirring for 24 hours at 120 ℃ under the nitrogen atmosphere, carrying out suction filtration, washing with alcohol, drying, using dichloromethane as an eluent, carrying out silica gel column chromatography, carrying out solid precipitation after concentration on the filtrate, and carrying out suction filtration to finally obtain a red compound L035(7.31g, the yield is 47.5%).
Specifically, the reaction formulae of steps (1) to (2) are as follows:
the compound L035 was analyzed and the results were as follows:
HPLC purity: greater than 99%.
Mass spectrum: calculated value 962.17; the test value was 963.52.
Elemental analysis:
the calculated values are: 64.91 percent of C; 4.92 percent of H; 2.91 percent of N; 3.33 percent of O; 19.98 percent of Ir;
the test values are: c, 64.90 percent; 4.93 percent of H; 2.92 percent of N; 3.32 percent of O; 19.99 percent of Ir.
The comparison of the calculated value and the test value proves that the measured value is basically consistent with the theoretical value, so that the organic iridium metal complex can be successfully synthesized by the technical scheme disclosed by the invention.
Example 6
The compound with the number of L041 is prepared by the following specific synthetic steps:
(1) using a nitrogen replacement reactor, and reacting in a nitrogen atmosphereA-041(85.2mmol, 22.94g) and IrCl were added into the reactor3·3H2O (28.4mmo1, 10g), 600mL of ethylene glycol ethyl ether and 200mL of purified water are refluxed at 120 ℃ for 24 hours under the nitrogen atmosphere, then the mixture is cooled to room temperature, precipitates are separated out, solid is obtained by suction filtration, and is sequentially leached by 50mL of water, 50mL of absolute ethyl alcohol and 50mL of petroleum ether and dried to obtain red powdery bridging ligand B-041(13.67g, the yield is 63%);
(2) adopting a nitrogen replacement reactor, adding B-041(8mmol, 12.22) and C-041(24mmol, 4.06g) into the reactor under the nitrogen atmosphere, adding 270mL of ethylene glycol ethyl ether and potassium carbonate (11.04g) into the system, stirring for 24 hours at 120 ℃ under the nitrogen atmosphere, carrying out suction filtration, washing with alcohol, drying, using dichloromethane as an eluent, carrying out silica gel column chromatography, concentrating the filtrate, precipitating a solid, and carrying out suction filtration to finally obtain a red compound L041(7.02g, the yield is 48.9%).
Specifically, the reaction formulae of steps (1) to (2) are as follows:
the compound L041 is detected and analyzed, and the specific results are as follows:
HPLC purity: greater than 99%.
Mass spectrum: calculated value 898.14; the test value was 899.21.
Elemental analysis:
the calculated values are: 66.87 percent of C; 5.05 percent of H; 3.12 percent of N; 3.56 percent of O; 21.40 percent of Ir;
the test values are: c, 66.88 percent; 5.04 percent of H; 3.13 percent of N; 3.55 percent of O; 21.41 percent of Ir.
The comparison of the calculated value and the test value proves that the measured value is basically consistent with the theoretical value, so that the organic iridium metal complex can be successfully synthesized by the technical scheme disclosed by the invention.
Example 7
The compound numbered L046 was prepared by the following specific synthetic procedure:
(1) adopting a nitrogen replacement reactor, under the nitrogen atmosphere,a-046(85.2mmol, 21.73g), IrCl were added to the reactor3·3H2O (28.4mmo1, 10g), 600mL of ethylene glycol ethyl ether and 200mL of purified water are refluxed at 120 ℃ for 24 hours under the atmosphere of nitrogen, then the mixture is cooled to room temperature, precipitates are separated out, solid is obtained by suction filtration, and is sequentially leached by 50mL of water, 50mL of absolute ethyl alcohol and 50mL of petroleum ether and dried to obtain red powdery bridging ligand B-046(13.26g, the yield is 61%);
(2) adopting a nitrogen replacement reactor, adding B-046(8mmol, 11.78g) and C-046(24mmol, 4.39g) into the reactor under the nitrogen atmosphere, adding 270mL of ethylene glycol ethyl ether and potassium carbonate (11.04g) into the system, stirring for 24 hours at 120 ℃ under the nitrogen atmosphere, carrying out suction filtration, washing with alcohol, drying, using dichloromethane as an eluent, carrying out silica gel column chromatography, carrying out solid precipitation after concentration on the filtrate, and carrying out suction filtration to finally obtain a red compound L046(6.95g, the yield is 49.2%).
Specifically, the reaction formulae of steps (1) to (2) are as follows:
the compound L046 is detected and analyzed, and the specific results are as follows:
HPLC purity: greater than 99%.
Mass spectrum: calculated value 884.11; the test value was 885.28.
Elemental analysis:
the calculated values are: 66.57 percent of C; 4.90 percent of H; 3.17 percent of N; 3.62 percent of O; 21.74 percent of Ir;
the test values are: c, 66.56 percent; 4.91 percent of H; 3.18 percent of N; 3.61 percent of O; 21.73 percent of Ir.
The comparison of the calculated value and the test value proves that the measured value is basically consistent with the theoretical value, so that the organic iridium metal complex can be successfully synthesized by the technical scheme disclosed by the invention.
Example 8
The compound with the serial number of L061 is prepared by the following specific synthetic steps:
(1) using a nitrogen displacement reactor in a nitrogen atmosphereNext, A-061(85.2mmol, 21.73g), IrCl was charged to the reactor3·3H2O (28.4mmo1, 10g), 600mL of ethylene glycol ethyl ether and 200mL of purified water are refluxed at 120 ℃ for 24 hours under the nitrogen atmosphere, then the mixture is cooled to room temperature, precipitates are separated out, solid is obtained by suction filtration, and is sequentially leached by 50mL of water, 50mL of absolute ethyl alcohol and 50mL of petroleum ether and dried to obtain red powdery bridging ligand B-061(13.26g, the yield is 61%);
(2) adopting a nitrogen replacement reactor, adding B-061(8mmol, 11.77g) and C-061(24mmol, 5.68g) into the reactor in a nitrogen atmosphere, adding 270mL of ethylene glycol ethyl ether and 11.04g of potassium carbonate into the system, stirring for 24 hours at 120 ℃ in the nitrogen atmosphere, carrying out suction filtration, washing with alcohol, drying, using dichloromethane as an eluent, carrying out silica gel column chromatography, concentrating the filtrate, precipitating a solid, and carrying out suction filtration to finally obtain a red compound L061(7.3g, the yield is 48.7%).
Specifically, the reaction formulae of steps (1) to (2) are as follows:
the compound L061 was analyzed, and the specific results were as follows:
HPLC purity: greater than 99%.
Mass spectrum: calculated value 938.12; the test value was 939.24.
Elemental analysis:
the calculated values are: 69.14 percent of C; 3.98 percent of H; 2.99 percent of N; 3.41 percent of O; 20.49 percent of Ir;
the test values are: 69.15 percent of C; 3.99 percent of H; 2.98 percent of N; 3.40 percent of O; 20.48 percent of Ir.
The comparison of the calculated value and the test value proves that the measured value is basically consistent with the theoretical value, so that the organic iridium metal complex can be successfully synthesized by the technical scheme disclosed by the invention.
Example 9
The compound with the number of L093 is prepared by the following specific synthetic steps:
(1) replacing the reactor with nitrogen gas in the presence of nitrogenA-093(85.2mmol, 25.67g), IrCl were added to the reactor under an atmosphere3·3H2O (28.4mmo1, 10g), 600mL of ethylene glycol ethyl ether and 200mL of purified water are refluxed at 120 ℃ for 24 hours under the nitrogen atmosphere, then the mixture is cooled to room temperature, precipitates are separated out, solid is obtained by suction filtration, and is sequentially leached by 50mL of water, 50mL of absolute ethyl alcohol and 50mL of petroleum ether and dried to obtain red powdery bridging ligand B-093(15.29g, the yield is 65%);
(2) adopting a nitrogen replacement reactor, adding B-093(8mmol, 13.25g) and C-095(24mmol, 5.74g) into the reactor under a nitrogen atmosphere, adding 270mL of ethylene glycol ethyl ether and potassium carbonate (11.04g) into the system, stirring at 120 ℃ for 24 hours under the nitrogen atmosphere, carrying out suction filtration, washing with alcohol, drying, using dichloromethane as an eluent, carrying out silica gel column chromatography, concentrating the filtrate, precipitating a solid, and carrying out suction filtration to finally obtain a red compound L093(7.84g, 47.5% of yield).
Specifically, the reaction formulae of steps (1) to (2) are as follows:
the compound L093 was analyzed, and the specific results were as follows:
HPLC purity: greater than 99%.
Mass spectrum: calculated value 1032.31; the test value was 1033.24.
Elemental analysis:
the calculated values are: 66.32 percent of C; 5.57 percent of H; 2.71 percent of N; 3.10 percent of O; 18.62 percent of Ir; 3.68 percent of F;
the test values are: 66.33 percent of C; 5.56 percent of H; 2.72 percent of N; 3.11 percent of O; 18.61 percent of Ir; f, 3.69 percent.
The comparison of the calculated value and the test value proves that the measured value is basically consistent with the theoretical value, so that the organic iridium metal complex can be successfully synthesized by the technical scheme disclosed by the invention.
Example 10
The compound with the number of L101 is prepared by the following specific synthetic steps:
(1) by usingThe reactor was purged with nitrogen, and A-101(85.2mmol, 22.94g) and IrCl were added to the reactor under a nitrogen atmosphere3·3H2O (28.4mmo1, 10g), 600mL of ethylene glycol ethyl ether and 200mL of purified water are refluxed at 120 ℃ for 24 hours under the nitrogen atmosphere, then the mixture is cooled to room temperature, precipitates are separated out, solid is obtained by suction filtration, and is sequentially leached by 50mL of water, 50mL of absolute ethyl alcohol and 50mL of petroleum ether and dried to obtain red powdery bridging ligand B-101(13.66g, the yield is 63%);
(2) adopting a nitrogen replacement reactor, adding B-101(8mmol, 12.22g) and C-101(24mmol, 5.74g) into the reactor under the nitrogen atmosphere, adding 270mL of ethylene glycol ethyl ether and potassium carbonate (11.04g) into the system, stirring for 24 hours at 120 ℃ under the nitrogen atmosphere, carrying out suction filtration, washing with alcohol, drying, using dichloromethane as an eluent, carrying out silica gel column chromatography, carrying out solid precipitation after filtrate concentration, and carrying out suction filtration to finally obtain a red compound L101(7.66g, yield 49.5%).
Specifically, the reaction formulae of steps (1) to (2) are as follows:
the compound L101 was analyzed, and the specific results are as follows:
HPLC purity: greater than 99%.
Mass spectrum: calculated value 968.27; the test value was 969.31.
Elemental analysis:
the calculated values are: 68.23 percent of C; 5.73 percent of H; 2.89 percent of N; 3.30 percent of O; 19.85 percent of Ir; 3.68 percent of F;
the test values are: 68.24 percent of C; 5.72 percent of H; 2.88 percent of N; 3.31 percent of O; 19.86 percent of Ir; f, 3.67 percent.
The comparison of the calculated value and the test value proves that the measured value is basically consistent with the theoretical value, so that the organic iridium metal complex can be successfully synthesized by the technical scheme disclosed by the invention.
Example 11
The compound with the number of L108 is prepared by the following specific synthetic steps:
(1) the reactor was purged with nitrogen and A-108(85.2mmol, 25.67g), IrCl were added to the reactor under a nitrogen atmosphere3·3H2O (28.4mmo1, 10g), 600mL of ethylene glycol ethyl ether and 200mL of purified water are refluxed at 120 ℃ for 24 hours under the nitrogen atmosphere, then the mixture is cooled to room temperature, precipitates are separated out, solid is obtained by suction filtration, and is sequentially leached by 50mL of water, 50mL of absolute ethyl alcohol and 50mL of petroleum ether and dried to obtain red powdery bridging ligand B-108(15.29g, the yield is 65%);
(2) adopting a nitrogen replacement reactor, adding B-108(8mmol, 13.25g) and C-108(24mmol, 5.09g) into the reactor under the nitrogen atmosphere, adding 270mL of ethylene glycol ethyl ether and potassium carbonate (11.04g) into the system, stirring for 24 hours at 120 ℃ under the nitrogen atmosphere, carrying out suction filtration, washing with alcohol, drying, using dichloromethane as an eluent, carrying out silica gel column chromatography, carrying out solid precipitation after concentration on the filtrate, and carrying out suction filtration to finally obtain a red compound L108(7.23g, yield 45%).
Specifically, the reaction formulae of steps (1) to (2) are as follows:
the compound L108 was analyzed, and the specific results were as follows:
HPLC purity: greater than 99%.
Mass spectrum: calculated value 1004.25; the test value was 1004.60.
Elemental analysis:
the calculated values are: c, 65.78; h is 5.32; f is 3.78; 19.14 parts of Ir; n is 2.79; o is 3.19.
The test values are: c, 65.79; h is 5.33; f is 3.79; 19.15 parts of Ir; 2.78 of N; o is 3.16.
The comparison of the calculated value and the test value proves that the measured value is basically consistent with the theoretical value, so that the organic iridium metal complex can be successfully synthesized by the technical scheme disclosed by the invention.
The preparation methods of other organic iridium complexes are the same as those described above, and are not repeated here, and the mass spectrum and the molecular formula of other organic iridium complexes are shown in table 1 below:
TABLE 1 molecular formula and Mass Spectrometry of other organic Iridium Metal complexes
| Complexes | Molecular formula | Calculated mass spectrum | Mass spectrometric test values |
| L008 | C47H39IrN2O2 | 856.06 | 857.13 |
| L027 | C53H45D6IrN2O2 | 946.26 | 947.62 |
| L050 | C53H49F2IrN2O2 | 976.20 | 977.18 |
| L063 | C57H51IrN2O2 | 988.26 | 989.51 |
| L087 | C49H31D12IrN2O2 | 896.19 | 897.23 |
| L098 | C55H51F4IrN2O2 | 1040.24 | 1040.58 |
| L120 | C53H47F4IrN2O2 | 1012.18 | 1012.49 |
EXAMPLE 12 electroluminescent device implementation
Coating with a thickness of
The ITO glass substrate of (1) was washed in distilled water for 2 times, ultrasonically for 30 minutes, repeatedly washed in distilled water for 2 times, ultrasonically for 10 minutes, and after the washing with distilled water was completed, solvents such as isopropyl alcohol, acetone, and methanol were ultrasonically washed in this order, dried, transferred to a plasma cleaning machine, washed for 5 minutes, and sent to an evaporation coater.
First, vapor deposition is carried out on the ITO (anode)
Followed by evaporation
Host substance 4,4'-N, N' -biphenyl dicarbazole ('CBP') and doping substance complex L00195:5 weight ratio are mixed for evaporation
Vapor deposition electron transport layer
Vapor deposition of electron injection layer
Evaporation cathode
And (4) preparing the organic electroluminescent device.
The luminous characteristics of the organic electroluminescent device obtained above were tested using a KEITHLEY model 2400 source measurement unit and a CS-2000 spectroradiometer to evaluate the driving voltage, lifetime, and current efficiency of the device.
Referring to the preparation method of the organic electroluminescent device, the organic iridium metal complex L001 is replaced by L008, L015, L016, L025, L027, L035, L041, L046, L050, L061, L063, L087, L093, L098, L101, L108 and L120 respectively, and the organic electroluminescent device of the corresponding organic iridium metal complex is prepared.
Comparative example 1:
an organic electroluminescent device in which an organic metal complex doped in a light-emitting layer has the following structure was prepared in the same manner as in example 11:
and the same examination as in example 12 was performed on the prepared organic electroluminescent device, and the results are shown in table 2 below.
Table 2 results of measuring performance of electroluminescent devices of example 12, comparative example 1 and doped with other organic iridium metal complexes
As can be seen from Table 2, the organic electroluminescent device prepared by using the organic iridium metal complex provided by the invention as a luminescent layer doping material is superior to the organic electroluminescent device of the comparative complex, the driving voltage is obviously reduced, and the current efficiency and the service life are obviously improved.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. An organic iridium metal complex is characterized in that the structural general formula of the organic iridium metal complex is shown as chemical formula 1:
wherein: r1, R2, R3, R4, R5, R6 and R7 each independently represent hydrogen, deuterium, amino, halogen, C1-C8 alkyl, C6-C18 aryl or C4-C12 aromatic heterocyclic group.
2. The organic iridium metal complex according to claim 1,
the halogen is one or more of F, Cl, Br and I, and is preferably F.
The C1-C8 alkyl is selected from substituted or non-substituted straight-chain alkyl, substituted or non-substituted branched-chain alkyl, substituted or non-substituted cycloalkyl; and substituents are selected from deuterium, amino, hydroxy, halogen, cyano;
the C6-C18 aryl is selected from substituted or unsubstituted aryl;
the C4-C12 aromatic heterocyclic group is selected from substituted or unsubstituted aromatic heterocyclic groups; and the substituents are selected from deuterium, amino, hydroxy, halogen, cyano.
3. A method for producing the organic iridium metal complex as claimed in claim 1 or 2, comprising the steps of:
(1) under the protection of nitrogen, mixing the compound A and iridium trichloride trihydrate, adding the mixture into a solvent I for heating reaction, performing suction filtration after the reaction is finished, leaching with water, absolute ethyl alcohol and petroleum ether in sequence, and drying to obtain a bridging ligand B;
(2) under the protection of nitrogen, mixing the bridged ligand B obtained in the step (1) with a compound C, adding the mixture into a solvent II for heating reaction, after the reaction is finished, sequentially performing suction filtration, alcohol washing, drying and silica gel column chromatography, and concentrating the filtrate to obtain the organic iridium metal complex shown in the chemical formula 1;
the synthetic route of the organic iridium metal complex shown in chemical formula 1 is as follows:
4. the method for producing an organic iridium metal complex according to claim 3, wherein in the step (1), the molar ratio of the compound A to iridium trichloride trihydrate is (2.5-4): 1;
the solvent I is ethylene glycol ethyl ether aqueous solution, and the volume ratio of the ethylene glycol ethyl ether to the water is (2.5-4) to 1;
the molar ratio of ethylene glycol ethyl ether to compound a was 73: 1.
5. The process for producing an organic iridium metal complex according to claim 3, wherein in the step (2), the molar ratio of the compound C to the bridging ligand B is (2.5 to 4): 1;
the solvent II is a mixed solution of ethylene glycol ethyl ether and anhydrous potassium carbonate;
the molar ratio of the ethylene glycol ethyl ether to the anhydrous potassium carbonate is 35: 1;
the molar ratio of ethylene glycol ethyl ether to compound C was 350: 1.
6. The method of preparing an organic iridium metal complex according to claim 3, wherein the reaction temperature in step (1) is 100 ℃ to 130 ℃ and the reaction time is 20 to 24 hours.
7. The method of preparing an organic iridium metal complex according to claim 3, wherein the reaction temperature in step (2) is 100 ℃ to 130 ℃ and the reaction time is 20 to 24 hours.
8. Use of the organic iridium metal complex as claimed in claim 1 or 2 in the preparation of an organic electroluminescent device.
9. An organic electroluminescent device is characterized by comprising a first electrode, an organic electroluminescent material layer and a second electrode which are sequentially evaporated; wherein the organic electroluminescent material layer includes the organic iridium metal complex of claim 1 or 2.
10. The organic electroluminescent device according to claim 9, wherein the organic electroluminescent material layer comprises one or more layers selected from a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron blocking layer, an electron transport layer, and an electron injection layer, which are sequentially evaporated, and at least one of the layers comprises the organic iridium metal complex according to claim 1 or 2.
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