CN110684053B - Complex and preparation method thereof, phosphorescent material, organic electroluminescent device, display screen and solar cell - Google Patents

Complex and preparation method thereof, phosphorescent material, organic electroluminescent device, display screen and solar cell Download PDF

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CN110684053B
CN110684053B CN201911216391.XA CN201911216391A CN110684053B CN 110684053 B CN110684053 B CN 110684053B CN 201911216391 A CN201911216391 A CN 201911216391A CN 110684053 B CN110684053 B CN 110684053B
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王辉
李小龙
李明
李建行
刘志远
段伟伟
马晓宇
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The invention relates to the field of organic photoelectric materials, and particularly discloses a complex and a preparation method thereof, a phosphorescent material, an organic electroluminescent device, a display screen and a solar cell, wherein the complex has the following structure:

Description

Complex and preparation method thereof, phosphorescent material, organic electroluminescent device, display screen and solar cell
Technical Field
The invention relates to the field of organic photoelectric materials, in particular to a complex and a preparation method thereof, a phosphorescent material, an organic electroluminescent device, a display screen and a solar cell.
Background
Electroluminescent devices are widely used in the field of electronic product manufacture as a display device that emits light when an electroluminescent material is excited. Electroluminescent devices can be classified into ac and dc types according to the excitation voltage, and both can be manufactured using a powdered or thin film electroluminescent material. The technical key point of improving the performance of the electroluminescent device is to improve the photochromic purity and efficiency of the electroluminescent material.
In general, a phosphorescent material has a greater luminous efficiency than a fluorescent material, and thus, the phosphorescent material is mostly used in fabricating an organic electroluminescent device. However, the above technical solutions have the following disadvantages in practical use: the existing phosphorescent material has the problem of low luminous efficiency.
Disclosure of Invention
The embodiment of the invention aims to provide a complex and a preparation method thereof, a phosphorescent material, an organic electroluminescent device, a display screen and a solar cell, so as to solve the problem that the luminous efficiency of the existing phosphorescent material provided in the background technology is insufficient.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
a complex has a structure shown in formula I:
Figure BDA0002299636630000011
wherein
m is 0, 1 or 2, n is 1, 2 or 3, and m + n is 3;
R1、R2、R3、R4、R5and R6Each independently selected from hydrogen, deuterium, nitro, amino, hydroxyl, halogen, cyano, mercapto, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C1-C8 alkoxy, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C4-C12 aromatic heterocyclic group, substituted or unsubstituted C10-C18 condensed ring group, and substituted or unsubstituted C5-C15 spiro ring group.
As a further scheme of the invention: in the formula I, R1And R2Each independently represents a mono-substituent, a di-substituent, a tri-substituent, a tetra-substituent or no substituent, R3、R4And R6Each independently represents a mono-substituent, a di-substituent or no substituent, R5Represents a mono-substituent, a di-substituent, a tri-substituent or no substituent.
As a still further scheme of the invention: in the formula I, R1、R2、R3、R4、R5And R6The substituent position is any position of the ring.
As a still further scheme of the invention: the alkyl is straight-chain alkyl, branched-chain alkyl, cycloalkyl, straight-chain alkyl substituted by at least 1 substituent, branched-chain alkyl substituted by at least 1 substituent or cycloalkyl substituted by at least 1 substituent; wherein, the substituent is one or more of deuterium, nitro, amino, hydroxyl, halogen, cyano, carbonyl or sulfydryl.
As a still further scheme of the invention: the above-mentioned aryl group is an unsubstituted aryl group or an aryl group substituted with at least 1 substituent; wherein, the substituent is one or more of deuterium, nitro, amino, hydroxyl, halogen, cyano, carbonyl or sulfydryl.
As a still further scheme of the invention: the above aromatic heterocyclic group is an unsubstituted heteroaryl group or an aromatic heterocyclic group substituted with at least 1 substituent; wherein the heteroatom in the heteroaryl group is nitrogen, sulfur or oxygen; the substituents are independently selected from halogen, deuterium, amino, cyano, nitro, hydroxyl or mercapto.
As a still further scheme of the invention: in the formula I, R1、R2、R3、R4、R5And R6Each independently forms a substituted or unsubstituted C3-C30 aliphatic ring, a substituted or unsubstituted C6-C18 aromatic ring, a substituted or unsubstituted C4-C18 aromatic heterocycle, a substituted or unsubstituted C10-C18 fused ring, or a substituted or unsubstituted C5-C18 spiro ring with the ring; wherein, the substituent on the substituent group is at least one or more selected from hydrogen, deuterium, nitro, amino, hydroxyl, halogen, cyano, carbonyl or sulfydryl.
As a still further scheme of the invention: r1And R2、R3And R4、R5And R6Form a substituted or unsubstituted C3-C18 aliphatic ring, a substituted or unsubstituted C6-C18 aromatic ring, a substituted or unsubstituted C4-C18 aromatic heterocycle, a substituted or unsubstituted C10-C18 fused ring, or a substituted or unsubstituted C5-C18 spiro ring; wherein, the substituent on the substituent group is at least one or more selected from deuterium, nitro, amino, hydroxyl, halogen, cyano, carbonyl or sulfydryl.
As a still further scheme of the invention: the hydrogen in the above groups or substituents may be deuterated.
As a still further scheme of the invention: the complex is selected from any one of the following structures:
Figure BDA0002299636630000031
wherein R is1、R2、R3、R4、R5And R6The radicals and their number of substituents are as defined in formula I and are not described in detail here.
Preferably, the complex has a structure shown in formula 3.
Preferably, the complex has any one of the following specific structures:
Figure BDA0002299636630000041
Figure BDA0002299636630000051
Figure BDA0002299636630000061
Figure BDA0002299636630000071
Figure BDA0002299636630000081
Figure BDA0002299636630000091
Figure BDA0002299636630000101
Figure BDA0002299636630000111
Figure BDA0002299636630000121
Figure BDA0002299636630000131
Figure BDA0002299636630000141
Figure BDA0002299636630000151
Figure BDA0002299636630000161
Figure BDA0002299636630000171
Figure BDA0002299636630000181
Figure BDA0002299636630000191
Figure BDA0002299636630000201
Figure BDA0002299636630000211
Figure BDA0002299636630000221
Figure BDA0002299636630000231
Figure BDA0002299636630000241
it should be noted that, only some specific structural forms are listed above, but the series of complexes are not limited to the above molecular structures, and any simple group, substituted group and substituted position can be simply transformed to obtain other specific molecular structures, which are not described in detail herein.
It is a further object of an embodiment of the present invention to provide a method for preparing a complex of any one of the above, comprising the steps of:
1) providing a compound X selected from any one of the following structures:
Figure BDA0002299636630000251
2) fully reacting the compound X provided in the step 1) with iridium trichloride to obtain an intermediate B;
3) fully reacting the intermediate B obtained in the step 2) with silver trifluoromethanesulfonate to obtain an intermediate C;
4) providing a compound Y selected from any one of the following structures:
Figure BDA0002299636630000252
5) fully reacting the intermediate C obtained in the step 3) with the compound Y provided in the step 4) to obtain the complex shown in the formula I.
Wherein R is1、R2、R3、R4、R5And R6The radicals and their number of substituents are as defined in formula I and are not described in detail here.
As a still further scheme of the invention: in the full reaction of the compound X provided in the step 1) and iridium trichloride, the molar ratio of the compound X to the iridium trichloride is 1-5: 0.8-1.2.
Preferably, in the full reaction of the compound X provided in the step 1) and iridium trichloride, a solvent is a mixed solution of ethylene glycol ethyl ether and water, and the ratio of the ethylene glycol ethyl ether to the water is 3: 1; the dosage of the solvent is 15-30 times of the mass of the iridium trichloride.
As a still further scheme of the invention: in the step of fully reacting the intermediate B obtained in the step 2) with silver trifluoromethanesulfonate, the molar ratio of the intermediate B to the silver trifluoromethanesulfonate is 0.9-1.1: 2-5.
As a still further scheme of the invention: in the step of fully reacting the intermediate C obtained in the step 3) with the compound Y provided in the step 4), the molar ratio of the intermediate C to the compound Y is 1.9-2.1: 2-4.
As a still further scheme of the invention: the specific synthetic route of the preparation method of the complex shown in the formula 1 is as follows:
Figure BDA0002299636630000271
as a still further scheme of the invention: the specific synthetic route of the preparation method of the complex shown in the formula 2 is as follows:
Figure BDA0002299636630000281
as a still further scheme of the invention: the specific synthetic route of the preparation method of the complex shown in the formula 3 is as follows:
Figure BDA0002299636630000291
another object of the embodiments of the present invention is to provide a complex prepared by the above preparation method of the complex.
It is another object of the embodiments of the present invention to provide a phosphorescent material, which comprises the above complex partially or completely.
It is another object of an embodiment of the present invention to provide an organic electroluminescent device, which partially includes the above-mentioned phosphorescent material.
As a still further scheme of the invention: the organic electroluminescent device includes: the organic electroluminescent device comprises a first electrode, a second electrode and an organic layer arranged between the first electrode and the second electrode, wherein the organic layer is a light-emitting layer and contains the phosphorescent material; the phosphorescent material partially or completely comprises the complex, and the complex is in a single form or is mixed with other substances and exists in an organic layer.
As a still further scheme of the invention: the organic layer at least comprises one or more of a hole injection layer, a hole transport layer, a layer with hole injection and hole transport functions, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a layer with electron transport and electron injection functions.
As a still further scheme of the invention: the organic layer of the organic electroluminescent device comprises a main material and a doping material, wherein the doping material is the complex provided by the embodiment of the invention, and the mixing ratio of the main material to the doping material is 90-99.5:0.5-10 according to the mass ratio.
Another object of the embodiments of the present invention is to provide a display panel, which partially includes the above organic electroluminescent device.
Another object of the embodiments of the present invention is to provide a solar cell, which partially includes the above organic electroluminescent device.
Another object of the embodiments of the present invention is to provide an application of the organic electroluminescent device in the preparation of organic solar cells, electronic paper, organic photoreceptors or organic thin film transistors. The organic electroluminescent device provided by the embodiment of the invention can be used for preparing products such as a luminescent device, an organic solar cell, electronic paper, an organic photoreceptor or an organic thin film transistor.
Compared with the prior art, the invention has the beneficial effects that:
the complex provided by the embodiment of the invention has good luminous efficiency, the wavelength of the complex is adjusted by selecting the ligand of a specific heterocycle for combination, the luminous efficiency of the obtained complex can be improved after the complex is prepared into an organic electroluminescent device, and the service life is long.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
A complex I-1, namely the complex numbered I-1, is synthesized by the following reaction formula:
Figure BDA0002299636630000311
in this example, the specific synthesis procedure of the complex I-1 is as follows:
1) a compound of formula A-1 (18.01g, 60mmol) and IrC1 were added to a reactor under a nitrogen atmosphere3·3H2O (7.05g, 20mmo1), adding a mixed solution consisting of 240mL of ethylene glycol ethyl ether and 80mL of purified water, refluxing for 24 hours under the protection of nitrogen, cooling to room temperature, separating out a precipitate, carrying out suction filtration on the precipitate to obtain a solid, washing the solid with water, absolute ethyl alcohol and petroleum ether in sequence, and drying to obtain a yellow powdery intermediate B-1 (the mass is 8.76g, and the yield is 53%) shown as a formula B-1;
2) weighing the intermediate B-1(8.26g and 5mmol) shown in the formula B-1 obtained in the step 1) in a nitrogen atmosphere, adding the intermediate B-1 into a container, adding silver trifluoromethanesulfonate (3.86g and 15mmol), adding 150mL of dichloromethane into the system, adding 50mL of methanol, refluxing for 24 hours in the nitrogen atmosphere, cooling to room temperature, performing column chromatography (short column) to obtain a filtrate, concentrating the filtrate until a solid is separated out, and obtaining a yellow powdery intermediate C-1 shown in the formula C-1 (the mass is 8.39g and the yield is 85%);
3) weighing the intermediate C-1(7.90g and 8mmol) shown in the formula C-1 obtained in the step 2) in a nitrogen atmosphere, adding the intermediate C-1 into a reactor, adding the compound shown in the formula A-1 (7.20g and 24mmol), adding 160mL of absolute ethyl alcohol into the system, refluxing for 24 hours in the nitrogen atmosphere, carrying out suction filtration, washing with alcohol, drying, carrying out silica gel column chromatography by using dichloromethane as a solvent, and concentrating the filtrate until a solid is separated out to obtain the yellow complex I-1 (the mass is 1.57g, and the yield is 18%).
The complex I-1 is detected and analyzed, and the specific result is as follows:
HPLC purity: greater than 99%.
Mass spectrum: calculated value 1090.21; the test value was 1090.13.
Elemental analysis:
the calculated values are: 62.80 percent of C; h, 3.05 percent; 17.63 percent of Ir; 7.71 percent of N; 8.81 percent of O;
the test values are: 62.81 percent of C; 3.06 percent of H; 17.64 percent of Ir; 7.70 percent of N; 8.79 percent of O.
Example 2
A complex I-7, namely the complex numbered I-7, is synthesized by the following reaction formula:
Figure BDA0002299636630000331
in this example, the specific synthesis procedure of the complex I-7 is as follows:
1) a compound of the formula A-7 (15g, 50mmol) was charged with IrC1 under a nitrogen atmosphere3·3H2O (7.05g, 20mmo1), adding a mixed solution composed of 300mL of ethylene glycol ethyl ether and 100mL of purified water, refluxing for 24 hours under the protection of nitrogen, cooling to room temperature, separating out a precipitate, performing suction filtration on the precipitate to obtain a solid, washing the solid with water, absolute ethyl alcohol and petroleum ether in sequence, and drying to obtain a yellow powdery intermediate B-7 (the mass is 6.94g, the yield is 42%) shown in the formula B-7;
2) weighing intermediate B-7(6.61g and 4mmol) shown in formula B-7 obtained in the step 1) in a nitrogen atmosphere, adding the intermediate B-7 into a container, adding silver trifluoromethanesulfonate (2.63g and 10mmol), adding 90mL of dichloromethane into the system, adding 30mL of methanol, refluxing for 24 hours in the nitrogen atmosphere, cooling to room temperature, performing column chromatography (short column) to obtain filtrate, concentrating the filtrate until solid is separated out, and obtaining intermediate C-7 shown in formula C-7 (the mass is 7.50g and the yield is 95%) in a yellow powder shape;
3) weighing the intermediate C-7(6.91g and 7mmol) shown in the formula C-7 obtained in the step 2) in a nitrogen atmosphere, adding the intermediate C-7 into a reactor, adding the compound shown in the formula D-7 (3.26g and 21mmol), adding 140mL of absolute ethyl alcohol into the system, refluxing for 24 hours in the nitrogen atmosphere, carrying out suction filtration, washing with alcohol, drying, carrying out silica gel column chromatography by using dichloromethane as a solvent, and concentrating the filtrate until a solid is separated out to obtain the yellow complex I-7 (the mass is 1.79g and the yield is 27%).
The complex I-7 is detected and analyzed, and the specific result is as follows:
HPLC purity: greater than 99%.
Mass spectrum: calculated value 945.19; the test value was 945.24.
Elemental analysis:
the calculated values are: 62.28 percent of C; 3.20 percent of H; 20.34 percent of Ir; 7.41 percent of N; 6.77 percent of O;
the test values are: 62.28 percent of C; 3.21 percent of H; 20.35 percent of Ir; 7.40 percent of N; o is 6.76 percent.
Example 3
A complex I-41, i.e., the complex numbered I-41, is synthesized by the reaction scheme shown in the following steps:
Figure BDA0002299636630000351
in this example, the specific synthetic procedure for the complex I-41 is as follows:
1) a compound of the formula D-41 (7.44g, 44mmol) and IrC1 were charged to the reactor under a nitrogen atmosphere3·3H2O (7.05g, 20mmo1), adding a mixed solution composed of 210mL of ethylene glycol ethyl ether and 70mL of purified water, refluxing for 24 hours under the protection of nitrogen, cooling to room temperature, separating out a precipitate, performing suction filtration on the precipitate to obtain a solid, washing the solid with water, absolute ethyl alcohol and petroleum ether in sequence, and drying to obtain a yellow powdery intermediate B-41 (the mass is 6.54g, the yield is 58%) shown as a formula B-41;
2) weighing the intermediate B-41(5.64g and 5mmol) shown in the formula B-41 obtained in the step 1) in a nitrogen atmosphere, adding the intermediate B-41 into a container, adding silver trifluoromethanesulfonate (3.94g and 15mmol), adding 150mL of dichloromethane into the system, adding 50mL of methanol, refluxing for 24 hours in the nitrogen atmosphere, cooling to room temperature, performing column chromatography (short column) to obtain a filtrate, concentrating the filtrate until a solid is separated out, and obtaining a yellow powdery intermediate C-41 shown in the formula C-41 (the mass is 6.66g and the yield is 90%);
3) weighing the intermediate C-41(6.66g and 9mmol) shown in the formula C-41 obtained in the step 2) in a nitrogen atmosphere, adding the intermediate C-41 into a reactor, adding the compound shown in the formula A-41 (6.75g and 22.5mmol), adding 130mL of absolute ethyl alcohol into the system, refluxing for 24 hours in the nitrogen atmosphere, carrying out suction filtration, washing with alcohol, drying, carrying out silica gel column chromatography by using dichloromethane as a solvent, and concentrating the filtrate until solid is separated out to obtain yellow complex I-41 (the mass is 1.19g, and the yield is 16%).
The complex I-41 is detected and analyzed, and the specific result is as follows:
HPLC purity: greater than 99%.
Mass spectrum: calculated value 828.21; the test value was 828.28.
Elemental analysis:
the calculated values are: 62.38 percent of C; 3.77 percent of H; 23.22 percent of Ir; 6.77 percent of N; 3.86 percent of O;
the test values are: 62.36 percent of C; 3.75 percent of H; 23.24 percent of Ir; 6.78 percent of N; o is 3.87 percent.
Example 4
A complex I-127, namely the complex numbered I-127, is synthesized by the reaction scheme shown in the following steps:
Figure BDA0002299636630000371
in this example, the specific synthetic procedure for the complex I-127 is as follows:
1) a compound of the formula D-127 (12.44g, 48mmol) and IrC1 were charged to the reactor under a nitrogen atmosphere3·3H2O(705g, 20mmo1), adding a mixed solution composed of 240mL of ethylene glycol ethyl ether and 80mL of purified water, refluxing for 24 hours under the protection of nitrogen atmosphere, cooling to room temperature, separating out a precipitate, carrying out suction filtration on the precipitate to obtain a solid, washing the solid with water, absolute ethyl alcohol and petroleum ether in sequence, and drying to obtain a yellow powdery intermediate B-127 (the mass is 6.40g, the yield is 43%) shown as a formula B-127;
2) weighing intermediate B-127(6.48g and 4mmol) shown in formula B-127 obtained in the step 1) in a nitrogen atmosphere, adding the intermediate B-127 into a container, adding silver trifluoromethanesulfonate (3.15g and 12mmol), adding 90mL of dichloromethane into the system, adding 30mL of methanol, refluxing for 24 hours in the nitrogen atmosphere, cooling to room temperature, performing column chromatography (short column) to obtain filtrate, concentrating the filtrate until solid is separated out, and obtaining intermediate C-127 (the mass is 7.07g and the yield is 96%) shown in formula C-127 as yellow powder;
3) weighing the intermediate C-127(6.44g, 7mmol) shown in the formula C-127 obtained in the step 2) in a nitrogen atmosphere, adding the intermediate C-127 into a reactor, adding the compound shown in the formula A-127 (6.60g, 21mmol), adding 130mL of absolute ethyl alcohol into the system, refluxing for 24 hours in the nitrogen atmosphere, carrying out suction filtration, washing with alcohol, drying, carrying out silica gel column chromatography by using dichloromethane as a solvent, and concentrating the filtrate until a solid is separated out to obtain the yellow complex I-127 (the mass is 1.86g, and the yield is 26%).
The complex I-127 is detected and analyzed, and the specific result is as follows:
HPLC purity: greater than 99%.
Mass spectrum: calculated value 1022.32; the test value was 1022.30.
Elemental analysis:
the calculated values are: 68.15 percent of C; 4.44 percent of H; 18.80 percent of Ir; 5.48 percent of N; 3.13 percent of O;
the test values are: 68.18 percent of C; 4.42 percent of H; 18.81 percent of Ir; 5.49 percent of N; 3.10 percent of O.
Example 5
A complex I-161, numbered I-161, is synthesized according to the following reaction scheme:
Figure BDA0002299636630000391
in this example, the specific synthesis steps of the complex I-161 are as follows:
1) a compound of the formula D-161 (12.48g, 66mmol) and IrC1 were charged to the reactor under a nitrogen atmosphere3·3H2O (7.05g, 20mmo1), adding a mixed solution composed of 210mL of ethylene glycol ethyl ether and 70mL of purified water, refluxing for 24 hours under the protection of nitrogen, cooling to room temperature, separating out a precipitate, performing suction filtration on the precipitate to obtain a solid, washing the solid with water, absolute ethyl alcohol and petroleum ether in sequence, and drying to obtain a yellow powdery intermediate B-161 shown as a formula B-161 (the mass is 5.80g, the yield is 48%);
2) weighing an intermediate B-161(5.44g, 4.5mmol) shown in the formula B-161 obtained in the step 1) in a nitrogen atmosphere, adding the intermediate B-161 into a container, adding silver trifluoromethanesulfonate (2.36g, 9mmol), adding 150mL of dichloromethane into the system, adding 50mL of methanol, refluxing for 24 hours under the protection of the nitrogen atmosphere, cooling to room temperature, performing column chromatography (short column) to obtain a filtrate, concentrating the filtrate until a solid is separated out, and obtaining a yellow powdery intermediate C-161 (the mass is 6.11g, and the yield is 87%) shown in the formula C-161;
3) weighing the intermediate C-161(5.46g, 7mmol) shown in the formula C-161 obtained in the step 2) in a nitrogen atmosphere, adding the intermediate C-161 (6.30g, 21mmol) into a reactor, adding the compound shown in the formula A-161 into the reactor, adding 120mL of absolute ethyl alcohol into the system, refluxing for 24 hours in the nitrogen atmosphere, carrying out suction filtration, washing with alcohol, drying, carrying out silica gel column chromatography by using dichloromethane as a solvent, and concentrating the filtrate until a solid is separated out to obtain the yellow complex I-161 (the mass is 0.97g, and the yield is 16%).
The complex I-161 is detected and analyzed, and the specific result is as follows:
HPLC purity: greater than 99%.
Mass spectrum: calculated value 868.31; the test value was 868.39.
Elemental analysis:
the calculated values are: 62.26 percent of C; 5.45 percent of H; 22.14 percent of Ir; 6.45 percent of N; 3.69 percent of O;
the test values are: 62.27 percent of C; 5.46 percent of H; 22.15 percent of Ir; 6.43 percent of N; and 3.68 percent of O.
Example 6
A complex I-168, namely the complex numbered I-168, is synthesized by the reaction formula:
Figure BDA0002299636630000411
in this example, the specific synthesis steps of the complex I-168 are as follows:
1) a compound of the formula D-168 (12.48g, 66mmol) was charged with IrC1 under a nitrogen atmosphere3·3H2O (7.05g, 20mmo1), adding a mixed solution composed of 360mL of ethylene glycol ethyl ether and 120mL of purified water, refluxing for 24 hours under the protection of nitrogen atmosphere, cooling to room temperature, separating out a precipitate, performing suction filtration on the precipitate to obtain a solid, washing the solid with water, absolute ethyl alcohol and petroleum ether in sequence, and drying to obtain a yellow powdery intermediate B-168 shown as a formula B-168 (the mass is 5.08g, and the yield is 42%);
2) weighing intermediate B-168(4.83g and 4mmol) shown in formula B-168 obtained in the step 1) in a nitrogen atmosphere, adding the intermediate B-168 into a container, adding silver trifluoromethanesulfonate (2.63g and 10mmol), adding 150mL of dichloromethane into the system, adding 50mL of methanol, refluxing for 24 hours in the nitrogen atmosphere, cooling to room temperature, performing column chromatography (short column) to obtain filtrate, concentrating the filtrate until solid is separated out, and obtaining intermediate C-168 shown in formula C-168 as yellow powder (the mass is 5.68g and the yield is 91%);
3) weighing the intermediate C-168(5.46g and 7mmol) shown in the formula C-168 obtained in the step 2) in a nitrogen atmosphere, adding the intermediate C-168 into a reactor, adding the compound shown in the formula A-168 (6.37g and 21mmol), adding 110mL of absolute ethyl alcohol into the system, refluxing for 24 hours in the nitrogen atmosphere, carrying out suction filtration, washing with alcohol, drying, carrying out silica gel column chromatography by using dichloromethane and toluene as solvents, and concentrating the filtrate until solid is separated out to obtain yellow complex I-168 (the mass is 0.91g, and the yield is 15%).
The complex I-168 is detected and analyzed, and the specific result is as follows:
HPLC purity: greater than 99%.
Mass spectrum: calculated value 871.33; the test value was 871.37.
Elemental analysis:
the calculated values are: 62.05 percent of C; 5.78 percent of H; 22.07 percent of Ir; 6.43 percent of N; 3.67 percent of O;
the test values are: 62.02 percent of C; 5.75 percent of H; 22.09 percent of Ir; 6.46 percent of N; and 3.68 percent of O.
Example 7
In the examples of the present invention, others are represented by the formulae I-2, I-3, I-4, I-5, I-6, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, I-18, I-19, I-20, I-21, I-22, I-23, I-24, I-25, I-26, I-27, I-28, I-29, I-30, I-31, I-32, I-33, I-34, I-35, I-36, I-37, Formula I-38, formula I-39, formula I-40, formula I-42, formula I-43, formula I-44, formula I-45, formula I-46, formula I-47, formula I-48, formula I-49, formula I-50, formula I-51, formula I-52, formula I-53, formula I-54, formula I-55, formula I-56, formula I-57, formula I-58, formula I-59, formula I-60, formula I-61, formula I-62, formula I-63, formula I-64, formula I-65, formula I-66, formula I-67, formula I-68, formula I-69, formula I-70, formula I-71, formula I-72, formula I-73, formula I-74, formula I-75, Formula I-76, formula I-77, formula I-78, formula I-79, formula I-80, formula I-81, formula I-82, formula I-83, formula I-84, formula I-85, formula I-86, formula I-87, formula I-88, formula I-89, formula I-90, formula I-91, formula I-92, formula I-93, formula I-94, formula I-95, formula I-96, formula I-97, formula I-98, formula I-99, formula I-100, formula I-101, formula I-102, formula I-103, formula I-104, formula I-105, formula I-106, formula I-107, formula I-108, formula I-109, formula I-110, formula I-111, formula I-112, formula I-80, formula I-91, formula I-93, Formula I-113, formula I-114, formula I-115, formula I-116, formula I-117, formula I-118, formula I-119, formula I-120, formula I-121, formula I-122, formula I-123, formula I-124, formula I-125, formula I-126, formula I-128, formula I-129, formula I-130, formula I-131, formula I-132, formula I-133, formula I-134, formula I-135, formula I-136, formula I-137, formula I-138, formula I-139, formula I-140, formula I-141, formula I-142, formula I-143, formula I-144, formula I-145, formula I-146, formula I-147, formula I-148, formula I-149, formula I-150, The synthesis methods of the complexes shown in the formulas I-151, I-152, I-153, I-154, I-155, I-156, I-157, I-158, I-159, I-160, I-162, I-163, I-164, I-165, I-166 or I-167 are basically the same as those in the above examples, and only corresponding raw materials need to be replaced, which is not repeated herein, and in this example, the mass spectrometry results of some other synthesis examples of the complexes are shown in Table 1.
TABLE 1 Mass Spectrometry results Table
Figure BDA0002299636630000431
Figure BDA0002299636630000441
Example 8
An organic electroluminescent device was prepared using the complex i-1 prepared in example 1, by a specific method comprising: coating with a thickness of
Figure BDA0002299636630000442
The ITO glass substrate is put in distilled water for cleaning for 2 times, ultrasonic cleaning is carried out for 30 minutes, the ITO glass substrate is repeatedly cleaned for 2 times by distilled water and ultrasonic cleaning is carried out for 10 minutes, after the cleaning by distilled water is finished, solvents such as isopropanol, acetone, methanol and the like are used for ultrasonic cleaning in sequence, drying is carried out, the ITO glass substrate is transferred into a plasma cleaning machine, and the ITO glass substrate is cleanedWashing for 5 minutes, and conveying to an evaporation machine; evaporating 4,4' -tri [ 2-naphthyl phenylamino ] group on ITO glass substrate (anode) under vacuum condition]Triphenylamine (thickness 60nm), NPB (thickness 60nm), CBP + complex I-1 (thickness 30nm), 2-methyl-8-hydroxyquinoline p-hydroxybiphenyl aluminum (thickness 10nm) as a hole blocking layer, Alq3 (thickness 40nm) as an electron transport layer, LiF (thickness 0.2nm) as an electron injection layer, and Al as a cathode of 150nm, thereby obtaining the organic electroluminescent device.
Wherein, the CBP + complex I-1 is expressed as that 10 percent (mass) of the complex I-1 is doped in CBP for mixed evaporation.
NPB, Alq used in the examples of the present invention3And the structural formula of CBP is as follows:
Figure BDA0002299636630000451
by referring to the above method, the complex I-1 is replaced by the complex I-2, the complex I-7, the complex I-8, the complex I-16, the complex I-25, the complex I-39, the complex I-41, the complex I-53, the complex I-85, the complex I-105, the complex I-127, the complex I-137, the complex I-159, the complex I-161 and the complex I-168 respectively, and the corresponding organic electroluminescent devices are prepared.
Comparative example 1
An organic electroluminescent device was fabricated as in example 8, wherein the corresponding complex was replaced with Ir (ppy) as compared with example 73The rest of the examples of the present invention were conducted in the same manner as in example 8 using Ir (ppy)3The structural formula of (A) is as follows:
Figure BDA0002299636630000452
the organic electroluminescent device prepared in this embodiment and the plurality of organic electroluminescent devices prepared in embodiment 8 are respectively subjected to performance testing, specifically, the obtained organic electroluminescent device is subjected to a light emitting characteristic test, and a KEITHLEY model 2400 source measuring unit and a CS-2000 spectroradiometer are adopted in the test to evaluate driving voltage, service life and light emitting efficiency. Specific performance test results are shown in table 2.
TABLE 2 table of Performance test results
Figure BDA0002299636630000453
Figure BDA0002299636630000461
As shown in Table 2, the organic electroluminescent device prepared by using the complex provided by the invention as a doping material of a light-emitting layer and the comparative compound Ir (ppy)3Compared with the organic electroluminescent device prepared by the doped material of the luminescent layer, the driving voltage is obviously reduced, and the luminous efficiency and the service life are obviously improved.
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.

Claims (5)

1. A complex, characterized in that the complex has any one of the specific structures shown below:
Figure FDA0003500344900000011
Figure FDA0003500344900000021
Figure FDA0003500344900000031
Figure FDA0003500344900000041
Figure FDA0003500344900000051
Figure FDA0003500344900000061
Figure FDA0003500344900000071
Figure FDA0003500344900000081
Figure FDA0003500344900000091
Figure FDA0003500344900000101
Figure FDA0003500344900000111
Figure FDA0003500344900000121
Figure FDA0003500344900000131
Figure FDA0003500344900000141
Figure FDA0003500344900000151
Figure FDA0003500344900000161
Figure FDA0003500344900000171
Figure FDA0003500344900000181
Figure FDA0003500344900000191
Figure FDA0003500344900000201
Figure FDA0003500344900000211
2. a phosphorescent material comprising the complex according to claim 1 partially or entirely.
3. An organic electroluminescent device, characterized in that it comprises partially the phosphorescent material as claimed in claim 2.
4. A display panel comprising, in part, the organic electroluminescent device according to claim 3.
5. A solar cell comprising, in part, the organic electroluminescent device of claim 3.
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