CN103145763B - Pyridine-based cyclometal ligand-platinum complex and its preparation method and application - Google Patents

Abstract

A novel cyclometal ligand-platinum complex and its preparation method and application, which belong to the field of electronic material technology. This novel cyclometal ligand-platinum complex is easy to obtain through template design, and a triphenylamine group, a quinoline group or a trifluoromethyl group is introduced into the material. The electronic structure and hole injection and transport properties of the material can be conveniently adjusted by adjusting the substituents on the nitrogen heteroaromatic ring. The complex synthesized by the present invention has good thermal stability and hole injection and transport properties, and has broad application prospects in the fields of organic electroluminescent materials, oxygen sensing materials, dyes and medicines. The oxygen sensor prepared by the complex has the advantages of simple structure, low cost, reliable operation, etc., and can be made into a portable oxygen sensor for promotion and use.

Description

Pyridine-based cyclometal ligand-platinum complex and its preparation method and application

technical field

The invention relates to a pyridine-based ring metal ligand-platinum complex and a preparation method and application thereof, belonging to the technical field of electronic materials.

Background technique

Cyclometallic ligand-platinum complexes have the characteristics of special rigid fused ring structure and good hole transport performance, and are widely used in the fields of organic photoelectric materials, oxygen sensors, dyes and medicines (Adv.Funct.Mater.2006, 16, 838–846; Eur. J. Inorg. Chem. 2006, 3676–3683). In recent years, organic electroluminescent materials and devices (Organic Light-Emitting Diodes, OLEDs) have broad application prospects in the new generation of display technology, which has attracted widespread attention and active participation from the scientific community and internationally renowned companies. Compared with devices and other common display technologies, organic electroluminescent materials have the advantages of easy design, high luminous efficiency, wide viewing angle, fast response speed, ultra-thin, light weight, and luminescent colors that can cover the entire visible light region. (Organometallics 2010, 29, 3912-3921).

The quinoline group and the aromatic ring form a conjugated molecule, which enhances the electrical conductivity, photoelectricity and nonlinear optical properties of the platinum complex. The ligand containing the quinoline group can effectively reduce the intermolecular stacking effect and promote Cyclometallic ligand-platinum complexes have high electroluminescent parameters. By adjusting the substituents of the quinolinyl cyclometallic ligands, the luminescence properties of the platinum complexes show a gradual change from orange to red. phenomenon (J.Phys.Chem.C, 2012, 116, 7526–7533).

Due to the strong electronegativity and small atomic radius of fluorine atoms, fluorine-containing compounds have many unique properties and have important application value in the fields of medicine and functional materials. Especially after introducing CF group in compound, because trifluoromethyl has very strong electronegativity, high stability and lipophilicity, therefore, trifluoromethyl is introduced in ring metal ligand _- platinum complex and can improve Thermal stability and emission wavelength of complexes.

Hole transport materials are an important part of organic electroluminescent devices. As hole transport materials, they must not only have a lower ionization potential to reduce the energy barrier between the hole transport layer and the anode, but also have a higher glass Temperature and better film formation, so as to increase the stability of the device and prolong the life of the device. Triphenylamine derivatives are the most widely used hole transport materials with high hole mobility and excellent performance (J. Mater. Chem., 2010, 20, 7472–7484). The ring metal ligand-platinum complex designed in the present invention has a higher glass transition temperature, and can be used as a hole transport material or a hole transport luminescent material in a high temperature resistant electroluminescent device. The oxygen sensor prepared by it has The utility model has the advantages of simple structure, low cost, reliable operation and the like, and can be made into a portable oxygen sensor for popularization.

Contents of the invention

The object of the present invention is to provide a novel ring metal ligand-platinum complex and its preparation method and application.

The technical scheme adopted in the present invention is: a novel ring metal ligand-platinum complex, a C^N type ring metal neutral ligand synthesized by an arylboronic acid compound and a halogenated nitrogen heteroaryl ring compound and acetylacetone co-complex Formed with platinum metal ions, its structure is as follows:

The halogenated nitrogen heteroaryl ring compound is selected from 2-bromopyridine, 2-bromo-5-nitropyridine, 2-bromo-5-picoline, 2-bromo-5-cyanopyridine, 2-bromo- 5-fluoropyridine, 2-bromo-6-picoline, 2-bromo-4-picoline, 2-bromo-5-trifluoromethylpyridine, 2-bromoquinoline or 2-chloropyrazine.

The arylboronic acid compound is selected from phenylboronic acid, 4-methylbenzeneboronic acid, 4-methoxyphenylboronic acid, 4-trifluoromethylbenzeneboronic acid, 4-cyanophenylboronic acid, 4-fluorophenylboronic acid, 4- (9-carbazolyl)phenylboronic acid, 4-triphenylamineboronic acid or 3-(N-phenyl)carbazoleboronic acid.

The preparation method of the novel ring metal ligand-platinum complex, the specific synthesis steps are as follows:

(1) Synthesis of C^N-type ring metal ligands: in the air, add 0.375mmol of arylboronic acid, 0.5mmol of potassium carbonate, 0.005mmol of palladium acetate, and 0.25mmol of halogenated nitrogen heteroaromatic compounds in the round bottom flask successively, Then, add 4 mL of ethanol-water mixed solution with a volume ratio of 3:1, and carry out Suzuki cross-coupling reaction at 80°C with magnetic stirring, and follow the reaction process by thin-layer chromatography. After the reaction is complete, add 15 mL of saturated saline, three times The reaction product was extracted with 15ml of ethyl acetate, the organic phases were combined, the filtrate was concentrated, and separated by column chromatography to obtain an analytically pure biaryl compound;

(2) Complex synthesis: Add 0.2mmol of potassium tetrachloroplatinate, 0.24mmol of biaryl compound and 6mL of ethylene glycol monoethyl ether/2mL water mixed solution into a round-bottomed two-necked flask, and magnetically stir at 100°C for 12h under nitrogen protection. Suction filtration after the reaction is over, wash the filter cake with n-hexane and ethanol respectively to obtain the dichloro bridge intermediate product; add the obtained dichloro bridge intermediate product, 1.0 mmol of sodium carbonate, 2.0 mmol of acetylacetone and 6 mL of ethyl acetate to a single-necked round bottom flask. Glycol monoethyl ether was magnetically stirred at 100° C. for 13 h under the protection of nitrogen. After the reaction was completed, the reaction was rotary evaporated in vacuum and separated by column chromatography to obtain an analytically pure cyclometal ligand-platinum complex.

The application of the novel ring metal ligand-platinum complex is used as a hole transport material and a material for making an oxygen sensor.

The above compounds include derivatives of any of the following:

Compound 1: the halogenated azaheteroaromatic compound is selected from 2-bromo-5-nitropyridine, and the aryl boronic acid is selected from 4-triphenylamine boronic acid.

Compound 2: the halogenated azaheteroaromatic compound is selected from 2-bromo-5-picoline, and the aryl boronic acid is selected from 4-triphenylamine boronic acid.

Compound 3: the halogenated azaheteroaromatic compound is selected from 2-bromo-5-cyanopyridine, and the aryl boronic acid is selected from 4-triphenylamine boronic acid.

Compound 4: the halogenated azaheteroaromatic compound is selected from 2-bromo-5-fluoropyridine, and the aryl boronic acid is selected from 4-triphenylamine boronic acid.

Compound 5: the halogenated azaheteroaromatic compound is selected from 2-bromo-6-picoline, and the aryl boronic acid is selected from 4-triphenylamine boronic acid.

Compound 6: the halogenated azaheteroaromatic compound is selected from 2-bromo-4-picoline, and the aryl boronic acid is selected from 4-triphenylamine boronic acid.

Compound 7: the halogenated azaheteroaromatic compound is selected from 2-bromo-5-trifluoromethylpyridine, and the aryl boronic acid is selected from 4-triphenylamine boronic acid.

Compound 8: the halogenated azaheteroaromatic compound is selected from 2-chloropyrazine, and the aryl boronic acid is selected from 4-triphenylamine boronic acid.

Compound 9: the halogenated azaheteroaromatic compound is selected from 2-bromo-5-trifluoromethylpyridine, and the aryl boronic acid is selected from phenylboronic acid.

Compound 10: the halogenated nitrogen heteroaromatic compound is selected from 2-bromo-5-trifluoromethylpyridine, and the aryl boronic acid is selected from 4-trifluoromethylphenylboronic acid.

Compound 11: the halogenated nitrogen heteroaromatic compound is selected from 2-bromo-5-trifluoromethylpyridine, and the aryl boronic acid is selected from 4-methoxyphenylboronic acid.

Compound 12: The halogenated nitrogen heteroaromatic compound is selected from 2-bromopyridine. The arylboronic acid is selected from 4-trifluoromethylphenylboronic acid.

Compound 13: the halogenated nitrogen heteroaromatic compound is selected from 2-bromo-5-trifluoromethylpyridine, and the aryl boronic acid compound is selected from 4-methylphenylboronic acid.

Compound 14: the halogenated nitrogen heteroaromatic compound is selected from 2-bromo-5-trifluoromethylpyridine, and the aryl boronic acid is selected from 4-cyanophenylboronic acid.

Compound 15: the halogenated nitrogen heteroaromatic compound is selected from 2-bromo-5-trifluoromethylpyridine, and the aryl boronic acid is selected from 4-fluorophenylboronic acid.

Compound 16: the halogenated nitrogen heteroaromatic compound is selected from 2-bromoquinoline, and the aryl boronic acid is selected from 4-methylphenylboronic acid.

Compound 17: the halogenated nitrogen heteroaromatic compound is selected from 2-bromoquinoline, and the aryl boronic acid is selected from 4-methoxyphenylboronic acid.

Compound 18: the halogenated nitrogen heteroaromatic compound is selected from 2-bromoquinoline, and the aryl boronic acid is selected from 4-trifluoromethylphenylboronic acid.

Compound 19: the halogenated nitrogen heteroaromatic compound is selected from 2-bromoquinoline, and the aryl boronic acid is selected from 4-cyanophenylboronic acid.

Compound 20: the halogenated nitrogen heteroaromatic compound is selected from 2-bromoquinoline, and the aryl boronic acid is selected from 4-fluorophenylboronic acid.

Compound 21: the halogenated azaheteroaromatic compound is selected from 2-bromoquinoline, and the aryl boronic acid is selected from 4-(9-carbazolyl)phenylboronic acid.

Compound 22: the halogenated azaheteroaromatic compound is selected from 2-bromoquinoline, and the aryl boronic acid is selected from 4-triphenylamine boronic acid.

Compound 23: the halogenated nitrogen heteroaromatic compound is selected from 2-bromoquinoline, and the aryl boronic acid is selected from 3-(N-phenyl)carbazole boronic acid.

The beneficial effects of the present invention are: the novel cyclometal ligand-platinum complex and its preparation method and application, the material is convenient and easy to obtain through template design, and triphenylamine, quinoline or trifluoroform are introduced into the material By adjusting the substituents on the azaaryl ring, the electronic structure and hole injection and transport properties of the material can be adjusted conveniently. The complex compound synthesized by the present invention has good thermal stability and hole injection and transport properties, and has wide application prospects in the fields of organic electroluminescent materials, oxygen sensing materials, dyes and medicines, and the oxygen sensor prepared with it The utility model has the advantages of simple structure, low cost, reliable operation, etc., and can be made into a portable oxygen sensor for popularization.

Description of drawings

Fig. 1 is a TGA chart of compound 7 of the present invention. _Tg = 320°C.

Fig. 2 is an ultraviolet-visible absorption diagram of a solution of compound 7 of the present invention.

Fig. 3 is a photoluminescence diagram of a solution of Compound 7 of the present invention.

detailed description

The above-mentioned technical scheme is to prepare the C^N type ring metal ligand biaryl compound through the Suzuki cross-coupling reaction of palladium-catalyzed halogenated nitrogen heteroaryl ring compound and arylboronic acid, and then the biaryl compound and tetrachloroplatinic acid Potassium reaction to prepare cyclometallic ligand-platinum complexes. The C^N type ring metal ligand biaryl compound is that the molar ratio of halogenated nitrogen heteroaromatic compound, aryl boronic acid, potassium carbonate and palladium acetate is 0.25:0.375:0.5:0.005 to 4mL and the volume ratio is 3:1 In the ethanol-water mixed solution, react in the air at 80°C for 60-120 minutes, add saturated brine after the reaction, extract the reaction product with ethyl acetate, combine the organic phases, concentrate the filtrate, and separate by column chromatography to obtain Analysis of pure biaryl compounds. Afterwards, potassium tetrachloroplatinate and biaryl compound were added to the 6mL/2mL ethylene glycol monoethyl ether/water mixed solution at a molar ratio of 0.20:0.24, and reacted at 100°C for 12 hours under the protection of nitrogen. Wash the filter cake with n-hexane and ethanol to obtain the intermediate product of dichloro bridge. Add dichloro bridge intermediates, sodium carbonate, and acetylacetone to 6 mL of ethylene glycol monoethyl ether, and react at 100°C for 13 hours under nitrogen protection. After the reaction is completed, vacuum rotary evaporation is obtained, and the analytically pure cyclometallic complex is obtained by column chromatography separation. body-platinum complexes. The present invention is a preparation method and application of a novel C^N-type ring metal ligand-platinum complex. The material is convenient and easy to obtain through template design, and the electronic structure and space of the material can be adjusted conveniently by adjusting the substituent on the aromatic ring. Cave injection and transport properties.

The synthesis of embodiment 1 compound 1

(1) Ligand synthesis: in the air, add 4-triphenylamine boronic acid (0.375mmol), potassium carbonate (0.5mmol), palladium acetate (0.005mmol), 2-bromo-5-nitro Pyridine (0.25mmol), then, add the ethanol-water mixed solution (4mL) that volume ratio is 3:1, carry out Suzuki cross-coupling reaction 60 minutes at 80 ℃ of magnetic stirring, follow the reaction process by thin-layer chromatography, the reaction is complete After that, add saturated brine (15mL), extract the reaction product with ethyl acetate (3×15ml), combine the organic phases, concentrate the filtrate, and separate by column chromatography to obtain analytically pure N,N-diphenyl-4 -(5-nitropyridyl-2-)aniline.

(2) Complex synthesis: Add potassium tetrachloroplatinate (0.2mmol) and N,N-diphenyl-4-(5-nitropyridyl-2-)aniline (0.24mmol) into a two-necked round-bottomed flask , 6mL/2mL ethylene glycol monoethyl ether/water mixed solution, magnetically stirred at 100°C for 12h under nitrogen protection, suction filtered after the reaction, and washed the filter cake with n-hexane and ethanol respectively to obtain a dichloro bridge intermediate product. Add the obtained dichloro bridge intermediate product, sodium carbonate (1.0mmol), acetylacetone (2.0mmol) and 6mL ethylene glycol monoethyl ether into a single-necked round bottom flask, stir magnetically at 100°C for 13h under the protection of nitrogen, and vacuum Rotary evaporation and separation by column chromatography gave analytically pure compound 1. The structure of the product was identified by ¹ HNMR, ¹³ CNMR and mass spectrometry, and the separation yield was 37.6%.

The synthesis of embodiment 2 compound 2

(1) Ligand synthesis: In the air, add 4-triphenylamine boronic acid (0.375mmol), potassium carbonate (0.5mmol), palladium acetate (0.005mmol), 2-bromo-5-methyl Pyridine (0.25mmol), then, add the ethanol-water mixed solution (4mL) that volume ratio is 3:1, carry out Suzuki cross-coupling reaction 60 minutes at 80 ℃ of magnetic stirring, follow the reaction process by thin-layer chromatography, the reaction is complete After that, add saturated brine (15mL), extract the reaction product with ethyl acetate (3×15ml), combine the organic phases, concentrate the filtrate, and separate by column chromatography to obtain analytically pure N,N-diphenyl-4 -(5-methylpyridyl-2-)aniline.

(2) Complex synthesis: Add potassium tetrachloroplatinate (0.2mmol) and N,N-diphenyl-4-(5-methylpyridyl-2-)aniline (0.24mmol) into a round-bottomed two-necked flask And 6mL/2mL ethylene glycol monoethyl ether/water mixed solution, magnetically stirred at 100°C for 12h under the protection of nitrogen, suction filtered after the reaction, and the filter cake was washed with n-hexane and ethanol respectively to obtain a dichloro bridge intermediate product. Add the obtained dichloro bridge intermediate product, sodium carbonate (1.0mmol), acetylacetone (2.0mmol) and 6mL ethylene glycol monoethyl ether into a single-necked round bottom flask, stir magnetically at 100°C for 13h under the protection of nitrogen, and vacuum Rotary evaporation and separation by column chromatography gave analytically pure compound 2. The structure of the product was identified by ¹ HNMR, ¹³ CNMR and mass spectrometry, and the separation yield was 41.6%.

The synthesis of embodiment 3 compound 3

(1) Ligand synthesis: In the air, add 4-triphenylamine boronic acid (0.375mmol), potassium carbonate (0.5mmol), palladium acetate (0.005mmol), 2-bromo-5-cyano Pyridine (0.25mmol), then, add the ethanol-water mixed solution (4mL) that volume ratio is 3:1, carry out Suzuki cross-coupling reaction 60 minutes at 80 ℃ of magnetic stirring, follow the reaction process by thin-layer chromatography, the reaction is complete After that, add saturated brine (15mL), extract the reaction product with ethyl acetate (3×15ml), combine the organic phases, concentrate the filtrate, and separate by column chromatography to obtain analytically pure N,N-diphenyl-4 -(5-cyanopyridyl-2-)aniline.

(2) Complex synthesis: Add potassium tetrachloroplatinate (0.2mmol) and N,N-diphenyl-4-(5-cyanopyridyl-2-)aniline (0.24mmol) into a round-bottomed two-necked flask And 6mL/2mL ethylene glycol monoethyl ether/water mixed solution, magnetically stirred at 100°C for 12h under the protection of nitrogen, suction filtered after the reaction, and the filter cake was washed with n-hexane and ethanol respectively to obtain a dichloro bridge intermediate product. Add the obtained dichloro bridge intermediate product, sodium carbonate (1.0mmol), acetylacetone (2.0mmol) and 6mL ethylene glycol monoethyl ether into a single-necked round bottom flask, stir magnetically at 100°C for 13h under the protection of nitrogen, and vacuum Rotary evaporation and separation by column chromatography gave analytically pure compound 3. The structure of the product was identified by ¹ HNMR, ¹³ CNMR and mass spectrometry, and the separation yield was 40.6%.

The synthesis of embodiment 4 compound 4

(1) Ligand synthesis: In air, add 4-triphenylamine boronic acid (0.375mmol), potassium carbonate (0.5mmol), palladium acetate (0.005mmol), 2-bromo-5-fluoro Pyridine (0.25mmol), then, add the ethanol-water mixed solution (4mL) that volume ratio is 3:1, carry out Suzuki cross-coupling reaction 60 minutes at 80 ℃ of magnetic stirring, follow the reaction process by thin-layer chromatography, the reaction is complete After that, add saturated brine (15mL), extract the reaction product with ethyl acetate (3×15ml), combine the organic phases, concentrate the filtrate, and separate by column chromatography to obtain analytically pure N,N-diphenyl-4 -(5-fluoropyridyl-2-)aniline.

(2) Complex synthesis: Add potassium tetrachloroplatinate (0.2mmol) and N,N-diphenyl-4-(5-fluoropyridyl-2-)aniline (0.24mmol) into a round-bottomed two-necked flask And 6mL/2mL ethylene glycol monoethyl ether/water mixed solution, magnetically stirred at 100°C for 12h under the protection of nitrogen, suction filtered after the reaction, and the filter cake was washed with n-hexane and ethanol respectively to obtain a dichloro bridge intermediate product. Add the obtained dichloro bridge intermediate product, sodium carbonate (1.0mmol), acetylacetone (2.0mmol) and 6mL ethylene glycol monoethyl ether into a single-necked round bottom flask, stir magnetically at 100°C for 13h under the protection of nitrogen, and vacuum Rotary evaporation and separation by column chromatography gave analytically pure compound 4. The structure of the product was identified by ¹ HNMR, ¹³ CNMR and mass spectrometry, and the separation yield was 40.6%.

The synthesis of embodiment 5 compound 5

(1) Ligand synthesis: in the air, add 4-triphenylamine boronic acid (0.375mmol), potassium carbonate (0.5mmol), palladium acetate (0.005mmol), 2-bromo-6-methyl Pyridine (0.25mmol), then, add the ethanol-water mixed solution (4mL) that volume ratio is 3:1, carry out Suzuki cross-coupling reaction 60 minutes at 80 ℃ of magnetic stirring, follow the reaction process by thin-layer chromatography, the reaction is complete After that, add saturated brine (15mL), extract the reaction product with ethyl acetate (3×15ml), combine the organic phases, concentrate the filtrate, and separate by column chromatography to obtain analytically pure N,N-diphenyl-4 -(6-methylpyridyl-2-)aniline.

(2) Complex synthesis: Add potassium tetrachloroplatinate (0.2mmol) and N,N-diphenyl-4-(6-methylpyridyl-2-)aniline (0.24mmol) into a round-bottomed two-necked flask And 6mL/2mL ethylene glycol monoethyl ether/water mixed solution, magnetically stirred at 100°C for 12h under the protection of nitrogen, suction filtered after the reaction, and the filter cake was washed with n-hexane and ethanol respectively to obtain a dichloro bridge intermediate product. Add the obtained dichloro bridge intermediate product, sodium carbonate (1.0mmol), acetylacetone (2.0mmol) and 6mL ethylene glycol monoethyl ether into a single-necked round bottom flask, stir magnetically at 100°C for 13h under the protection of nitrogen, and vacuum Rotary evaporation and separation by column chromatography gave analytically pure compound 5. The structure of the product was identified by ¹ HNMR, ¹³ CNMR and mass spectrometry, and the separation yield was 34.8%.

The synthesis of embodiment 6 compound 6

(1) Ligand synthesis: in the air, add 4-triphenylamine boronic acid (0.375mmol), potassium carbonate (0.5mmol), palladium acetate (0.005mmol), 2-bromo-4-methyl Pyridine (0.25mmol), then, add the ethanol-water mixed solution (4mL) that volume ratio is 3:1, carry out Suzuki cross-coupling reaction 60 minutes at 80 ℃ of magnetic stirring, follow the reaction process by thin-layer chromatography, the reaction is complete After that, add saturated brine (15mL), extract the reaction product with ethyl acetate (3×15ml), combine the organic phases, concentrate the filtrate, and separate by column chromatography to obtain analytically pure N,N-diphenyl-4 -(4-methylpyridyl-2-)aniline.

(2) Complex synthesis: Add potassium tetrachloroplatinate (0.2mmol) and N,N-diphenyl-4-(4-methylpyridyl-2-)aniline (0.24mmol) into a round-bottomed two-necked flask And 6mL/2mL ethylene glycol monoethyl ether/water mixed solution, magnetically stirred at 100°C for 12h under the protection of nitrogen, suction filtered after the reaction, and the filter cake was washed with n-hexane and ethanol respectively to obtain a dichloro bridge intermediate product. Add the obtained dichloro bridge intermediate product, sodium carbonate (1.0mmol), acetylacetone (2.0mmol) and 6mL ethylene glycol monoethyl ether into a single-necked round bottom flask, stir magnetically at 100°C for 13h under the protection of nitrogen, and vacuum Rotary evaporation and separation by column chromatography gave analytically pure compound 6. The structure of the product was identified by ¹ HNMR, ¹³ CNMR and mass spectrometry, and the separation yield was 27.8%.

The synthesis of embodiment 7 compound 7

(1) Ligand synthesis: In the air, add 4-triphenylamine boric acid (0.375mmol), potassium carbonate (0.5mmol), palladium acetate (0.005mmol), 2-bromo-5-trifluoro Pyridine (0.25mmol), then, add the ethanol-water mixed solution (4mL) that volume ratio is 3:1, carry out Suzuki cross-coupling reaction 60 minutes at 80 ℃ of magnetic stirring, follow the reaction process by thin-layer chromatography, After the reaction is complete, add saturated brine (15mL), extract the reaction product with ethyl acetate (3×15ml), combine the organic phases, concentrate the filtrate, and separate by column chromatography to obtain analytically pure N,N-diphenyl -4-(5-trifluoromethylpyridyl-2-)aniline.

(2) Synthesis of complexes: Potassium tetrachloroplatinate (0.2mmol), N,N-diphenyl-4-(5-trifluoromethylpyridyl-2-)aniline (0.24 mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution, magnetically stirred at 100°C for 12h under nitrogen protection, suction filtered after the reaction was completed, and the filter cake was washed with n-hexane and ethanol respectively to obtain a dichloro bridge intermediate product. Add the obtained dichloro bridge intermediate product, sodium carbonate (1.0mmol), acetylacetone (2.0mmol) and 6mL ethylene glycol monoethyl ether into a single-necked round bottom flask, stir magnetically at 100°C for 13h under the protection of nitrogen, and vacuum Rotary evaporation and separation by column chromatography gave analytically pure compound 7. The structure of the product was identified by ¹ HNMR, ¹³ CNMR and mass spectrometry, and the separation yield was 50.3%.

The synthesis of embodiment 8 compound 8

(1) Ligand synthesis: In the air, add 4-triphenylamine boronic acid (0.375mmol), potassium carbonate (0.5mmol), palladium acetate (0.005mmol), 2-chloropyrazine (0.25mmol) to the round bottom flask successively ), then add ethanol-water mixed solution (4mL) with a volume ratio of 3:1, carry out Suzuki cross-coupling reaction at 80°C for 60 minutes with magnetic stirring, follow the reaction process by thin layer chromatography, after the reaction is complete, add saturated brine (15mL), the reaction product was extracted with ethyl acetate (3×15ml), the organic phases were combined, the filtrate was concentrated, and separated by column chromatography to obtain analytically pure N,N-diphenyl-4-(pyrazine Base-2,4-)aniline.

(2) Complex synthesis: Add potassium tetrachloroplatinate (0.2mmol), N,N-diphenyl-4-(pyrazinyl-2-4-)aniline (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution, magnetically stirred at 100°C for 12h under nitrogen protection, suction filtered after the reaction, and the filter cake was washed with n-hexane and ethanol respectively to obtain a dichloro bridge intermediate product. Add the obtained dichloro bridge intermediate product, sodium carbonate (1.0mmol), acetylacetone (2.0mmol) and 6mL ethylene glycol monoethyl ether into a single-necked round bottom flask, stir magnetically at 100°C for 13h under the protection of nitrogen, and vacuum Rotary evaporation and separation by column chromatography gave analytically pure compound 8. The structure of the product was identified by ¹ HNMR, ¹³ CNMR and mass spectrometry, and the separation yield was 5.3%.

The synthesis of embodiment 9 compound 9

(1) Ligand synthesis: In the air, add phenylboronic acid (0.375mmol), potassium carbonate (0.5mmol), palladium acetate (0.005mmol), 2-bromo-5-trifluoromethylpyridine successively to the round bottom flask (0.25mmol), then, add the ethanol-water mixed solution (4mL) that volume ratio is 3:1, carry out Suzuki cross-coupling reaction 60 minutes at 80 ℃ of magnetic stirring, after reaction is complete, add saturated saline (15mL), The reaction product was extracted with ethyl acetate (3×15ml), the organic phases were combined, the filtrate was concentrated, and separated by column chromatography to obtain analytically pure 2-phenyl-5-trifluoromethylpyridine.

(2) Complex synthesis: Add potassium tetrachloroplatinate (0.2mmol), 2-phenyl-5-trifluoromethylpyridine (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/ The water mixed solution was magnetically stirred at 100° C. for 12 h under the protection of nitrogen. After the reaction was completed, it was suction filtered, and the filter cake was washed with n-hexane and ethanol respectively to obtain a dichloro bridge intermediate product. Add the obtained dichloro-bridge intermediate, sodium carbonate (1.0 mmol), acetylacetone (2.0 mmol) and 6 mL of ethylene glycol monoethyl ether into a single-necked round-bottomed flask, and stir magnetically at 100 ° C for 13 h under nitrogen protection. After the reaction is completed, vacuum spin Evaporated and separated by column chromatography to obtain analytically pure compound 9. The structure of the product was identified by ¹ HNMR, ¹³ CNMR and mass spectrometry, and the separation yield was 70.4%.

The synthesis of embodiment 10 compound 10

(1) Ligand synthesis: In air, add 4-trifluoromethylphenylboronic acid (0.375mmol), potassium carbonate (0.5mmol), palladium acetate (0.005mmol), 2-bromo-5 -Trifluoromethylpyridine (0.25mmol), then, add ethanol-water mixed solution (4mL) with a volume ratio of 3:1, and carry out Suzuki cross-coupling reaction at 80°C for 60 minutes with magnetic stirring. After the reaction is complete, add saturated brine (15mL), the reaction product was extracted with ethyl acetate (3×15ml), the organic phases were combined, the filtrate was concentrated, and separated by column chromatography to obtain analytically pure 2-(4-trifluoromethylphenyl)- 5-Trifluoromethylpyridine.

(2) Complex synthesis: Add potassium tetrachloroplatinate (0.2mmol), 2-(4-trifluoromethylphenyl)-5-trifluoromethylpyridine (0.24mmol) and 6mL to a two-necked round-bottomed flask /2mL ethylene glycol monoethyl ether/water mixed solution, magnetically stirred at 100°C for 12h under the protection of nitrogen, suction filtered after the reaction, and the filter cake was washed with n-hexane and ethanol respectively to obtain a dichloro bridge intermediate product. Add the obtained dichloro-bridge intermediate, sodium carbonate (1.0 mmol), acetylacetone (2.0 mmol) and 6 mL of ethylene glycol monoethyl ether into a single-necked round-bottomed flask, and stir magnetically at 100 ° C for 13 h under nitrogen protection. After the reaction is completed, vacuum spin evaporated and separated by column chromatography to obtain analytically pure compound 10. The structure of the product was identified by ¹ HNMR, ¹³ CNMR and mass spectrometry, and the separation yield was 37.1%.

The synthesis of embodiment 11 compound 11

(1) Ligand synthesis: In air, add 4-methoxyphenylboronic acid (0.375mmol), potassium carbonate (0.5mmol), palladium acetate (0.005mmol), 2-bromo-5- Trifluoromethylpyridine (0.25mmol), then, add ethanol-water mixed solution (4mL) with a volume ratio of 3:1, and carry out Suzuki cross-coupling reaction at 80°C for 60 minutes with magnetic stirring. After the reaction is complete, add saturated salt water (15mL), the reaction product was extracted with ethyl acetate (3×15ml), the organic phases were combined, the filtrate was concentrated, and separated by column chromatography to obtain analytically pure 2-(4-methoxyphenyl)-5- Trifluoromethylpyridine.

(2) Complex synthesis: Add potassium tetrachloroplatinate (0.2mmol), 2-(4-methoxyphenyl)-5-trifluoromethylpyridine (0.24mmol) and 6mL/ 2mL of ethylene glycol monoethyl ether/water mixed solution was magnetically stirred at 100°C for 12h under the protection of nitrogen. After the reaction was completed, it was suction filtered, and the filter cake was washed with n-hexane and ethanol respectively to obtain a dichloro bridge intermediate product. Add the obtained dichloro-bridge intermediate, sodium carbonate (1.0 mmol), acetylacetone (2.0 mmol) and 6 mL of ethylene glycol monoethyl ether into a single-necked round-bottomed flask, and stir magnetically at 100 ° C for 13 h under nitrogen protection. After the reaction is completed, vacuum spin Evaporated and separated by column chromatography to obtain analytically pure compound 11. The structure of the product was identified by ¹ HNMR, ¹³ CNMR and mass spectrometry, and the separation yield was 41.2%.

The synthesis of embodiment 12 compound 12

(1) Ligand synthesis: In the air, add 4-trifluoromethylphenylboronic acid (0.375mmol), potassium carbonate (0.5mmol), palladium acetate (0.005mmol), 2-bromopyridine ( 0.25mmol), then, add the ethanol-water mixed solution (4mL) that volume ratio is 3:1, carry out Suzuki cross-coupling reaction 60 minutes at 80 ℃ of magnetic stirring, after the reaction is complete, add saturated saline (15mL), use The reaction product was extracted with ethyl acetate (3×15ml), the organic phases were combined, the filtrate was concentrated, and separated by column chromatography to obtain analytically pure 2-(4-trifluoromethylphenyl)pyridine.

(2) Complex synthesis: Add potassium tetrachloroplatinate (0.2mmol), 2-(4-trifluoromethylphenyl)pyridine (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether into a round-bottomed two-necked flask /water mixed solution, magnetically stirred at 100° C. for 12 h under the protection of nitrogen, suction filtered after the reaction, and the filter cake was washed with n-hexane and ethanol respectively to obtain a dichloro bridge intermediate product. Add the obtained dichloro-bridge intermediate, sodium carbonate (1.0 mmol), acetylacetone (2.0 mmol) and 6 mL of ethylene glycol monoethyl ether into a single-necked round-bottomed flask, and stir magnetically at 100 ° C for 13 h under nitrogen protection. After the reaction is completed, vacuum spin Evaporated and separated by column chromatography to obtain analytically pure compound 12. The structure of the product was identified by ¹ HNMR, ¹³ CNMR and mass spectrometry, and the separation yield was 70.4%.

The synthesis of embodiment 13 compound 13

(1) Ligand synthesis: in air, add 4-methylphenylboronic acid (0.375mmol), potassium carbonate (0.5mmol), palladium acetate (0.005mmol), 2-bromo-5-tris Fluoromethylpyridine (0.25mmol), then, add ethanol-water mixed solution (4mL) with a volume ratio of 3:1, carry out Suzuki cross-coupling reaction at 80°C for 60 minutes with magnetic stirring, and track the reaction progress by thin-layer chromatography , after the reaction is complete, add saturated brine (15mL), extract the reaction product with ethyl acetate (3 × 15ml), combine the organic phases, concentrate the filtrate, and separate by column chromatography to obtain analytically pure 2-(4-methanol) phenyl)-5-trifluoromethylpyridine.

(2) Complex synthesis: Add potassium tetrachloroplatinate (0.2mmol), 2-(4-methylphenyl)-5-trifluoromethylpyridine (0.24mmol) and 6mL/2mL to a two-necked round-bottomed flask Ethylene glycol monoethyl ether/water mixed solution was magnetically stirred at 100°C for 12 hours under the protection of nitrogen. After the reaction was completed, it was suction filtered, and the filter cake was washed with n-hexane and ethanol respectively to obtain a dichloro bridge intermediate product. Add the obtained dichloro-bridge intermediate, sodium carbonate (1.0 mmol), acetylacetone (2.0 mmol) and 6 mL of ethylene glycol monoethyl ether into a single-necked round-bottomed flask, and stir magnetically at 100 ° C for 13 h under nitrogen protection. After the reaction is completed, vacuum spin Evaporated, separated by column chromatography to obtain analytically pure compound 13. The structure of the product was identified by ¹ HNMR, ¹³ CNMR and mass spectrometry, and the separation yield was 41.1%.

The synthesis of embodiment 14 compound 14

(1) Ligand synthesis: in air, add 4-cyanophenylboronic acid (0.375mmol), potassium carbonate (0.5mmol), palladium acetate (0.005mmol), 2-bromo-5-tris Fluoromethylpyridine (0.25mmol), then, add ethanol-water mixed solution (4mL) with a volume ratio of 3:1, and carry out Suzuki cross-coupling reaction at 80°C for 60 minutes with magnetic stirring. After the reaction is complete, add saturated saline (15mL), the reaction product was extracted with ethyl acetate (3×15ml), the organic phases were combined, the filtrate was concentrated, and separated by column chromatography to obtain analytically pure 2-(4-cyanophenyl)-5-trifluoro picoline.

(2) Complex synthesis: Add potassium tetrachloroplatinate (0.2mmol), 2-(4-cyanophenyl)-5-trifluoromethylpyridine (0.24mmol) and 6mL/2mL into a two-necked round-bottomed flask Ethylene glycol monoethyl ether/water mixed solution was magnetically stirred at 100° C. for 12 hours under the protection of nitrogen. After the reaction, the filter cake was washed with n-hexane and ethanol while suction filtering to obtain a dichloro bridge intermediate product. Add the obtained dichloro bridge intermediate product, sodium carbonate (1.0mmol), acetylacetone (2.0mmol) and 6mL ethylene glycol monoethyl ether into a single-necked round bottom flask, stir magnetically at 100°C for 13h under nitrogen protection, and vacuum Rotary evaporation and separation by column chromatography gave analytically pure compound 14. The structure of the product was identified by ¹ HNMR, ¹³ CNMR and mass spectrometry, and the separation yield was 43.6%.

The synthesis of embodiment 15 compound 15

(1) Ligand synthesis: in air, add 4-fluorophenylboronic acid (0.375mmol), potassium carbonate (0.5mmol), palladium acetate (0.005mmol), 2-bromo-5-tris Fluoromethylpyridine (0.25mmol), then, add ethanol-water mixed solution (4mL) with a volume ratio of 3:1, and carry out Suzuki cross-coupling reaction at 80°C for 60 minutes with magnetic stirring. After the reaction is complete, add saturated saline (15mL), the reaction product was extracted with ethyl acetate (3×15ml), the organic phases were combined, the filtrate was concentrated, and separated by column chromatography to obtain analytically pure 2-(4-fluorophenyl)-5-trifluoro picoline.

(2) Complex synthesis: Add potassium tetrachloroplatinate (0.2mmol), 2-(4-fluorophenyl)-5-trifluoromethylpyridine (0.24mmol) and 6mL/2mL to a two-necked round-bottomed flask Ethylene glycol monoethyl ether/water mixed solution was magnetically stirred at 100°C for 12 hours under the protection of nitrogen. After the reaction was completed, it was suction filtered, and the filter cake was washed with n-hexane and ethanol respectively to obtain a dichloro bridge intermediate product. Add the obtained dichloro-bridge intermediate, sodium carbonate (1.0 mmol), acetylacetone (2.0 mmol) and 6 mL of ethylene glycol monoethyl ether into a single-necked round-bottomed flask, and stir magnetically at 100 ° C for 13 h under nitrogen protection. After the reaction is completed, vacuum spin Evaporated and separated by column chromatography to obtain analytically pure compound 15. The structure of the product was identified by ¹ HNMR, ¹³ CNMR and mass spectrometry, and the separation yield was 39.4%.

The synthesis of embodiment 16 compound 16

(1) Ligand synthesis: In the air, add 4-methylphenylboronic acid (0.375mmol), potassium carbonate (0.5mmol), palladium acetate (0.005mmol), 2-bromoquinoline (0.25mmol) to the round bottom flask successively mmol), then, add ethanol-water mixed solution (4mL) with a volume ratio of 3:1, carry out Suzuki cross-coupling reaction at 80°C for 60 minutes with magnetic stirring, after the reaction is complete, add saturated saline (15mL), and The reaction product was extracted with ethyl ester (3×15ml), the organic phases were combined, the filtrate was concentrated, and separated by column chromatography to obtain analytically pure 2-(4-methylphenyl)quinoline.

(2) Complex synthesis: Add potassium tetrachloroplatinate (0.2mmol), 2-(4-methylphenyl)quinoline (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/ The water mixed solution was magnetically stirred at 100° C. for 12 h under the protection of nitrogen. After the reaction was completed, it was suction filtered, and the filter cake was washed with n-hexane and ethanol respectively to obtain a dichloro bridge intermediate product. Add the obtained dichloro-bridge intermediate, sodium carbonate (1.0 mmol), acetylacetone (2.0 mmol) and 6 mL of ethylene glycol monoethyl ether into a single-necked round-bottomed flask, and magnetically stir at 100 ° C for 13 h under nitrogen protection. After the reaction is complete, vacuum spin Evaporate, and separate by column chromatography to obtain analytically pure compound 16. The structure of the product was identified by ¹ HNMR, ¹³ CNMR and mass spectrometry, and the separation yield was 51.8%. .

The synthesis of embodiment 17 compound 17

(1) Ligand synthesis: In air, add 4-methoxyphenylboronic acid (0.375mmol), potassium carbonate (0.5mmol), palladium acetate (0.005mmol), 2-bromoquinoline ( 0.25mmol), then, add the ethanol-water mixed solution (4mL) that volume ratio is 3:1, carry out Suzuki cross-coupling reaction 60 minutes at 80 ℃ of magnetic stirring, after the reaction is complete, add saturated saline (15mL), use The reaction product was extracted with ethyl acetate (3×15ml), the organic phases were combined, the filtrate was concentrated, and separated by column chromatography to obtain analytically pure 2-(4-methoxyphenyl)quinoline.

(2) Complex synthesis: Add potassium tetrachloroplatinate (0.2mmol), 2-(4-methoxyphenyl)quinoline (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether into a round-bottomed two-necked flask /water mixed solution, magnetically stirred at 100° C. for 12 h under the protection of nitrogen, suction filtered after the reaction, and the filter cake was washed with n-hexane and ethanol respectively to obtain a dichloro bridge intermediate product. Add the obtained dichloro-bridge intermediate, sodium carbonate (1.0 mmol), acetylacetone (2.0 mmol) and 6 mL of ethylene glycol monoethyl ether into a single-necked round-bottomed flask, and stir magnetically at 100 ° C for 13 h under nitrogen protection. After the reaction is completed, vacuum spin Evaporated and separated by column chromatography to obtain analytically pure compound 17. The structure of the product was identified by ¹ HNMR, ¹³ CNMR and mass spectrometry, and the separation yield was 46.8%.

The synthesis of embodiment 18 compound 18

(1) Ligand synthesis: In the air, add 4-trifluoromethylphenylboronic acid (0.375mmol), potassium carbonate (0.5mmol), palladium acetate (0.005mmol), 2-bromoquinoline to the round bottom flask successively (0.25mmol), then, add the ethanol-water mixed solution (4mL) that volume ratio is 3:1, carry out Suzuki cross-coupling reaction 60 minutes at 80 ℃ of magnetic stirring, after reaction is complete, add saturated saline (15mL), The reaction product was extracted with ethyl acetate (3×15ml), the organic phases were combined, the filtrate was concentrated, and separated by column chromatography to obtain analytically pure 2-(4-trifluoromethylphenyl)quinoline.

(2) Complex synthesis: Add potassium tetrachloroplatinate (0.2mmol), 2-(4-trifluoromethylphenyl) quinoline (0.24mmol) and 6mL/2mL ethylene glycol mono The ether/water mixed solution was magnetically stirred at 100°C for 12 hours under the protection of nitrogen. After the reaction was completed, it was suction-filtered, and the filter cake was washed with n-hexane and ethanol respectively to obtain a dichloro bridge intermediate product. Add the obtained dichloro-bridge intermediate, sodium carbonate (1.0 mmol), acetylacetone (2.0 mmol) and 6 mL of ethylene glycol monoethyl ether into a single-necked round-bottomed flask, and stir magnetically at 100 ° C for 13 h under nitrogen protection. After the reaction is completed, vacuum spin Evaporated and separated by column chromatography to obtain analytically pure compound 18. The structure of the product was identified by ¹ HNMR, ¹³ CNMR and mass spectrometry, and the separation yield was 41.7%.

The synthesis of embodiment 19 compound 19

(1) Ligand synthesis: In the air, add 4-cyanophenylboronic acid (0.375mmol), potassium carbonate (0.5mmol), palladium acetate (0.005mmol), 2-bromoquinoline (0.25mmol) to the round bottom flask successively mmol), then, add ethanol-water mixed solution (4mL) with a volume ratio of 3:1, carry out Suzuki cross-coupling reaction at 80°C for 60 minutes with magnetic stirring, after the reaction is complete, add saturated saline (15mL), and The reaction product was extracted with ethyl ester (3×15ml), the organic phases were combined, the filtrate was concentrated, and separated by column chromatography to obtain analytically pure 2-(4-cyanophenyl)quinoline.

(2) Complex synthesis: Add potassium tetrachloroplatinate (0.2mmol), 2-(4-cyanophenyl)quinoline (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/ The water mixed solution was magnetically stirred at 100° C. for 12 h under the protection of nitrogen. After the reaction was completed, it was suction filtered, and the filter cake was washed with n-hexane and ethanol respectively to obtain a dichloro bridge intermediate product. Add the obtained dichloro-bridge intermediate, sodium carbonate (1.0 mmol), acetylacetone (2.0 mmol) and 6 mL of ethylene glycol monoethyl ether into a single-necked round-bottomed flask, and stir magnetically at 100 ° C for 13 h under nitrogen protection. After the reaction is completed, vacuum spin Evaporated, separated by column chromatography to obtain analytically pure compound 19. The structure of the product was identified by ¹ HNMR, ¹³ CNMR and mass spectrometry, and the separation yield was 49.6%.

The synthesis of embodiment 20 compound 20

(1) Ligand synthesis: In the air, add 4-fluorophenylboronic acid (0.375mmol), potassium carbonate (0.5mmol), palladium acetate (0.005mmol), 2-bromoquinoline (0.25mmol) to the round bottom flask successively ), then, add ethanol-water mixed solution (4mL) with a volume ratio of 3:1, carry out Suzuki cross-coupling reaction at 80°C for 60 minutes with magnetic stirring, track the reaction process by thin-layer chromatography, after the reaction is complete, add saturated Brine (15mL), the reaction product was extracted with ethyl acetate (3×15ml), the organic phases were combined, the filtrate was concentrated, and separated by column chromatography to obtain analytically pure 2-(4-fluorophenyl)quinoline.

(2) Complex synthesis: Add potassium tetrachloroplatinate (0.2mmol), 2-(4-fluorophenyl)quinoline (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water into a round-bottomed two-necked flask The mixed solution was magnetically stirred at 100° C. for 12 h under the protection of nitrogen. After the reaction was completed, it was filtered with suction, and the filter cake was washed with n-hexane and ethanol respectively to obtain a dichloro bridge intermediate product. Add the obtained dichloro-bridge intermediate, sodium carbonate (1.0 mmol), acetylacetone (2.0 mmol) and 6 mL of ethylene glycol monoethyl ether into a single-necked round-bottomed flask, and stir magnetically at 100 ° C for 13 h under nitrogen protection. After the reaction is completed, vacuum spin Evaporated, separated by column chromatography to obtain analytically pure compound 20. The structure of the product was identified by ¹ HNMR, ¹³ CNMR and mass spectrometry, and the separation yield was 49.1%.

The synthesis of embodiment 21 compound 21

(1) Ligand synthesis: In air, add 4-(N-carbazolyl)phenylboronic acid (0.375mmol), potassium carbonate (0.5mmol), palladium acetate (0.005mmol), 2- Bromoquinoline (0.25mmol), then, add the ethanol-water mixed solution (4mL) that volume ratio is 3:1, carry out Suzuki cross-coupling reaction 60 minutes at 80 ℃ of magnetic stirring, follow the reaction process by thin-layer chromatography, After the reaction was complete, saturated brine (15mL) was added, the reaction product was extracted with ethyl acetate (3×15ml), the organic phases were combined, the filtrate was concentrated, and separated by column chromatography to obtain analytically pure 2-(4-(N -carbazolyl)phenyl)quinoline.

(2) Complex synthesis: Add potassium tetrachloroplatinate (0.2mmol), 2-(4-(N-carbazolyl)phenyl)quinoline (0.24mmol) and 6mL/2mL ethyl alcohol into a two-necked round-bottomed flask Glycol monoethyl ether/water mixed solution was magnetically stirred at 100° C. for 12 hours under nitrogen protection. After the reaction was completed, the intermediate product was washed with normal hexane and ethanol while suction filtering. Add the obtained intermediate product, sodium carbonate (1.0 mmol), acetylacetone (2.0 mmol) and 6 mL of ethylene glycol monoethyl ether into a single-necked round-bottom flask, and stir magnetically at 100 °C for 13 h under nitrogen protection. Column chromatography separated to obtain analytically pure compound 21. The structure of the product was identified by ¹ HNMR, ¹³ CNMR and mass spectrometry, and the separation yield was 57.2%.

The synthesis of embodiment 22 compound 22

(1) Ligand synthesis: in the air, add triphenylamine boronic acid (0.375mmol), potassium carbonate (0.5mmol), palladium acetate (0.005mmol), 2-bromoquinoline (0.25mmol) successively in the round bottom flask, Then, add the ethanol-water mixed solution (4mL) that volume ratio is 3:1, under 80 ℃ reaction temperature, magnetic stirring, carry out Suzuki cross-coupling reaction 60 minutes, track reaction process by thin-layer chromatography, after reaction is complete , adding saturated brine (15mL), extracting the reaction product with ethyl acetate (3×15ml), combining the organic phases, concentrating the filtrate, and separating by column chromatography to obtain analytically pure 2-(4-(N,N- Diphenylamino)phenyl)quinoline.

(2) Complex synthesis: Add potassium tetrachloroplatinate (0.2mmol), 2-(4-(N,N-diphenylamino)phenyl)quinoline (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution, magnetically stirred at 100°C for 12h under the protection of nitrogen, suction filtered after the reaction, and the filter cake was washed with n-hexane and ethanol respectively to obtain a dichloro bridge intermediate product. Add the obtained dichloro-bridge intermediate, sodium carbonate (1.0 mmol), acetylacetone (2.0 mmol) and 6 mL of ethylene glycol monoethyl ether into a single-necked round-bottomed flask, and stir magnetically at 100 ° C for 13 h under nitrogen protection. After the reaction is completed, vacuum spin After steaming and separation by column chromatography, analytically pure compound 22 was obtained. The structure of the product was identified by ¹ HNMR, ¹³ CNMR and mass spectrometry, and the separation yield was 38.7%.

The synthesis of embodiment 23 compound 23

(1) Ligand synthesis: In air, add 3-(N-phenyl)carbazolylboronic acid (0.375mmol), potassium carbonate (0.5mmol), palladium acetate (0.005mmol), 2 -Bromoquinoline (0.25mmol), then, add the ethanol-water mixed solution (4mL) that volume ratio is 3:1, carry out Suzuki cross-coupling reaction 60 minutes at 80 ℃ of magnetic stirring, follow the reaction process by thin-layer chromatography , after the reaction is complete, add saturated brine (15mL), extract the reaction product with ethyl acetate (3 × 15ml), combine the organic phases, concentrate the filtrate, and separate through column chromatography to obtain analytically pure 2-((3- (N-phenyl)carbazolyl)phenyl)quinoline.

(2) Complex synthesis: add potassium tetrachloroplatinate (0.2mmol), 2-((3-(N-phenyl)carbazolyl)phenyl)quinoline (0.24mmol) and 6mL/2mL ethylene glycol monoethyl ether/water mixed solution, magnetically stirred at 100°C for 12h under the protection of nitrogen, suction filtered after the reaction, and the filter cake was washed with n-hexane and ethanol respectively to obtain a dichloro bridge intermediate product. Add the obtained dichloro-bridge intermediate, sodium carbonate (1.0 mmol), acetylacetone (2.0 mmol) and 6 mL of ethylene glycol monoethyl ether into a single-necked round-bottomed flask, and stir magnetically at 100 ° C for 13 h under nitrogen protection. After the reaction is completed, vacuum spin After steaming and separation by column chromatography, analytically pure compound 23 was obtained. The structure of the product was identified by ¹ HNMR, ¹³ CNMR and mass spectrometry, and the isolated yield was 21.7%.

Claims (3)

1. A novel ring metal ligand-platinum complex, characterized in that: the C-N type ring metal neutral ligand synthesized by arylboronic acid compound and halogenated nitrogen heteroaromatic ring compound and acetylacetone jointly complex platinum metal ions Formed, its structure is as follows: 2. the preparation method of novel ring metal ligand-platinum complex according to claim 1, is characterized in that: the specific synthetic steps of described platinum complex are as follows: (1) Synthesis of C-N-type ring metal ligands: in the air, add 0.375mmol of arylboronic acid, 0.5mmol of potassium carbonate, 0.005mmol of palladium acetate, and 0.25mmol of halogenated nitrogen heteroaryl ring compound to the round bottom flask successively, and then, Add 4 mL of ethanol-water mixed solution with a volume ratio of 3:1, and carry out Suzuki cross-coupling reaction at 80°C with magnetic stirring, and follow the reaction progress by thin-layer chromatography. After the reaction is complete, add 15 mL of saturated saline, and use 15 mL for three times. The reaction product was extracted with ethyl acetate, the organic phases were combined, the filtrate was concentrated, and separated by column chromatography to obtain an analytically pure biaryl compound; (2) Complex synthesis: Add 0.2mmol of potassium tetrachloroplatinate, 0.24mmol of biaryl compound and 6mL of ethylene glycol monoethyl ether/2mL water mixed solution into a round-bottomed two-necked flask, and magnetically stir at 100°C for 12h under nitrogen protection. Suction filtration after the reaction is over, wash the filter cake with n-hexane and ethanol respectively to obtain the dichloro bridge intermediate product; add the obtained dichloro bridge intermediate product, 1.0 mmol of sodium carbonate, 2.0 mmol of acetylacetone and 6 mL of ethyl acetate to a single-necked round bottom flask. Glycol monoethyl ether was magnetically stirred at 100° C. for 13 h under the protection of nitrogen. After the reaction was completed, the reaction was rotary evaporated in vacuum and separated by column chromatography to obtain an analytically pure cyclometal ligand-platinum complex. 3. The application of the novel cyclometal ligand-platinum complex according to claim 1, characterized in that: the platinum complex is used to make materials for oxygen sensors.