Synthesis method and application of platinum complexes with different configurations regulated by a chlorine source

Abstract

The present invention discloses a method for synthesizing platinum complexes with different configurations regulated by a chlorine source and its application. The method for synthesizing platinum complexes with different configurations uses a cyclometalated platinum chloride complex coordinated by N^C^N as a precursor, introduces a strong-field isocyanide ligand at the fourth coordination site of the precursor, and synthesizes platinum complexes with different configurations by regulating the chlorine source participating in the reaction. The platinum complexes with different configurations include cationic platinum complexes with the chlorine source removed and molecular platinum complexes with the chlorine source added. The silver salts used for removing the chlorine source are silver nitrate, silver perchlorate, silver hexafluorophosphate or silver trifluoromethanesulfonate, and the chlorine sources added are selected from sodium chloride, potassium chloride, cesium chloride, N-chlorosuccinimide or tetrabutylammonium chloride. The platinum complexes synthesized by the present invention have high purity, solve the bottleneck problem that it is difficult to efficiently synthesize platinum complexes with different configurations in the case of chlorine ions participating in the reaction for a long time, and the platinum complexes with different configurations will exhibit significantly different luminescent colors and luminescent properties, and have a wide range of uses.

Description

Technical Field

[0001] The present invention relates to a method for synthesizing platinum complexes with different configurations regulated by a chlorine source and its applications, belonging to the technical field of luminescent materials. Background Art

[0002] In recent years, people have shown great interest in synthesizing cyclometalated platinum complexes with environment-responsive color and light-changing properties. Such materials have been widely used in fields such as encrypted documents, sensors, and optoelectronic devices due to their obvious color and light-changing behaviors in response to external stimuli such as pressure, solvents, and temperature.

[0003] Most platinum complexes have a four-coordinate square planar structure. Molecules are prone to form dimers or polymers through interactions such as Pt···Pt and π-π stacking in the axial direction, inducing the formation of supramolecular self-assembled aggregates, which usually exhibit color and light-changing behaviors induced by external stimuli such as solvents, temperature, and pressure. In addition, due to the rigid bonding mode of the cyclometalated ligand, it can well overcome the distortion in the excited state, greatly reducing non-radiative transitions. Introducing an isocyanide strong-field ligand with stimulus-responsive characteristics can raise the energy level of the deactivating d-d state, showing good luminescence properties. However, in the synthesis process of isocyanide cyclometalated platinum complexes, due to the presence of chloride ions, there are usually both bidentate-coordinated molecular-type isocyanide platinum complexes and tridentate-coordinated cationic platinum complexes, and it is difficult to isolate high-purity specific-configuration isocyanide platinum complexes. Summary of the Invention

[0004] The present invention provides a method for synthesizing platinum complexes with different configurations regulated by a chlorine source and its applications. By regulating the chlorine source participating in the reaction, the configuration of the platinum complex is regulated, and then its luminescence performance is regulated, effectively solving the practical problem that it is difficult to synthesize high-purity specific-configuration cyclometalated platinum complexes in the presence of chloride ions in existing cyclometalated platinum complexes.

[0005] To solve the above technical problems, the technical solutions adopted by the present invention are as follows:

[0006] A method for synthesizing platinum complexes with different configurations regulated by a chlorine source uses a cyclometalated platinum chloride complex coordinated by N^C^N as a precursor, introduces a strong-field isocyanide ligand at the fourth coordination site of the precursor, and synthesizes platinum complexes with different configurations by regulating the chlorine source participating in the reaction. The platinum complexes with different configurations include cationic platinum complexes (cationic platinum complexes coordinated by N^C^N) with the chlorine source removed and molecular-type platinum complexes (molecular-type platinum complexes coordinated by C^N) with the chlorine source added. The chlorine source (counter anion) removed is selected from silver nitrate, silver perchlorate, silver hexafluorophosphate, or silver trifluoromethanesulfonate, and the chlorine source added is selected from sodium chloride (NaCl), potassium chloride (KCl), cesium chloride (CsCl), N-chlorosuccinimide (NCS), or tetrabutylammonium chloride (TBAC).

[0007] The above synthesis method of platinum complexes with different configurations regulated by chlorine source can accurately synthesize isocyanide platinum complexes with different configurations by removing or adding chlorine source in the reaction. The isocyanide platinum complexes with different configurations will exhibit color and light change behaviors in response to multiple external stimuli such as solvents, concentrations, and pressures, and can be widely used in fields such as new anti-counterfeiting materials and stimulus-responsive materials.

[0008] To improve the luminescence performance, the N^C^N coordinated cyclometalated platinum complex is (-)-(N^C^N)PtCl containing F substituents, and its structural formula is: The isocyanide ligand is 2,6-dimethylphenyl isocyanide, and the synthesis routes of platinum complexes with different configurations are as follows:

[0009]

[0010] This application effectively solves the problem that it is difficult to synthesize high-purity isocyanide cyclometalated platinum complexes in the presence of chloride ions at the present stage. Different configurations of cyclometalated platinum complexes can be obtained by regulating the chlorine source participating in the reaction; different configurations of cyclometalated platinum complexes will exhibit different luminescence colors and luminescence performances.

[0011] The cationic isocyanide platinum complex (N^C^N coordinated cationic isocyanide platinum complex) obtained by removing the chlorine source in this application will exhibit red luminescence, yellow luminescence, or orange coloration; the molecular isocyanide platinum complex (C^N coordinated molecular isocyanide platinum complex) obtained by adding the chlorine source will exhibit green luminescence. This application provides a new strategy for the personalized synthesis of cyclometalated platinum complexes with specific configurations.

[0012] The cationic isocyanide platinum complex obtained by removing the chlorine source in this application can be used as a solvent-responsive material, pressure-responsive material, concentration-responsive material, or directly as a luminescent material, etc.; the molecular isocyanide platinum complex obtained by adding the chlorine source can be directly used as a luminescent material, etc.

[0013] As one of the preferred implementation schemes, the synthesis of the cationic isocyanide platinum complex with the chlorine source removed includes the following steps:

[0014] 1.1) Dissolve the N^C^N coordinated cyclometalated platinum chloride complex precursor in dichloromethane to obtain Solution 1;

[0015] 1.2) Dissolve the silver salt in distilled water to obtain Solution 2;

[0016] 1.3) Mix Solution 1 and Solution 2. Under argon protection, slowly add dropwise a dichloromethane solution containing the isocyanide ligand (about 40 - 60 drops per minute). After the addition is complete, continue the reaction at room temperature for 8 - 12 hours. Wash the resulting mixture with distilled water, collect the organic phase, dry by centrifugation, evaporate the solvent by rotary evaporation, and dry under vacuum to obtain the target product, the cationic isocyanide platinum complex coordinated by N^C^N;

[0017] To improve the yield and purity, and thus improve the luminescence performance, the molar amount of the silver salt is 1 - 5 times, preferably 2.5 - 3.5 times, the molar amount of the precursor of the cyclometalated platinum chloride complex coordinated by N^C^N; the molar amount of the isocyanide ligand is 0.5 - 2 times, preferably 0.8 - 1.2 times, the molar amount of the precursor of the cyclometalated platinum chloride complex coordinated by N^C^N.

[0018] To further improve the yield and purity, in step 1.2), the silver salt is silver nitrate, silver perchlorate, silver hexafluorophosphate or silver trifluoromethanesulfonate, preferably silver perchlorate, silver hexafluorophosphate or silver trifluoromethanesulfonate, more preferably silver trifluoromethanesulfonate.

[0019] As one preferred implementation, the synthesis of the molecular isocyanide platinum complex with a chlorine source includes the following steps:

[0020] 2.1) Dissolve the precursor of the cyclometalated platinum chloride complex coordinated by N^C^N in dichloromethane to obtain Solution 1;

[0021] 2.2) Under argon protection, slowly add dropwise a dichloromethane solution containing the isocyanide ligand. After the addition is complete, stir at room temperature for 1 hour, add the chlorine source, and continue to stir at room temperature for 8 - 12 hours. After evaporating the solvent, wash with methanol and dry under vacuum to obtain the target product, the molecular isocyanide platinum complex coordinated by C^N.

[0022] Through the control of the reaction steps and the selection of raw materials in this application, a complex with high purity and high stability is obtained.

[0023] To further improve the yield and purity, the molar amount of the isocyanide ligand is 0.5 - 2 times, preferably 0.8 - 1.2 times, the molar amount of the precursor of the cyclometalated platinum chloride complex coordinated by N^C^N; the molar amount of the chlorine source is 1 - 5 times, preferably 2.5 - 3.5 times, the molar amount of the precursor of the cyclometalated platinum chloride complex coordinated by N^C^N.

[0024] To further improve the yield and purity, in step 2.2), the chlorine source is sodium chloride (NaCl), potassium chloride (KCl), cesium chloride (CsCl), N-chlorosuccinimide (NCS) or tetrabutylammonium chloride (TBAC). Preferably, it is sodium chloride (NaCl), potassium chloride (KCl), cesium chloride (CsCl), or tetrabutylammonium chloride (TBAC), and more preferably tetrabutylammonium chloride.

[0025] The different configurations of platinum complexes prepared in this application can be used in high-tech fields such as new anti-counterfeiting materials, biological probes, stimulus-responsive materials, or three-dimensional displays.

[0026] For technologies not mentioned in the present invention, reference is made to the prior art.

[0027] Advantages of the present invention:

[0028] 1. This application provides a simple and effective method for synthesizing different configurations of isocyanoplatinum complexes. Different configurations of platinum complexes can be synthesized by regulating the chlorine source participating in the reaction.

[0029] 2. The different configurations of platinum complexes synthesized in this application will exhibit significantly different luminescent colors and luminescent properties, providing a new way for the personalized customization of platinum complexes with specific configurations.

[0030] 3. The different configurations of platinum complexes synthesized in this application have high purity, solving the long-term bottleneck problem that it is difficult to efficiently synthesize different configurations of platinum complexes in the case of chloride ions participating in the reaction. It is easy to promote and has strong repeatability.

[0031] 4. By introducing isocyanide ligands in this application, the obtained platinum complexes have stimulus-responsive characteristics and can be widely used in fields such as new anti-counterfeiting materials, biological probes, three-dimensional displays, and stimulus-responsive materials. Description of the Drawings

[0032] Figure 1 are photos of different luminescent colors of Example 4 and Example 11 under sunlight and ultraviolet light (λ = 365 nm) (Ambient light in the figure represents sunlight, and UV light represents ultraviolet light)

[0033] Figure 2 is the 1H NMR spectrum of the cationic platinum complex obtained by removing the chlorine source in Example 4;

[0034] Figure 3 is the 1H NMR spectrum of the molecular platinum complex obtained by adding the chlorine source in Example 11;

[0035] Figure 4 is the crystal structure of the cationic platinum complex obtained by removing the chlorine source in Example 4;

[0036] Figure 5It is the crystal structure of the molecular platinum complex with a chlorine source added in Example 11;

[0037] Figure 6 It is the emission spectra of the cationic platinum complex with the chlorine source removed in Example 4 at different concentrations in dichloromethane solvent;

[0038] Figure 7 It is the emission spectra of the molecular platinum complex with a chlorine source added in Example 11 at different concentrations in dichloromethane solvent;

[0039] Figure 8 It is the application image of the cationic platinum complex with the chlorine source removed in Example 4 in response to pressure stimuli. (In the figure, Ambient light represents sunlight, UV light represents ultraviolet light, Grinding represents grinding, and CH2Cl2 represents dichloromethane). Detailed implementation manners

[0040] To better understand the present invention, the content of the present invention will be further clarified below in conjunction with examples, but the content of the present invention is not limited to the following examples only.

[0041] In each example, the preparation of the platinum chloride complex precursor coordinated by N^C^N refers to Yang Q Y, Zhang H H, Qi X W, et al. Mechanochromic luminescence properties of fluoro-substituted pinene-containing cyclometalated platinum(II) complexes with multiple triplet excited states[J]. Dalton Transactions, 2021, 50(25): 8938-8946. The specific implementation method is as follows:

[0042] A mixture of 5-acetyl-2-fluorobenzeneboronic acid (1.82 g, 10 mmol), 2-bromo-3-fluoropyridine (1.93 g, 11 mmol), cesium carbonate (6.52 g, 20 mmol) and tetrakis(triphenylphosphine)palladium (347 mg, 0.3 mmol) was dissolved in a mixed solution of 1,4-dioxane (20 mL) and water (20 mL), and refluxed for 24 hours (95 °C) under argon protection. After cooling to room temperature, the solvent was evaporated, and the organic phase was washed successively with 50 mL of dichloromethane and 50 mL of brine with a mass fraction of 26.47% and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (petroleum ether / ethyl acetate = 10:1, v / v) to obtain a white solid (yield: 80%).

[0043] Iodine (2.67 g, 10.5 mmol) dissolved in 20 mL of pyridine was slowly added (about 50 drops per minute) to a 30 mL pyridine solution containing the above-mentioned white solid product. After reacting for 24 hours under argon protection at 105 °C, the solvent was evaporated, and the solid residue was washed with ether to obtain a yellow powder.

[0044] To a 50 mL ethanol solution of the above yellow powder (4.2 g, 10 mmol) were successively added 1R-(-)-myrtenal (1.58 g, 10.5 mmol) and ammonium acetate (1.54 g, 20 mmol), and the mixture was stirred for 24 hours under argon protection at 85 °C. After cooling and evaporating the ethanol, the organic phase was washed successively with 50 mL of dichloromethane and 50 mL of 26.47% brine and dried over anhydrous sodium sulfate. The purified ligand, a white powder (yield: 70%), was obtained by column chromatography (petroleum ether / ethyl acetate = 10:1, v / v).

[0045] The ligand (345 mg, 1 mmol) and potassium chloroplatinate (415 mg, 1 mmol) were dissolved in glacial acetic acid solution (20 mL), and the mixture was stirred at 110 °C for 3 days to obtain a red powder of the N^C^N coordinated platinum chloride complex. The organic phase was washed successively with 50 mL of dichloromethane and 50 mL of 26.47% brine and dried over anhydrous sodium sulfate. After evaporating the solvent, the crude product was purified by silica column chromatography (petroleum ether / dichloromethane = 1:1, v / v) (yield: 75%) to obtain the N^C^N coordinated platinum chloride complex.

[0046] In each example, the room temperature was 20 - 25 °C, the dropping rate for slow addition was 50 drops per minute, and a purity greater than 99.999% was regarded as 100%.

[0047] Example 1 Synthesis of Cationic Platinum Complexes with Chlorine Source Removed

[0048] The N^C^N coordinated platinum chloride complex precursor (100 mg, 0.17 mmol) was dissolved in 15 mL of dichloromethane solution. Subsequently, silver trifluoromethanesulfonate (44 mg, 0.17 mmol) was dissolved in 15 mL of distilled water. The above two solutions were mixed and stirred, and under argon protection, a 10 mL dichloromethane solution of 2,6-dimethylphenyl isocyanide (11 mg, 0.085 mmol) was slowly added dropwise. After the addition was complete, the mixture was stirred at room temperature for 8 hours. The mixture was washed with distilled water, the organic phase was collected, dried by centrifugation, the solvent was evaporated, and after vacuum drying, the target product, the N^C^N coordinated cationic platinum complex, a red solid (yield 30%, purity 75%), was obtained.

[0049] Example 2 Synthesis of Cationic Platinum Complexes with Chlorine Source Removed

[0050] Dissolve the N^C^N coordinated platinum chloride complex precursor (100 mg, 0.17 mmol) in 15 mL of dichloromethane solution. Subsequently, dissolve silver trifluoromethanesulfonate (220 mg, 0.85 mmol) in 15 mL of distilled water. Mix the above two solutions and stir. Under argon protection, slowly add dropwise a 10 mL dichloromethane solution of 2,6-dimethylphenyl isocyanide (11 mg, 0.085 mmol). After the addition is complete, stir at room temperature for 12 hours. Wash the mixture with distilled water, collect the organic phase, dry by centrifugation, evaporate the solvent by rotary evaporation, and dry under vacuum to obtain the target product, the N^C^N coordinated cationic platinum complex, a red solid (yield 43%, purity 78%).

[0051] Example 3 Synthesis of Cationic Platinum Complex with Chlorine Source Removed

[0052] Dissolve the N^C^N coordinated platinum chloride complex precursor (100 mg, 0.17 mmol) in 15 mL of dichloromethane solution. Subsequently, dissolve silver trifluoromethanesulfonate (44 mg, 0.17 mmol) in 15 mL of distilled water. Mix the above two solutions and stir. Under argon protection, slowly add dropwise a 10 mL dichloromethane solution of 2,6-dimethylphenyl isocyanide (44 mg, 0.34 mmol). After the addition is complete, stir at room temperature for 10 hours. Wash the mixture with distilled water, collect the organic phase, dry by centrifugation, evaporate the solvent by rotary evaporation, and dry under vacuum to obtain the target product, the N^C^N coordinated cationic platinum complex, a red solid (yield 62%, purity 81%).

[0053] Example 4 Synthesis of Cationic Platinum Complex with Chlorine Source Removed

[0054] Dissolve the N^C^N coordinated platinum chloride complex precursor (100 mg, 0.17 mmol) in 15 mL of dichloromethane solution. Subsequently, dissolve silver trifluoromethanesulfonate (132 mg, 0.51 mmol) in 15 mL of distilled water. Mix the above two solutions and stir. Under argon protection, slowly add dropwise a 10 mL dichloromethane solution of 2,6-dimethylphenyl isocyanide (22 mg, 0.17 mmol). After the addition is complete, stir at room temperature for 10 hours. Wash the mixture with distilled water, collect the organic phase, dry by centrifugation, evaporate the solvent by rotary evaporation, and dry under vacuum to obtain the target product, the N^C^N coordinated cationic platinum complex, a red solid (yield 99%, purity 100%). The proton nuclear magnetic resonance spectrum is as Figure 2 shown.

[0055] Example 5 Synthesis of Cationic Platinum Complex with Chlorine Source Removed

[0056] Dissolve the N^C^N coordinated platinum chloride complex precursor (100 mg, 0.17 mmol) in 15 mL of dichloromethane solution. Subsequently, dissolve silver nitrate (87 mg, 0.51 mmol) in 15 mL of distilled water. Mix the above two solutions and stir. Under argon protection, slowly add dropwise a 10 mL dichloromethane solution of 2,6-dimethylphenyl isocyanide (22 mg, 0.17 mmol). After the addition is complete, stir at room temperature for 10 hours. Wash the mixture with distilled water, collect the organic phase, dry by centrifugation, evaporate the solvent by rotary evaporation, and then dry under vacuum to obtain the target product, the N^C^N coordinated cationic platinum complex, a red solid (yield 70%, purity 90%).

[0057] Example 6 Synthesis of Cationic Platinum Complex with Chlorine Source Removed

[0058] Dissolve the N^C^N coordinated platinum chloride complex precursor (100 mg, 0.17 mmol) in 15 mL of dichloromethane solution. Subsequently, dissolve silver perchlorate (106 mg, 0.51 mmol) in 15 mL of distilled water. Mix the above two solutions and stir. Under argon protection, slowly add dropwise a 10 mL dichloromethane solution of 2,6-dimethylphenyl isocyanide (22 mg, 0.17 mmol). After the addition is complete, stir at room temperature for 10 hours. Wash the mixture with distilled water, collect the organic phase, dry by centrifugation, evaporate the solvent by rotary evaporation, and then dry under vacuum to obtain the target product, the N^C^N coordinated cationic platinum complex, a red solid (yield 81%, purity 91%).

[0059] Example 7 Synthesis of Cationic Platinum Complex with Chlorine Source Removed

[0060] Dissolve the N^C^N coordinated platinum chloride complex precursor (100 mg, 0.17 mmol) in 15 mL of dichloromethane solution. Subsequently, dissolve silver hexafluorophosphate (129 mg, 0.51 mmol) in 15 mL of distilled water. Mix the above two solutions and stir. Under argon protection, slowly add dropwise a 10 mL dichloromethane solution of 2,6-dimethylphenyl isocyanide (22 mg, 0.17 mmol). After the addition is complete, stir at room temperature for 10 hours. Wash the mixture with distilled water, collect the organic phase, dry by centrifugation, evaporate the solvent by rotary evaporation, and then dry under vacuum to obtain the target product, the N^C^N coordinated cationic platinum complex, a red solid (yield 77%, purity 85%).

[0061] Example 8 Synthesis of Molecular Platinum Complex with Chlorine Source Added

[0062] Dissolve the N^C^N coordinated platinum chloride complex precursor (100 mg, 0.17 mmol) in 15 mL of dichloromethane solution. Under argon protection, slowly drip into 15 mL of dichloromethane solution containing 2,6-dimethylphenyl isocyanide (11 mg, 0.085 mmol). After the addition is complete, stir at room temperature for 1 hour, add (47 mg, 0.17 mmol) of tetrabutylammonium chloride, continue to stir at room temperature for 8 hours, evaporate the solvent, wash with methanol, and dry under vacuum to obtain the target product, the C^N coordinated molecular platinum complex, a green solid (yield: 35%, purity 78%).

[0063] Example 9 Synthesis of Molecular Platinum Complex with Added Chlorine Source

[0064] Dissolve the N^C^N coordinated platinum chloride complex precursor (100 mg, 0.17 mmol) in 15 mL of dichloromethane solution. Under argon protection, slowly drip into 15 mL of dichloromethane solution containing 2,6-dimethylphenyl isocyanide (11 mg, 0.085 mmol). After the addition is complete, stir at room temperature for 1 hour, add (235 mg, 0.85 mmol) of tetrabutylammonium chloride, continue to stir at room temperature for 12 hours, evaporate the solvent, wash with methanol, and dry under vacuum to obtain the target product, the C^N coordinated molecular platinum complex, a green solid (yield: 40%, purity 80%).

[0065] Example 10 Synthesis of Molecular Platinum Complex with Added Chlorine Source

[0066] Dissolve the N^C^N coordinated platinum chloride complex precursor (100 mg, 0.17 mmol) in 15 mL of dichloromethane solution. Under argon protection, slowly drip into 15 mL of dichloromethane solution containing 2,6-dimethylphenyl isocyanide (44 mg, 0.34 mmol). After the addition is complete, stir at room temperature for 1 hour, add (47 mg, 0.17 mmol) of tetrabutylammonium chloride, continue to stir at room temperature for 10 hours, evaporate the solvent, wash with methanol, and dry under vacuum to obtain the target product, the C^N coordinated molecular platinum complex, a green solid (yield: 80%, purity 88%).

[0067] Example 11 Synthesis of Molecular Platinum Complex with Added Chlorine Source

[0068] Dissolve the N^C^N - coordinated platinum chloride complex precursor (100 mg, 0.17 mmol) in 15 mL of dichloromethane solution. Under argon protection, slowly drip into 15 mL of dichloromethane solution containing 2,6 - dimethylphenyl isocyanide (22 mg, 0.17 mmol). After the addition is complete, stir at room temperature for 1 hour, add (141 mg, 0.51 mmol) of tetrabutylammonium chloride, continue to stir at room temperature for 10 hours. After evaporating the solvent, wash with methanol and dry under vacuum to obtain the target product, the C^N - coordinated molecular platinum complex, a green solid (yield: 99%, purity 100%). The proton nuclear magnetic resonance spectrum is as Figure 3 shown.

[0069] Example 12 Synthesis of Molecular Platinum Complex with Added Chlorine Source

[0070] Dissolve the N^C^N - coordinated platinum chloride complex precursor (100 mg, 0.17 mmol) in 15 mL of dichloromethane solution. Under argon protection, slowly drip into 15 mL of dichloromethane solution containing 2,6 - dimethylphenyl isocyanide (22 mg, 0.17 mmol). After the addition is complete, stir at room temperature for 1 hour, add (30 mg, 0.51 mmol) of sodium chloride, continue to stir at room temperature for 10 hours. After evaporating the solvent, wash with methanol and dry under vacuum to obtain the target product, the C^N - coordinated molecular platinum complex, a green solid (yield: 75%, purity 87%).

[0071] Example 13 Synthesis of Molecular Platinum Complex with Added Chlorine Source

[0072] Dissolve the N^C^N - coordinated platinum chloride complex precursor (100 mg, 0.17 mmol) in 15 mL of dichloromethane solution. Under argon protection, slowly drip into 15 mL of dichloromethane solution containing 2,6 - dimethylphenyl isocyanide (22 mg, 0.17 mmol). After the addition is complete, stir at room temperature for 1 hour, add (38 mg, 0.51 mmol) of potassium chloride, continue to stir at room temperature for 10 hours. After evaporating the solvent, wash with methanol and dry under vacuum to obtain the target product, the C^N - coordinated molecular platinum complex, a green solid (yield: 66%, purity 90%).

[0073] Example 14 Synthesis of Molecular Platinum Complex with Added Chlorine Source

[0074] Dissolve the N^C^N coordinated platinum chloride complex precursor (100 mg, 0.17 mmol) in 15 mL of dichloromethane solution. Under argon protection, slowly dropwise add 15 mL of dichloromethane solution containing 2,6-dimethylphenyl isocyanide (22 mg, 0.17 mmol). After the addition is complete, stir at room temperature for 1 hour, add cesium chloride (86 mg, 0.51 mmol), continue to stir at room temperature for 10 hours. After evaporating the solvent, wash with methanol and dry under vacuum to obtain the target product, the C^N coordinated molecular platinum complex, a green solid (yield: 60%, purity 85%).

[0075] Example 15 Synthesis of Molecular Platinum Complex with Added Chlorine Source

[0076] Dissolve the N^C^N coordinated platinum chloride complex precursor (100 mg, 0.17 mmol) in 15 mL of dichloromethane solution. Under argon protection, slowly dropwise add 15 mL of dichloromethane solution containing 2,6-dimethylphenyl isocyanide (22 mg, 0.17 mmol). After the addition is complete, stir at room temperature for 1 hour, add N-chlorosuccinimide (68 mg, 0.51 mmol), continue to stir at room temperature for 10 hours. After evaporating the solvent, wash with methanol and dry under vacuum to obtain the target product, the C^N coordinated molecular platinum complex, a green solid (yield: 30%, purity 80%).

[0077] Figure 1 For the different luminescence color photos of Example 4 and Example 11 under sunlight and ultraviolet light (λ = 365 nm) (in the figure, CH2Cl2 / Acetone is dichloromethane / acetone with a volume ratio of 1:1, and CH3Cl / MeOH is chloroform / methanol with a volume ratio of 1:1), dissolve the N^C^N coordinated cationic platinum complex in a mixed solvent of dichloromethane / acetone (v:v = 1:1), and slowly volatilize at room temperature to obtain red luminescent crystals; dissolve the N^C^N coordinated cationic platinum complex in a mixed solvent of chloroform / methanol (v:v = 1:1), and slowly volatilize at room temperature to obtain yellow luminescent crystals; dissolve the C^N coordinated molecular platinum complex in a mixed solvent of dichloromethane / acetone (v:v = 1:1), and slowly volatilize at room temperature to obtain green luminescent crystals; Figure 2 and Figure 3 are the 1H NMR spectra of Example 4 and Example 11 respectively; Figure 4 and Figure 5 are the crystal structures of Example 4 and Example 11 respectively, with stable and unique configurations and a purity of 100%; Figure 6 is the emission spectrum diagram of the cationic platinum complex with the chlorine source removed prepared in Example 4 at different concentrations in dichloromethane solvent, from Figure 6It can be seen that the emission spectra of the cationic platinum complex in dichloromethane solutions with different concentrations all show an emission peak with a fine structure, where the maximum emission wavelength is located at 493 nm, and there is also a shoulder peak at 523 nm. As the concentration increases, a new shoulder peak appears at 620 nm, and the luminescence intensity gradually increases with the concentration. This is mainly due to the concentration-induced molecular packing, forming aggregates and generating aggregate-state emission; Figure 7 Emission spectra of the molecular platinum complex with added chlorine source prepared in Example 11 at different concentrations in dichloromethane solvent. From Figure 7 It can be seen that the emission peaks of the molecular platinum complex in dichloromethane solutions with different concentrations do not change with the increase in concentration, and the maximum emission wavelength is located at 493 nm, confirming that the molecular platinum complex cannot undergo effective packing; Figure 8 Schematic diagram showing that the cationic platinum complex exhibits reversible luminescence color in response to external pressure. From Figure 8 It can be seen that the cationic platinum complex exhibits an obvious mechanochromic luminescence phenomenon. After grinding in an agate mortar for two seconds, an orange solid is obtained, and the luminescence changes from bright red to orange. By adding dichloromethane or fumigating with dichloromethane vapor for one second, the original red-luminescent sample can be easily generated; proving that the cationic platinum complex can be used as a stimulus-responsive material.

Claims

1. A method for synthesizing platinum complexes with different configurations regulated by a chlorine source, characterized in that: Using a cyclometalated platinum chloride complex coordinated with N^C^N as a precursor, a strong-field isocyanide ligand is introduced at the fourth coordination site of the precursor. By regulating the chlorine source participating in the reaction, platinum complexes with different configurations are synthesized. The platinum complexes with different configurations include cationic platinum complexes with the chlorine source removed and molecular platinum complexes with the chlorine source added. The silver salts used to remove the chlorine source are silver nitrate, silver perchlorate, silver hexafluorophosphate or silver trifluoromethanesulfonate, and the chlorine sources added are selected from sodium chloride, potassium chloride, cesium chloride, N-chlorosuccinimide or tetrabutylammonium chloride; The N^C^N-coordinated cyclometalated platinum chloride complex is (-)-(N^C^N)PtCl containing an F substituent, and its structural formula is: ; the isocyanide ligand is 2,6-dimethylphenyl isocyanide; the synthetic routes of platinum complexes with different configurations are as follows: 。 2. The synthesis method according to claim 1, characterized in that: The synthesis of the cationic platinum complex with the chlorine source removed includes the following steps: 1.1) Dissolve the cyclometalated platinum chloride complex precursor coordinated with N^C^N in dichloromethane to obtain Solution 1; 1.2) Dissolve the silver salt in distilled water to obtain Solution 2; 1.3) Mix Solution 1 and Solution 2. Under argon protection, dropwise add a dichloromethane solution containing the isocyanide ligand. After the addition is complete, continue to react at room temperature for 8 - 12 hours. Wash the resulting mixture with distilled water, collect the organic phase, dry by centrifugation, rotary evaporate the solvent, and dry under vacuum to obtain the target product, the cationic platinum complex with the chlorine source removed.

3. The synthesis method according to claim 2, characterized in that: The molar amount of the silver salt used is 1 - 5 times the molar amount of the cyclometalated platinum chloride complex precursor coordinated with N^C^N, and the molar amount of the isocyanide ligand used is 0.5 - 2 times the molar amount of the cyclometalated platinum chloride complex precursor coordinated with N^C^N.

4. The synthesis method according to claim 2, characterized in that: In Step 1.2), the silver salt is silver perchlorate, silver hexafluorophosphate or silver trifluoromethanesulfonate.

5. The synthesis method according to claim 1 or 2, characterized in that: The synthesis of the molecular platinum complex with the chlorine source added includes the following steps: 2.1) Dissolve the cyclometalated platinum chloride complex precursor coordinated with N^C^N in dichloromethane to obtain Solution 1; 2.2) Under argon protection, slowly dropwise add a dichloromethane solution containing the isocyanide ligand. After the addition is complete, stir at room temperature for 1 hour, add the chlorine source, and continue to stir at room temperature for 8 - 12 hours. After rotary evaporating the solvent, wash with methanol and dry under vacuum to obtain the target product.

6. The synthesis method according to claim 5, characterized in that: The molar amount of the isocyanide ligand used is 0.5 - 2 times the molar amount of the cyclometalated platinum chloride complex precursor coordinated with N^C^N, and the molar amount of the chlorine source used is 1 - 5 times the molar amount of the cyclometalated platinum chloride complex precursor coordinated with N^C^N.

7. Use of platinum complexes with different configurations prepared by the synthesis method according to any one of claims 1-6, characterized in that: For novel anti-counterfeiting materials, stimuli-responsive materials or three-dimensional displays.

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