Tetranuclear metal complexes with stimulus-responsive properties, their preparation methods and applications

Abstract

This invention relates to the field of organic optoelectronic materials technology, and particularly to tetranuclear metal complexes with stimulus-responsive properties, their preparation methods, and applications. The phosphorescent platinum(II)-copper(I) tetranuclear metal complex exhibits a structural formula that allows it to induce changes in phosphorescence emission wavelength under different solvent or mechanical stimuli. This invention employs an electric field-induced redox method to prepare this complex. This method is convenient, does not require highly toxic chemical reagents, is environmentally friendly, and directly yields high-purity complex crystals. Based on its stimulus-responsive properties, the phosphorescent platinum(II)-copper(I) tetranuclear metal complex can be applied to optical anti-counterfeiting labels, exhibiting significant photoluminescence changes, high optical stability, and reversibility, making it a high-performance optical anti-counterfeiting material.

Description

Technical Field

[0001] This invention relates to the field of organic optoelectronic materials technology, and in particular to phosphorescent platinum(II)-copper(I) tetranuclear metal complexes with stimulus-responsive properties, their preparation methods and applications. Background Technology

[0002] Smart materials are a new type of material that can sense changes in its surrounding environment and respond accordingly. In recent years, smart materials have shown significant application potential in human production and daily life, attracting widespread attention from researchers in both the business and academic communities. Stimulus-responsive materials are a type of smart material; they are materials whose optical properties change reversibly under different external stimuli, such as light, mechanical force, steam, electric fields, or temperature. Due to their potential applications in sensors, imaging, information storage, and anti-counterfeiting, they are receiving increasing attention.

[0003] However, research on the application of stimulus-responsive phosphorescent materials is still relatively limited and requires further investigation and development. Furthermore, existing stimulus-responsive phosphorescent materials do not respond sensitively or significantly to changes in the microenvironment, which restricts their application in real-world situations. Therefore, it is necessary to develop a stimulus-responsive phosphorescent material that responds faster, more sensitively, and more significantly to changes in the microenvironment.

[0004] Therefore, existing technologies still need to be improved and developed. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the present invention provides a phosphorescent platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties, its preparation method and application, aiming to solve the problem that the existing stimulus-responsive phosphorescent materials are not sensitive and significant enough in responding to the microenvironment.

[0006] The inventors discovered that cyanide anions, as compact and high-performance bridging ligands, have found wide application in coordination chemistry, forming numerous inorganic and organometallic supramolecular structures. Their distinct heterodentate nature allows for electron binding to different metal centers, thus enabling the design of functional materials with interesting physical and chemical properties. Cyanide-containing d 8 Complexes, especially platinum(II) complexes, possess abundant excited states and are highly sensitive to minute changes in their surrounding environment, making them ideal candidates for constructing stimulus-responsive luminescent materials. However, the chemical synthesis of cyanide-containing compounds typically requires the use of highly toxic chemical reagents and stringent reaction conditions.

[0007] Based on this, this invention designs a phosphorescent platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties. Furthermore, this invention employs an electric field-induced redox method to prepare the phosphorescent platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties. This preparation method is convenient to operate, avoids the use of highly toxic chemical reagents, and can directly obtain high-purity complex crystals without further purification, thus well meeting the needs of "green synthesis." Simultaneously, this invention provides the application of the stimulus-responsive platinum(II)-copper(I) tetranuclear metal complex in optical anti-counterfeiting. Optical anti-counterfeiting labels made from it exhibit significant photoluminescence changes, high optical stability, and reversibility, making it a high-performance optical anti-counterfeiting material with significant application prospects in optical anti-counterfeiting.

[0008] Specifically, the technical solution of the present invention is as follows:

[0009] In a first aspect, the present invention provides a phosphorescent platinum(II)-copper(I) tetranuclear metal complex having stimulus-responsive properties, wherein the structural formula of the phosphorescent platinum(II)-copper(I) tetranuclear metal complex is shown in Formula I:

[0010]

[0011] A second aspect of the present invention provides a method for preparing a phosphorescent platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties, wherein the preparation method includes the steps of:

[0012] Provide the compound shown in Formula II:

[0013]

[0014] The compound shown in Formula II is dissolved in an organic solvent to obtain a compound solution;

[0015] The compound solution is added to an electrochemical device, which is then connected to a counter electrode and a working electrode. A bias voltage is applied to the compound solution, and after a preset reaction time under the bias voltage, crystals are obtained on the working electrode. After separation, a phosphorescent platinum(II)-copper(I) tetranuclear metal complex of formula I is obtained.

[0016] Optionally, the counter electrode is a platinum wire electrode, and the working electrode is a copper foil.

[0017] Optionally, the organic solvent is acetonitrile, and the concentration range of the compound solution is 1×10⁻⁶. -4 M–1×10 -3 M.

[0018] Optionally, the bias voltage range is 1V–6V, and the preset time range is 30s–60s.

[0019] Optionally, the method for preparing the compound represented by Formula II includes the steps of:

[0020] The reaction of phenylboronic acid and bromopyridine yields phenylpyridine;

[0021] The phenylpyridine was reacted with potassium chloroplatinate to obtain a platinum dichlorobridge;

[0022] The platinum dichlorobridge was reacted with tetrabutylammonium cyanide to obtain the compound shown in Formula II.

[0023] Optionally, the step of reacting phenylboronic acid and bromopyridine to obtain phenylpyridine specifically includes:

[0024] Phenylated acid, pyridine bromide, potassium carbonate, and tetra(triphenylphosphine)palladium were mixed to obtain a mixture;

[0025] Tetrahydrofuran, ethanol, and deionized water are mixed to obtain a mixed solvent;

[0026] The mixture was dissolved in the mixed solvent, heated and stirred under an inert atmosphere for 12 hours, and then purified to obtain pure phenylpyridine.

[0027] Optionally, the step of reacting the phenylpyridine with potassium chloroplatinate to obtain a platinum dichlorobridge specifically includes:

[0028] A mixed solution was obtained by mixing phenylpyridine, potassium chloroplatinate, 2-ethoxyethanol and water.

[0029] The mixed solution was heated to 110°C under an inert atmosphere and then stirred and refluxed for 24 hours. After purification, the platinum dichloride bridge was obtained.

[0030] Optionally, the step of reacting the platinum dichlorobridge with tetrabutylammonium cyanide to obtain the compound represented by Formula II specifically includes:

[0031] Tetrabutylammonium cyanide and platinum dichlorobridge were added to a solution of dichloromethane, heated under reflux for 5 hours, and purified to obtain the compound shown in Formula II.

[0032] A third aspect of the present invention provides the application of phosphorescent platinum(II)-copper(I) tetranuclear metal complexes with stimulus-responsive properties in optical anti-counterfeiting;

[0033] And / or, the application of phosphorescent platinum(II)-copper(I) tetranuclear metal complexes with stimulus-responsive properties prepared by the preparation method described in this invention in optical anti-counterfeiting.

[0034] Beneficial Effects: This invention provides a phosphorescent platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties, its preparation method, and its applications. The phosphorescent platinum(II)-copper(I) tetranuclear metal complex is prepared using an electric field-induced redox method. This preparation method is convenient, does not require highly toxic chemical reagents, is environmentally friendly, and directly yields high-purity complex crystals. The complex can induce changes in phosphorescence emission wavelength under different solvents or mechanical stimuli. Based on the stimulus-responsive properties of the phosphorescent platinum(II)-copper(I) tetranuclear metal complex, it can be used to fabricate optical anti-counterfeiting labels, exhibiting significant photoluminescence changes, high optical stability, and reversibility. It is a high-performance optical anti-counterfeiting material with significant application prospects in optical anti-counterfeiting. Attached Figure Description

[0035] Figure 1 This is a schematic diagram of the electrochemical device for the phosphorescent platinum(II)-copper(I) tetranuclear metal complex in Example 2 of the present invention.

[0036] Figure 2 The image shows the X-ray single-crystal diffraction crystal structure of the phosphorescent platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties obtained in Example 2 of this invention.

[0037] Figure 3 This is a field emission scanning electron microscope image of the phosphorescent platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties prepared in Example 2 of the present invention.

[0038] Figure 4 The infrared spectrum of the phosphorescent platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties prepared in Example 2 of this invention is shown.

[0039] Figure 5 The emission spectra of the phosphorescent platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties prepared in Example 2 of this invention are shown in three emission states.

[0040] Figure 6 The graph shows the emission intensity changes of the three emission states of the phosphorescent platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive characteristics prepared in Example 2 of this invention under continuous irradiation with 365nm wavelength ultraviolet light for 120 min.

[0041] Figure 7 This is a graph showing the change in emission wavelength of the phosphorescent platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties prepared in Example 2 of the present invention as it repeatedly switches between three emission states.

[0042] Figure 8This is a schematic diagram and a black-and-white photograph of an anti-counterfeiting label made using a phosphorescent platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties, as shown in Example 3 of this invention. Detailed Implementation

[0043] This invention provides phosphorescent platinum(II)-copper(I) tetranuclear metal complexes with stimulus-responsive properties, their preparation methods, and applications. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention is further described in detail below.

[0044] The phosphorescent platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties according to embodiments of the present invention, wherein the structural formula of the phosphorescent platinum(II)-copper(I) tetranuclear metal complex is shown in Formula I:

[0045]

[0046] This embodiment provides a phosphorescent platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties. This complex can induce changes in phosphorescence emission wavelength under different solvents or mechanical stimuli. Typically, stimulus-responsive phosphorescent materials have a response time of several minutes and a phosphorescence wavelength change range within 100 nm. However, the complex in this embodiment can respond to the microenvironment within seconds, with a phosphorescence wavelength change reaching 140 nm (500 nm–640 nm), demonstrating a more significant response.

[0047] An embodiment of the present invention discloses a method for preparing a phosphorescent platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties, wherein the preparation method includes the following steps:

[0048] Provide the compound shown in Formula II:

[0049]

[0050] The compound shown in Formula II is dissolved in an organic solvent to obtain a compound solution;

[0051] The compound solution is added to an electrochemical device, which is then connected to a counter electrode and a working electrode. A bias voltage is applied to the compound solution, and after a preset reaction time under the bias voltage, crystals are obtained on the working electrode. After separating the crystals, the phosphorescent platinum(II)-copper(I) tetranuclear metal complex of Formula I can be obtained.

[0052] In this embodiment, the phosphorescent platinum(II)-copper(I) tetranuclear metal complex was prepared by an electric field-induced redox method. This method is simple to operate, low in cost, has mild reaction conditions, and does not require the use of highly toxic chemical reagents, thus well meeting the needs of "green synthesis".

[0053] In one embodiment, the method for preparing the compound represented by Formula II includes the steps of:

[0054] The reaction of phenylboronic acid and bromopyridine yields phenylpyridine;

[0055] The phenylpyridine was reacted with potassium chloroplatinate to obtain a platinum dichlorobridge;

[0056] The platinum dichlorobridge was reacted with tetrabutylammonium cyanide to obtain the compound shown in Formula II.

[0057] In one embodiment, the step of reacting phenylboronic acid and bromopyridine to obtain phenylpyridine specifically includes:

[0058] Phenylated acid, pyridine bromide, potassium carbonate, and tetra(triphenylphosphine)palladium were mixed to obtain a mixture;

[0059] Tetrahydrofuran, ethanol, and deionized water are mixed to obtain a mixed solvent;

[0060] The mixture was dissolved in the mixed solvent, heated and stirred under an inert atmosphere for 12 hours, and then purified to obtain pure phenylpyridine.

[0061] In one embodiment, the step of reacting the phenylpyridine with potassium chloroplatinate to obtain a platinum dichlorobridge specifically includes:

[0062] A mixed solution was obtained by mixing phenylpyridine, potassium chloroplatinate, 2-ethoxyethanol and water.

[0063] The mixed solution was heated to 110°C under an inert atmosphere and then stirred and refluxed for 24 hours. After purification, the platinum dichloride bridge was obtained.

[0064] In one embodiment, the step of reacting the platinum dichlorobridge with tetrabutylammonium cyanide to obtain the compound represented by Formula II specifically includes:

[0065] Tetrabutylammonium cyanide and platinum dichlorobridge were added to a solution of dichloromethane, heated under reflux for 5 hours, and purified to obtain the compound shown in Formula II.

[0066] In one embodiment, the counter electrode is a platinum wire electrode, and the working electrode is a copper foil.

[0067] In one embodiment, the organic solvent is acetonitrile.

[0068] In one embodiment, the concentration range of the compound solution is 1 × 10⁻⁶. -4 M–1×10 -3 M, such as 1×10 - 3M.

[0069] In one embodiment, the bias voltage ranges from 1V to 6V (e.g., 3V), the preset time ranges from 30s to 60s (e.g., 60s), and the reaction temperature is room temperature.

[0070] The application of phosphorescent platinum(II)-copper(I) tetranuclear metal complexes with stimulus-responsive properties in optical anti-counterfeiting according to embodiments of the present invention.

[0071] Phosphorescent platinum(II)-copper(I) tetranuclear metal complexes can induce changes in phosphorescence emission wavelengths under different solvent or mechanical stimuli. Based on their stimulus-responsive properties, phosphorescent platinum(II)-copper(I) tetranuclear metal complexes can be applied to optical anti-counterfeiting labels. Anti-counterfeiting labels made from phosphorescent platinum(II)-copper(I) tetranuclear metal complexes with stimulus-responsive properties exhibit significant photoluminescence changes, high optical stability, and reversible stimulus-responsive characteristics, making them a high-performance optical anti-counterfeiting material. Phosphorescent platinum(II)-copper(I) tetranuclear metal complexes with stimulus-responsive properties have significant application prospects in anti-counterfeiting.

[0072] The present invention will be further described below through specific embodiments.

[0073] Unless otherwise specified, the experimental procedures involved in the following embodiments are all routine procedures; the reagents and materials used are commercially available unless otherwise specified. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the scope of protection of the invention.

[0074] Example 1

[0075] The specific synthetic route and steps for preparing the compound shown in Formula II are as follows:

[0076]

[0077] Preparation of phenylpyridine: Phenyboric acid (12 mmol, 1.467 g), bromopyridine (8 mmol, 1.267 g), potassium carbonate (48 mmol, 4.49 g), and tetrakis(triphenylphosphine)palladium (5 mol%, 463 mg) were mixed to obtain a mixture. The mixture was dissolved in a solvent of tetrahydrofuran (30 mL), ethanol (15 mL), and deionized water (10 mL). The mixture was heated and stirred under reflux for 12 hours under an inert nitrogen atmosphere. After cooling to room temperature, water was added, and the mixture was extracted three times with ethyl acetate. The organic phase was evaporated to dryness to remove the solvent, and the product was separated by short silica gel chromatography. Phenylpyridine was obtained by eluing with ethyl acetate and n-hexane (n-hexane to ethyl acetate volume ratio of 8:1). The yield was 70%.

[0078] NMR characterization data of phenylpyridine: 1 H NMR (400MHz, CDCl3): δ = 8.71 (d, J = 4.4Hz, 1H), 8.00 (d, J = 4.8Hz, 2H), 7.77-7 .72(m,2H),7.48(t,J=7.6Hz,2H),7.42(t,J=7.2Hz,1H),7.25-7.21(m,1H). 13 C NMR (101MHz, CDCl3): δ157.49, 149.71, 139.44, 136.75, 128.97, 128.77, 126.94, 122.11, 120.57.

[0079] Preparation of platinum dichlorobridge: Phenylpyridine (0.58 mmol, 89.8 mg), potassium chloroplatinate (0.48 mmol, 200 mg), 2-ethoxyethanol (6 mL), and water (2 mL) were mixed to obtain a mixed solution. This mixed solution was heated to 110 °C under an inert nitrogen atmosphere and then stirred under reflux for 24 h. After cooling the reaction solution to room temperature, 20 mL of deionized water was added, resulting in a yellow precipitate. The solution was filtered off, and the precipitate was washed with deionized water to obtain an olive-green solid, i.e., the platinum dichlorobridge. The yield was 96%.

[0080] Preparation of the compound represented by Formula II: Tetrabutylammonium cyanide (0.5 mmol) and platinum dichlorobridge (0.1 mmol) were added to a solution of dichloromethane, heated to reflux, and after 5 hours, the reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation, and the mixture was separated by short silica gel chromatography. Ethyl acetate was used as the eluent, and the mixture was dried by rotary evaporation to obtain the crude product. The crude product was then dissolved in an appropriate amount of dichloromethane and recrystallized by diethyl ether diffusion to obtain the compound represented by Formula II (platinum(II) complex). The yield was 15%.

[0081] NMR characterization data of the compound represented by Formula II: 1 H NMR (400MHz, CDCl3): δ = 9.48 (d, J = 8Hz, 1H), 8.22 (d, J = 8Hz, 1H), 7.83 (td, J = 8Hz, 8Hz, 1H), 7.72 (m, 1H ),7.54(d,J=8Hz,1H),7.19(m,1H),7.10(m,1H),3.36(m,8H),1.71(m,8H),1.41(m,8H),0.99(m,12H).

[0082] Example 2

[0083] The preparation of phosphorescent platinum(II)-copper(I) tetranuclear metal complexes, the specific synthetic route and steps are as follows:

[0084]

[0085] The compound of formula II obtained in Example 1 was dissolved in acetonitrile to obtain a compound solution (the concentration of the compound solution was 1 × 10⁻⁶). -3 M). Use as follows Figure 1 The electrochemical apparatus shown uses a platinum wire as the counter electrode and a copper foil as the working electrode. A 3V bias voltage is applied to the compound solution, and the reaction is carried out for 60 seconds at room temperature. Under a microscope, blocky transparent crystals can be observed forming at the bottom of the electrolytic cell. After separation, a phosphorescent platinum(II)-copper(I) tetranuclear metal complex is obtained.

[0086] NMR characterization data of phosphorescent platinum(II)-copper(I) tetranuclear metal complexes: 1 H NMR (400MHz, DMSO-d6): δ = 9.11 (s, 2H), 8.12 (s, 4H), 9.97 (m, 4H), 7.46 (s, 2H), 7.18 (m, 4H), 3.34 (s, 12H).

[0087] Example 3

[0088] like Figure 8 As shown, an ink was prepared using the phosphorescent platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties obtained in Example 2 and a solvent. This ink was then filled into a template, and the solvent was removed to produce a dynamic photoluminescent color-changing anti-counterfeiting label. Under ultraviolet light, the anti-counterfeiting label emits green light. By adding different solvents (an aqueous solution of dichloromethane and tetrabutylammonium cyanide), the color of the anti-counterfeiting label can be changed to orange and blue-green, respectively. This dynamic photoluminescent color-changing property greatly enhances the security of the anti-counterfeiting label.

[0089] X-ray single-crystal diffraction tests, such as Figure 2 As shown, this indicates that the single crystal is a phosphorescent platinum(II)-copper(I) tetranuclear metal complex.

[0090] The morphology of the obtained crystals was observed using a scanning electron microscope (SEM), such as... Figure 3 As shown, the obtained phosphorescent platinum(II)-copper(I) tetranuclear metal complex is in the form of rod-shaped crystals and is uniformly distributed.

[0091] Infrared spectroscopy is a powerful tool for characterizing complex structures. The infrared spectra of phosphorescent platinum(II)-copper(I) tetranuclear metal complexes exhibiting stimulus-responsive properties are shown below. Figure 4 As shown in the figure, the characteristic absorption peaks of representative functional groups are all marked in the figure, with the peak at 2146 cm⁻¹. -1 This is the absorption peak for the C≡N bond stretching vibration, at 1608 cm⁻¹. -1 and 1482cm -1The absorption peak is the C=C stretching vibration peak, at 752 cm⁻¹. -1 The absorption peak is due to the bending vibration of the aromatic ring. The infrared spectrum of the phosphorescent platinum(II)-copper(I) tetranuclear metal complex exhibiting stimulus-responsive properties matches its chemical structure well.

[0092] The emission spectra of the phosphorescent platinum(II)-copper(I) tetranuclear metal complex in three emission states are as follows: Figure 5 As shown, the emission wavelengths of its three emission states are 500nm, 530nm, and 640nm, respectively.

[0093] The photostability of platinum(II)-copper(I) tetranuclear metal complexes with stimulus-responsive properties was tested under three emission states, which is of great significance for their practical applications. For example... Figure 6 As shown, after continuous irradiation with 365 nm ultraviolet light for 120 min, the emission intensity and maximum wavelength of the phosphorescent platinum(II)-copper(I) tetranuclear metal complex crystal remained almost unchanged in the three emission states. Subsequently, the reversibility of the stimulus-response properties of the phosphorescent platinum(II)-copper(I) tetranuclear metal complex was tested, as shown... Figure 7 As shown, by exposing the complex crystals to a specific solvent, the emission wavelength of the phosphorescent platinum(II)-copper(I) tetranuclear metal complex repeatedly varied between 500 nm, 530 nm, and 640 nm. After five cycles, compared to the initial state, the emission wavelength of the phosphorescent platinum(II)-copper(I) tetranuclear metal complex remained almost unchanged in each emission state. These results demonstrate that the phosphorescent platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties provided by this invention exhibits excellent photostability and reversibility, making it suitable for long-term optical anti-counterfeiting applications.

[0094] In summary, the platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties provided by this invention utilizes an electric field-induced redox synthesis method. This method is convenient to operate, does not require the use of highly toxic chemical reagents, and can directly obtain high-purity complex crystals, making it a green and environmentally friendly synthesis method. The anti-counterfeiting label made from the platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties provided by this invention exhibits significant photoluminescence changes, high optical stability, and reversibility, making it a high-performance optical anti-counterfeiting material.

[0095] It should be understood that the application of the present invention is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.

Claims

1. A method for preparing a phosphorescent platinum(II)-copper(I) tetranuclear metal complex having a stimuli-responsive property, characterized by, The phosphorescent platinum(II)-copper(I) tetranuclear metal complex has a structural formula as shown in Formula I: The preparation method of the phosphorescent platinum(II)-copper(I) tetranuclear metal complex comprises the steps of: providing a compound shown in formula II: dissolving the compound shown in formula II in an organic solvent to obtain a compound solution; adding the compound solution to an electrochemical device, connecting a counter electrode and a working electrode to the electrochemical device, applying a bias voltage to the compound solution, obtaining a crystal on the working electrode after reacting for a preset time under the bias voltage, and obtaining the phosphorescent platinum(II)-copper(I) tetranuclear metal complex shown in formula I after separating the crystal.

2. The method for preparing the phosphorescent platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties according to claim 1, characterized in that, The counter electrode is a platinum wire electrode, and the working electrode is a copper foil.

3. The method for preparing the phosphorescent platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties according to claim 1, characterized in that, The organic solvent is acetonitrile, the concentration of the compound solution ranges from 1 x 10 -4 M-1 x 10 -3 M.

4. The method for preparing the phosphorescent platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties according to claim 1, characterized in that, The bias voltage ranges from 1 V to 6 V, and the preset time ranges from 30 s to 60 s.

5. The method for preparing the phosphorescent platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties according to claim 1, characterized in that, The preparation method of the compound shown in formula II comprises the steps of: reacting phenylboronic acid and bromopyridine to obtain phenylpyridine; reacting the phenylpyridine and potassium chloroplatinate to obtain platinum dichloride bridge; reacting the platinum dichloride bridge with tetrabutylammonium cyanide to obtain the compound shown in formula II.

6. The method for preparing the phosphorescent platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties according to claim 5, characterized in that, The step of reacting phenylboronic acid and bromopyridine to obtain phenylpyridine specifically comprises: mixing phenylboronic acid, bromopyridine, potassium carbonate, and tetrakis(triphenylphosphine)palladium to obtain a mixture; mixing tetrahydrofuran, ethanol, and deionized water to obtain a mixed solvent; dissolving the mixture in the mixed solvent, heating and stirring under an inert atmosphere, and refluxing for 12 hours, and then purifying to obtain pure phenylpyridine.

7. The method for preparing the phosphorescent platinum(II)-copper(I) tetranuclear metal complex with stimulus-responsive properties according to claim 5, characterized in that, The step of reacting the phenylpyridine and potassium chloroplatinate to obtain platinum dichloride bridge specifically comprises: mixing phenylpyridine, potassium chloroplatinate, 2-ethoxyethanol, and water to obtain a mixed solution; heating the mixed solution to 110°C under an inert atmosphere, stirring and refluxing for 24 hours, and then purifying to obtain the platinum dichloride bridge.

8. The method of claim 5, wherein the method is characterized by, The step of reacting the platinum dichloride bridge with tetrabutylammonium cyanide to obtain the compound shown in formula II specifically comprises: adding tetrabutylammonium cyanide and platinum dichloride bridge to a dichloromethane solution, heating and refluxing for 5 hours, and then purifying to obtain the compound shown in formula II. The preparation method of the phosphorescent platinum(II)-copper(I) tetranuclear metal complex comprises the steps of: providing a compound shown in formula II: dissolving the compound shown in formula II in an organic solvent to obtain a compound solution; adding the compound solution to an electrochemical device, connecting a counter electrode and a working electrode to the electrochemical device, applying a bias voltage to the compound solution, obtaining a crystal on the working electrode after reacting for a preset time under the bias voltage, and obtaining the phosphorescent platinum(II)-copper(I) tetranuclear metal complex shown in formula I after separating the crystal. The counter electrode is a platinum wire electrode, and the working electrode is a copper foil. The bias voltage ranges from 1 V to 6 V, and the preset time ranges from 30 s to 60 s. The preparation method of the compound shown in formula II comprises the steps of: reacting phenylboronic acid and bromopyridine to obtain phenylpyridine; reacting the phenylpyridine and potassium chloroplatinate to obtain platinum dichloride bridge; reacting the platinum dichloride bridge with tetrabutylammonium cyanide to obtain the compound shown in formula II. The step of reacting phenylboronic acid and bromopyridine to obtain phenylpyridine specifically comprises: mixing phenylboronic acid, bromopyridine, potassium carbonate, and tetrakis(triphenylphosphine)palladium to obtain a mixture; mixing tetrahydrofuran, ethanol, and deionized water to obtain a mixed solvent; dissolving the mixture in the mixed solvent, heating and stirring under an inert atmosphere, and refluxing for 12 hours, and then purifying to obtain pure phenylpyridine. The step of reacting the phenylpyridine and potassium chloroplatinate to obtain platinum dichloride bridge specifically comprises: mixing phenylpyridine, potassium chloroplatinate, 2-ethoxyethanol, and water to obtain a mixed solution; heating the mixed solution to 110°C under an inert atmosphere, stirring and refluxing for 24 hours, and then purifying to obtain the platinum dichloride bridge. The step of reacting the platinum dichloride bridge with tetrabutylammonium cyanide to obtain the compound shown in formula II specifically comprises: adding tetrabutylammonium cyanide and platinum dichloride bridge to a dichloromethane solution, heating and refluxing for 5 hours, and then purifying to obtain the compound shown in formula II.

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