Rhodamine-diacetylene Schiff base conjugate, preparation method, application and photochromic method of metal ion complex based on rhodamine-diacetylene Schiff base conjugate

Abstract

The invention discloses a rhodamine-diacetylene Schiff base conjugate, a preparation method, application and a photochromic method of a metal ion complex based on the rhodamine-diacetylene Schiff base conjugate, and the preparation method of the rhodamine-diacetylene Schiff base conjugate comprises the following steps: 1a) dissolving rhodamine hydrazide and a diacetylene-salicylaldehyde conjugate in ethanol; a reaction mixture is obtained; and (2a) carrying out a stirring reaction on the reaction mixture obtained in the step (1a) under a heating condition, cooling to room temperature after the reaction is completed, removing the solvent, and carrying out column chromatography elution to obtain the rhodamine-diacetylene Schiff base conjugate, the conjugate, the preparation method, the application and the photochromic method based on the conjugate metal ion complex can be applied to the field of information encryption.

Description

Technical Field

[0001] This invention relates to a conjugate, its preparation method, its application, and a method for photochromism using metal ion complexes based on the conjugate. Specifically, it relates to a rhodamine-diacetylene Schiff base conjugate, its preparation method, its application, and a method for photochromism using metal ion complexes based on the rhodamine-diacetylene Schiff base conjugate. Background Technology

[0002] The era of big data showcases a modern society characterized by the rapid development of information technology. In recent years, information technology has continued to advance and has been widely applied to various fields, including people's daily lives, the economy, and the military. At the same time, the consideration of information security has increasingly become a focus of attention. Information leaks can threaten economic and military security, leading to serious social problems. Therefore, information security is receiving increasing attention, and the demand for high-security information encryption materials and methods is particularly urgent.

[0003] Stimulus-responsive optical materials exhibit altered optical properties in response to specific external stimuli such as heat, light, electricity, and force, thus possessing potential applications in information encryption. However, single-stimulus-responsive materials are easily decrypted, resulting in low security. Furthermore, they typically involve cumbersome and complex synthesis and purification processes, which are time-consuming and labor-intensive, and their functionality is limited. These issues significantly restrict the application of stimulus-responsive optical materials. Compared to single-stimulus-responsive materials, multi-stimulus-responsive optical materials offer higher information storage capacity. By encoding information in different optical states of the material and setting multiple specific stimulus conditions as decryption "keys," the hidden information is revealed only when all conditions are met simultaneously. This approach reduces the workload of synthesis, improves synthesis efficiency, and further increases the difficulty of cracking encrypted information, significantly enhancing the security of information transmission and enabling highly secure encryption and decryption processes. Therefore, designing and synthesizing high-performance, easily synthesized multi-stimulus-responsive optical materials has significant research value and application prospects. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a rhodamine-diacetylene Schiff base conjugate, its preparation method, its application, and a photochromic method for metal ion complexes based thereon. This conjugate, its preparation method, its application, and the photochromic method for metal ion complexes based on the conjugate can be applied to the field of information encryption.

[0005] To achieve the above objectives, this invention discloses a rhodamine-diacetylene Schiff base conjugate with the following chemical structure: .

[0006] This invention discloses a method for preparing a rhodamine-diacetylene Schiff base conjugate, comprising the following steps: 1a) Rhodamine hydrazide and diacetylene-salicylaldehyde conjugate were dissolved in ethanol to obtain a reaction mixture; 2a) The reaction mixture obtained in step 1a) was stirred under heating conditions. After the reaction was completed, it was cooled to room temperature, the solvent was removed, and then eluted by column chromatography to obtain the rhodamine-diacetylene Schiff base conjugate.

[0007] Furthermore, in step 1a), the ratio of rhodamine hydrazide, diacetylene-salicylaldehyde conjugate and ethanol in the mixture is 1.8 mmol: (1.5-2.2) mmol: (40-60) mL.

[0008] Furthermore, the heating temperature in step 2a) is (50-80) °C; The stirring reaction time in step 2a) is (24-48) h; In step 2a), during the column chromatography elution process, a mixture of petroleum ether and ethyl acetate with a boiling range of (60-90) °C is used as the eluent, wherein the volume ratio of petroleum ether to ethyl acetate is (10:1)-(4:1).

[0009] This invention discloses a Cu-based rhodamine-diacetylene Schiff base conjugate. 2+ Applications of photochromic compounds.

[0010] This invention discloses a Cu-based rhodamine-diacetylene Schiff base conjugate. 2+ A method for preparing a photochromic solution of a complex includes the following steps: 1b) Weigh out rhodamine-diacetylene Schiff base conjugate, 10,12-pentacarbondiyneic acid, tetrahydrofuran, and ethanol. Dissolve the rhodamine-diacetylene Schiff base conjugate and 10,12-pentacarbondiyneic acid in a mixed solvent of tetrahydrofuran and ethanol, respectively, to obtain tetrahydrofuran and ethanol solutions of the rhodamine-diacetylene Schiff base conjugate and 10,12-pentacarbondiyneic acid. The rhodamine-diacetylene Schiff base conjugate is dissolved in tetrahydrofuran and ethanol, respectively. The concentration of the rhodamine-diaethyne Schiff base conjugate in tetrahydrofuran and ethanol solutions was (1-5) mM, and the volume ratio of tetrahydrofuran to ethanol was (1:4)-(1:1); the concentration of 10,12-tetrapentacardiyne acid in tetrahydrofuran and ethanol solutions was (1-5) mM, and the volume ratio of tetrahydrofuran to ethanol was (1:4)-(1:1). 2b) Place the tetrahydrofuran and ethanol solutions of the rhodamine-diethynyl Schiff base conjugate and the tetrahydrofuran and ethanol solutions of 10,12-tetrapentacardiyne acid obtained in step 1b) into centrifuge tubes in sequence, and then add ethanol and water to the centrifuge tubes to obtain a mixed solution containing both the rhodamine-diethynyl Schiff base conjugate and 10,12-tetrapentacardiyne acid in ethanol and water. Then heat and sonicate the solution, cool it to room temperature, and refrigerate it for later use. 3b) The mixed solution of ethanol and water containing rhodamine-diacetylene Schiff base conjugate and 10,12-tetradecanoic acid obtained in step 2b) during low-temperature refrigeration was brought back to room temperature, and metal ions Cu were added to it. 2+ An aqueous solution of Cu, after being left to stand at room temperature, yields a Cu that is photochromic and contains a rhodamine-diacetylene Schiff base conjugate. 2+ A complex and a mixed solution of ethanol and water of 10,12-pentadecanodiyne.

[0011] Furthermore, step 2b) contains a mixed solution of ethanol and water containing both rhodamine-diacetylene Schiff base conjugate and 10,12-tetradecanoic acid, wherein the concentration of the rhodamine-diacetylene Schiff base conjugate is (25-50) μM, the concentration ratio of the rhodamine-diacetylene Schiff base conjugate to 10,12-tetradecanoic acid is (1:3)-(1:5), the volume ratio of ethanol to water is (1:9)-(2:3), the temperature of the ultrasonic heating is (50-70) °C, the time of the ultrasonic heating is (0.5-2) h, the temperature of the refrigerator is (0-4) °C, and the time of the refrigerator refrigeration is (12-48) h.

[0012] Furthermore, the Cu obtained in step 3b) that is photochromic and contains a rhodamine-diacetylene Schiff base conjugate is also capable of photochromic operation. 2+ A complex and a mixed solution of ethanol and water of 10,12-pentacardiyneic acid, wherein the rhodamine-diaethynyl Schiff base conjugate reacts with Cu 2+ The concentration ratio was (1:10)-(1:25), and the time to place it at room temperature was (5-30) min.

[0013] This invention discloses a Cu-based rhodamine-diacetylene Schiff base conjugate. 2+ The method for photochromism of complexes includes the following steps: 1c) Cu containing both rhodamine-diacetylene Schiff base conjugates 2+ A mixed solution of the complex and 10,12-pentacarbazinoic acid in ethanol and water, after being irradiated with 365 nm ultraviolet light, changed from colorless to purplish-red; when placed in the dark at room temperature, the color of the mixed solution returned to colorless. 2c) Cu containing both rhodamine-diacetylene Schiff base conjugates 2+ A mixed solution of the complex and 10,12-tetracarbodiyne in ethanol and water, after being irradiated with 254 nm ultraviolet light, changed from colorless to blue; after being irradiated with 365 nm ultraviolet light, the color of the mixed solution changed from blue to purple; and after being placed in the dark at room temperature, the color of the mixed solution returned from purple to blue. 3c) Cu containing both rhodamine-diacetylene Schiff base conjugates 2+ A mixed solution of the complex and 10,12-pentacarbazinoic acid in ethanol and water, after being irradiated with 365 nm ultraviolet light, changed from colorless to purplish-red; after being further irradiated with 254 nm ultraviolet light, the color of the mixed solution changed from purplish-red to purple; and when placed in the dark at room temperature, the color of the mixed solution changed from purple to blue.

[0014] Furthermore, in steps 1c), 2c), and 3c), the irradiation time with 365nm ultraviolet light is (2-5) min, the irradiation time with 254nm ultraviolet light is (2-5) min, and the time placed in the dark at room temperature is (5-10) min.

[0015] The present invention has the following beneficial effects: This invention relates to a method for preparing a rhodamine-diacetylene Schiff base conjugate, its application, and a method for photochromism using metal ion complexes based on the rhodamine-diacetylene Schiff base conjugate. Specifically, the rhodamine parent compound is selected as the fluorophore, and the rhodamine, 2,4-dihydroxybenzaldehyde, and 10,12-tetradecanoic acid are linked together via hydrazolysis and a Schiff base reaction to synthesize the rhodamine-diacetylene Schiff base conjugate. Rhodamine compounds possess a large molar absorptivity, a long ultraviolet absorption band, a long fluorescence emission band, and good optical stability. The Schiff base structure can coordinate with metal ions, is easy to synthesize and separate, and has a high yield. Introducing a salicylaldehyde Schiff base structure onto the rhodamine parent compound not only simplifies the synthesis process but also enables efficient coordination between the target compound and metal ions. This coordination can promote the ring-opening reaction of the rhodamine structure. Furthermore, by altering the types of metal ions, the stimulation conditions required for rhodamine ring-opening can be precisely controlled, thereby achieving precise control over the material's optical response. Ordered diacetylene groups can undergo polymerization under 254nm ultraviolet light irradiation to generate a blue polymer. Introducing diacetylene groups into the target molecule can leverage the photostimulation-responsive characteristics of diacetylene structures, thus introducing a multiple photostimulation-responsive mechanism into the molecular system and achieving the functional advantages of multi-stimulation-responsive optical materials.

[0016] This invention contains Cu containing both rhodamine-diacetylene Schiff base conjugate and other compounds.2+ A mixture of the complex and ethanol and water containing 10,12-pentacarbazinoic acid exhibits a series of distinct photochromic properties: upon irradiation with 365 nm ultraviolet light, the color of the mixture changes from colorless to purplish-red; upon being placed in the dark at room temperature, the color returns to colorless; upon irradiation with 254 nm ultraviolet light, the color changes from colorless to blue; upon further irradiation with 365 nm ultraviolet light, the color changes from blue to purple; upon being placed in the dark at room temperature, the color returns to blue; upon further irradiation with 365 nm ultraviolet light, the color changes from colorless to purplish-red; upon further irradiation with 254 nm ultraviolet light, the color changes from purplish-red to purple; upon being placed in the dark at room temperature, the color changes from purple to blue. The rhodamine-diacetylene Schiff base conjugate provided by this invention can complex with metal ions to produce photochromic materials with dual-band ultraviolet light stimulation response properties. It has the advantages of simple synthesis method, low cost and simple and convenient operation. The complex stimulation response properties of this molecule can improve its confidentiality and security in information encryption and decryption, and has great application potential in the field of information encryption. Attached Figure Description

[0017] To more clearly illustrate the technical solutions of the embodiments of this application, the drawings used in the description of the embodiments of this application will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0018] Figure 1 In this invention, the rhodamine-diaethyne Schiff base conjugate and 10,12-tetradecanoic acid are reacted in ethanol and water with Cu. 2+ The photos show the images before (left) exposure to 365nm light, after (right) exposure to 365nm light, and after recovery in the dark (left).

[0019] Figure 2 In this invention, the rhodamine-diaethyne Schiff base conjugate and 10,12-tetradecanoic acid are reacted in ethanol and water with Cu. 2+ The UV-Vis absorption spectra were then obtained before, after, and after being exposed to 365nm light and then restored in the dark.

[0020] Figure 3 In this invention, the rhodamine-diaethyne Schiff base conjugate and 10,12-tetradecanoic acid are reacted in ethanol and water with Cu. 2+The photos show the images before (left) illumination, after (middle) illumination, after (right) illumination, and after recovery from darkness (middle).

[0021] Figure 4 In this invention, the rhodamine-diaethyne Schiff base conjugate and 10,12-tetradecanoic acid are reacted in ethanol and water with Cu. 2+ The UV-Vis absorption spectra were obtained before, after, and after being exposed to 254nm light, then after being further exposed to 365nm light, and after being restored in the dark.

[0022] Figure 5 In this invention, the rhodamine-diaethyne Schiff base conjugate and 10,12-tetradecanoic acid are reacted in ethanol and water with Cu. 2+ The images are shown before exposure to 365nm light (from left to right: first centrifuge tube), after exposure to 365nm light (second centrifuge tube), after further exposure to 254nm light (third centrifuge tube), and after recovery in the dark (fourth centrifuge tube).

[0023] Figure 6 In this invention, the rhodamine-diaethyne Schiff base conjugate and 10,12-tetradecanoic acid are reacted in ethanol and water with Cu. 2+ The UV-Vis absorption spectra were obtained before, after, and after being exposed to 365nm light, then after being further exposed to 254nm light, and after being restored in the dark. Detailed Implementation

[0024] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] In the description of this invention, it should be understood that the terms "comprising" and "including" indicate the presence of the described features, integrals, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, integrals, steps, operations, elements, components and / or collections thereof.

[0026] It should also be understood that the terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to limit the invention. As used in this specification and the appended claims, the singular forms “a,” “an,” and “the” are intended to include the plural forms unless the context clearly indicates otherwise.

[0027] It should also be further understood that the term "and / or" as used in this specification and the appended claims refers to any combination and all possible combinations of one or more of the associated listed items, and includes such combinations. For example, A and / or B can represent three cases: A alone, A and B simultaneously, and B alone. Additionally, the character " / " in this invention generally indicates that the preceding and following objects have an "or" relationship.

[0028] It should be understood that although terms such as first, second, third, etc., may be used in the embodiments of the present invention to describe the preset range, these preset ranges should not be limited to these terms. These terms are only used to distinguish the preset ranges from one another. For example, without departing from the scope of the embodiments of the present invention, the first preset range may also be referred to as the second preset range, and similarly, the second preset range may also be referred to as the first preset range.

[0029] Depending on the context, the word "if" as used here can be interpreted as "when," "when," "in response to determination," or "in response to detection." Similarly, depending on the context, the phrase "if determination" or "if detection (of the stated condition or event)" can be interpreted as "when determination," "in response to determination," "when detection (of the stated condition or event)," or "in response to detection (of the stated condition or event)."

[0030] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. The components of the embodiments of the present invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations. Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0031] The accompanying drawings illustrate various structural schematic diagrams according to embodiments disclosed in this invention. These drawings are not to scale, and some details have been enlarged for clarity, and some details may have been omitted. The shapes of the various regions and layers shown in the drawings, as well as their relative sizes and positional relationships, are merely exemplary and may deviate from reality due to manufacturing tolerances or technical limitations. Furthermore, those skilled in the art can design regions / layers with different shapes, sizes, and relative positions as needed.

[0032] The chemical structure of the rhodamine-diacetylene Schiff base conjugate described in this invention is as follows: .

[0033] Example 1 The preparation method of the rhodamine-diacetylene Schiff base conjugate of the present invention includes the following steps: 1a) Rhodamine hydrazide and diacetylene-salicylaldehyde conjugate were dissolved in ethanol to obtain a reaction mixture; 2a) The reaction mixture obtained in step 1a) was stirred under heating conditions. After the reaction was completed, the mixture was cooled to room temperature, the solvent was removed, and then eluted by column chromatography to obtain the rhodamine-diacetylene Schiff base conjugate.

[0034] In step 1a), the ratio of rhodamine hydrazide, diacetylene-salicylaldehyde conjugate, and ethanol in the mixture is 1.8 mmol: 1.5 mmol: 60 mL. The heating temperature in step 2a) is 78°C; The stirring reaction time in step 2a) is 36 hours; In step 2a), during the column chromatography elution process, a mixture of petroleum ether and ethyl acetate with a boiling range of (60-90) °C is used as the eluent, wherein the volume ratio of petroleum ether to ethyl acetate is 6:1.

[0035] Example 2 The preparation method of the rhodamine-diacetylene Schiff base conjugate of the present invention includes the following steps: 1a) Rhodamine hydrazide and diacetylene-salicylaldehyde conjugate were dissolved in ethanol to obtain a reaction mixture; 2a) The reaction mixture obtained in step 1a) was stirred under heating conditions. After the reaction was completed, the mixture was cooled to room temperature, the solvent was removed, and then eluted by column chromatography to obtain the rhodamine-diacetylene Schiff base conjugate.

[0036] In step 1a), the ratio of rhodamine hydrazide, diacetylene-salicylaldehyde conjugate, and ethanol in the mixture is 1.8 mmol: 2.2 mmol: 40 mL. The heating temperature in step 2a) is 50°C; The stirring reaction time in step 2a) is 48 hours; In step 2a), during the column chromatography elution process, a mixture of petroleum ether and ethyl acetate with a boiling range of (60-90) °C is used as the eluent, wherein the volume ratio of petroleum ether to ethyl acetate is 10:1.

[0037] Example 3 The preparation method of the rhodamine-diacetylene Schiff base conjugate of the present invention includes the following steps: 1a) Rhodamine hydrazide and diacetylene-salicylaldehyde conjugate were dissolved in ethanol to obtain a reaction mixture; 2a) The reaction mixture obtained in step 1a) was stirred under heating conditions. After the reaction was completed, the mixture was cooled to room temperature, the solvent was removed, and then eluted by column chromatography to obtain the rhodamine-diacetylene Schiff base conjugate.

[0038] In step 1a), the ratio of rhodamine hydrazide, diacetylene-salicylaldehyde conjugate, and ethanol in the mixture is 1.8 mmol: 1.8 mmol: 50 mL. The heating temperature in step 2a) is 60°C; The stirring reaction time in step 2a) is 24 hours; In step 2a), during the column chromatography elution process, a mixture of petroleum ether and ethyl acetate with a boiling range of (60-90) °C is used as the eluent, wherein the volume ratio of petroleum ether to ethyl acetate is 4:1.

[0039] The rhodamine-diacetylene Schiff base conjugate described in this invention was subjected to proton NMR and carbon NMR spectroscopy, and the results are as follows: Nuclear magnetic resonance hydrogen spectroscopy determination: 1 H NMR (400 MHz, CDCl3), δ (ppm): 11.07 (s, 1H), 9.18 (s, 1H), 7.97 (d, J = 6.5 Hz, 1H), 7.52 (m, 2H), 7.17 (d, J = 6.8 Hz, 1H), 7.07(d, J = 7.2 Hz, 1H), 6.57 (s, 1H), 6.53-6.46 (m, 5H), 6.25 (d, J = 8.8 Hz, 2H), 3.32 (q, J = 6.5 Hz, 8H), 2.49 (t, 2H), 2.23 (t, 4H), 1.68 (m, 2H), 1.50 (t,4H), 1.36-1.25 (m, 26H), 1.15 (t, J = 6.1 Hz, 12H), 0.88 (t, J = 6.7 Hz, 3H).

[0040] Carbon NMR spectroscopy determination: 13C NMR (100 MHz, CDCl3), δ (ppm): 171.7, 164.1, 159.7,153.5, 152.8, 151.8, 150.6, 149.0, 133.4, 132.0, 129.9, 128.5, 128.0, 124.1,123.2, 116.6, 112.5, 110.2, 108.0, 105.2, 97.8, 77.5, 77.4, 66.4, 65.3, 65.2,44.3, 34.3, 31.9, 29.6, 29.4, 29.3, 29.05, 29.01, 28.9, 28.83, 28.80, 28.7, 28.3, 28.2, 24.8, 22.6, 19.1, 14.1, 12.6.

[0041] The Cu of the rhodamine-diacetylene Schiff base conjugate 2+ Applications of photochromic compounds.

[0042] Example 4 The Cu of the rhodamine-diacetylene Schiff base conjugate described in this invention 2+ The method for preparing a photochromic solution of a complex includes the following steps: 1b) Weigh out the rhodamine-diacetylene Schiff base conjugate, 10,12-pentadecanedioic acid, tetrahydrofuran, and ethanol. Then dissolve the rhodamine-diacetylene Schiff base conjugate and 10,12-pentadecanedioic acid in a mixed solvent of tetrahydrofuran and ethanol to obtain tetrahydrofuran and ethanol solutions of rhodamine-diacetylene Schiff base conjugate and 10,12-pentadecanedioic acid, respectively. The concentration of the rhodamine-diacetylene Schiff base conjugate in the tetrahydrofuran and ethanol solution is 2 mM, and the volume ratio of tetrahydrofuran to ethanol is 1:1. The concentration of 10,12-pentadecanedioic acid in the tetrahydrofuran and ethanol solution is 2 mM, and the volume ratio of tetrahydrofuran to ethanol is 1:1.

[0043] 2b) Place the tetrahydrofuran and ethanol solutions of the rhodamine-diethynyl Schiff base conjugate and the tetrahydrofuran and ethanol solutions of 10,12-tetrapentacardiyne acid obtained in step 1b) into centrifuge tubes in sequence, and then add ethanol and water to the centrifuge tubes to obtain a mixed solution containing both the rhodamine-diethynyl Schiff base conjugate and 10,12-tetrapentacardiyne acid in ethanol and water. Then heat and sonicate the solution, cool it to room temperature, and refrigerate it for later use.

[0044] 3b) The mixed solution of ethanol and water containing rhodamine-diacetylene Schiff base conjugate and 10,12-tetradecanoic acid obtained in step 2b) during low-temperature refrigeration was brought back to room temperature, and metal ions Cu were added to it. 2+ An aqueous solution of Cu, after being left at room temperature for a period of time, yields a Cu that is photochromic and contains a rhodamine-diacetylene Schiff base conjugate. 2+ A complex and a mixed solution of ethanol and water of 10,12-pentadecanodiyne.

[0045] Step 2b) contains a mixed solution of ethanol and water containing both rhodamine-diacetylene Schiff base conjugate and 10,12-tetradecanoic acid, wherein the concentration of the rhodamine-diacetylene Schiff base conjugate is 50 μM, the concentration ratio of the rhodamine-diacetylene Schiff base conjugate to 10,12-tetradecanoic acid is 1:3, the volume ratio of ethanol to water is 3:7, the heating and ultrasonication temperature is 65°C, the heating and ultrasonication time is 1 h, the refrigerator temperature is 4°C, and the refrigerator time is 12 h.

[0046] The Cu obtained in step 3b) is photochromic and contains a rhodamine-diacetylene Schiff base conjugate. 2+ A complex and a mixed solution of ethanol and water of 10,12-pentacardiyneic acid, wherein the rhodamine-diaethynyl Schiff base conjugate reacts with Cu 2+ The concentration ratio was 1:20, and the time to place it at room temperature was 10 minutes.

[0047] Example 5 The Cu of the rhodamine-diacetylene Schiff base conjugate described in this invention 2+ The method for preparing a photochromic solution of a complex includes the following steps: 1b) Weigh out the rhodamine-diacetylene Schiff base conjugate, 10,12-pentadecanedioic acid, tetrahydrofuran, and ethanol. Dissolve the rhodamine-diacetylene Schiff base conjugate and 10,12-pentadecanedioic acid in a mixed solvent of tetrahydrofuran and ethanol to obtain tetrahydrofuran and ethanol solutions of rhodamine-diacetylene Schiff base conjugate and 10,12-pentadecanedioic acid, respectively. The concentration of the rhodamine-diacetylene Schiff base conjugate in the tetrahydrofuran and ethanol solution is 1 mM, and the volume ratio of tetrahydrofuran to ethanol is 1:4. The concentration of 10,12-pentadecanedioic acid in the tetrahydrofuran and ethanol solution is 1 mM, and the volume ratio of tetrahydrofuran to ethanol is 1:4.

[0048] 2b) Place the tetrahydrofuran and ethanol solutions of the rhodamine-diethynyl Schiff base conjugate and the tetrahydrofuran and ethanol solutions of 10,12-tetrapentacardiyne acid obtained in step 1b) into centrifuge tubes in sequence, and then add ethanol and water to the centrifuge tubes to obtain a mixed solution containing both the rhodamine-diethynyl Schiff base conjugate and 10,12-tetrapentacardiyne acid in ethanol and water. Then heat and sonicate the solution, cool it to room temperature, and refrigerate it for later use.

[0049] 3b) The mixed solution of ethanol and water containing rhodamine-diacetylene Schiff base conjugate and 10,12-tetradecanoic acid obtained in step 2b) during low-temperature refrigeration was brought back to room temperature, and metal ions Cu were added to it. 2+ An aqueous solution of Cu, after being left at room temperature for a period of time, yields a Cu that is photochromic and contains a rhodamine-diacetylene Schiff base conjugate. 2+ A complex and a mixed solution of ethanol and water of 10,12-pentadecanodiyne.

[0050] Step 2b) involves a mixed solution of ethanol and water containing both rhodamine-diacetylene Schiff base conjugate and 10,12-tetradecanoic acid, wherein the concentration of the rhodamine-diacetylene Schiff base conjugate is 25 μM, the concentration ratio of the rhodamine-diacetylene Schiff base conjugate to 10,12-tetradecanoic acid is 1:5, the volume ratio of ethanol to water is 1:9, the heating and ultrasonication temperature is 50°C, the heating and ultrasonication time is 1.5 h, the refrigerator temperature is 2°C, and the refrigerator time is 36 h.

[0051] The Cu obtained in step 3b) is photochromic and contains a rhodamine-diacetylene Schiff base conjugate. 2+ A complex and a mixed solution of ethanol and water of 10,12-pentacardiyneic acid, wherein the rhodamine-diaethynyl Schiff base conjugate reacts with Cu 2+ The concentration ratio was 1:10, and the time to place it at room temperature was 20 minutes.

[0052] Example 6 The Cu of the rhodamine-diacetylene Schiff base conjugate described in this invention 2+ The method for preparing a photochromic solution of a complex includes the following steps: 1b) Weigh out the rhodamine-diacetylene Schiff base conjugate, 10,12-pentadecanedioic acid, tetrahydrofuran, and ethanol. Then dissolve the rhodamine-diacetylene Schiff base conjugate and 10,12-pentadecanedioic acid in a mixed solvent of tetrahydrofuran and ethanol to obtain tetrahydrofuran and ethanol solutions of rhodamine-diacetylene Schiff base conjugate and 10,12-pentadecanedioic acid, respectively. The concentration of the rhodamine-diacetylene Schiff base conjugate in the tetrahydrofuran and ethanol solution is 5 mM, and the volume ratio of tetrahydrofuran to ethanol is 3:7. The concentration of 10,12-pentadecanedioic acid in the tetrahydrofuran and ethanol solution is 5 mM, and the volume ratio of tetrahydrofuran to ethanol is 3:7.

[0053] 2b) Place the tetrahydrofuran and ethanol solutions of the rhodamine-diethynyl Schiff base conjugate and the tetrahydrofuran and ethanol solutions of 10,12-tetrapentacardiyne acid obtained in step 1b) into centrifuge tubes in sequence, and then add ethanol and water to the centrifuge tubes to obtain a mixed solution containing both the rhodamine-diethynyl Schiff base conjugate and 10,12-tetrapentacardiyne acid in ethanol and water. Then heat and sonicate the solution, cool it to room temperature, and refrigerate it for later use.

[0054] 3b) The mixed solution of ethanol and water containing rhodamine-diacetylene Schiff base conjugate and 10,12-tetradecanoic acid obtained in step 2b) during low-temperature refrigeration was brought back to room temperature, and metal ions Cu were added to it. 2+ An aqueous solution of Cu, after being left at room temperature for a period of time, yields a Cu that is photochromic and contains a rhodamine-diacetylene Schiff base conjugate. 2+ A complex and a mixed solution of ethanol and water of 10,12-pentadecanodiyne.

[0055] Step 2b) involves a mixed solution of ethanol and water containing both rhodamine-diacetylene Schiff base conjugate and 10,12-tetradecanoic acid, wherein the concentration of the rhodamine-diacetylene Schiff base conjugate is 40 μM, the concentration ratio of the rhodamine-diacetylene Schiff base conjugate to 10,12-tetradecanoic acid is 1:3.5, the volume ratio of ethanol to water is 1:4, the heating and ultrasonication temperature is 70°C, the heating and ultrasonication time is 0.5 h, the refrigerator temperature is 3°C, and the refrigerator time is 48 h.

[0056] The Cu obtained in step 3b) is photochromic and contains a rhodamine-diacetylene Schiff base conjugate. 2+ A complex and a mixed solution of ethanol and water of 10,12-pentacardiyneic acid, wherein the rhodamine-diaethynyl Schiff base conjugate reacts with Cu 2+The concentration ratio was 1:25, and the time to place it at room temperature was 15 minutes.

[0057] Example 7 The Cu of the rhodamine-diacetylene Schiff base conjugate described in this invention 2+ The method for preparing a photochromic solution of a complex includes the following steps: 1b) Weigh out the rhodamine-diacetylene Schiff base conjugate, 10,12-pentadecanedioic acid, tetrahydrofuran, and ethanol. Dissolve the rhodamine-diacetylene Schiff base conjugate and 10,12-pentadecanedioic acid in a mixed solvent of tetrahydrofuran and ethanol to obtain tetrahydrofuran and ethanol solutions of rhodamine-diacetylene Schiff base conjugate and 10,12-pentadecanedioic acid, respectively. The concentration of the rhodamine-diacetylene Schiff base conjugate in the tetrahydrofuran and ethanol solution is 3 mM, and the volume ratio of tetrahydrofuran to ethanol is 2:3. The concentration of 10,12-pentadecanedioic acid in the tetrahydrofuran and ethanol solution is 3 mM, and the volume ratio of tetrahydrofuran to ethanol is 2:3.

[0058] 2b) Place the tetrahydrofuran and ethanol solutions of the rhodamine-diethynyl Schiff base conjugate and the tetrahydrofuran and ethanol solutions of 10,12-tetrapentacardiyne acid obtained in step 1b) into centrifuge tubes in sequence, and then add ethanol and water to the centrifuge tubes to obtain a mixed solution containing both the rhodamine-diethynyl Schiff base conjugate and 10,12-tetrapentacardiyne acid in ethanol and water. Then heat and sonicate the solution, cool it to room temperature, and refrigerate it for later use.

[0059] 3b) The mixed solution of ethanol and water containing rhodamine-diacetylene Schiff base conjugate and 10,12-tetradecanoic acid obtained in step 2b) during low-temperature refrigeration was brought back to room temperature, and metal ions Cu were added to it. 2+ An aqueous solution of Cu, after being left at room temperature for a period of time, yields a Cu that is photochromic and contains a rhodamine-diacetylene Schiff base conjugate. 2+ A complex and a mixed solution of ethanol and water of 10,12-pentadecanodiyne.

[0060] Step 2b) involves a mixed solution of ethanol and water containing both rhodamine-diacetylene Schiff base conjugate and 10,12-tetradecanoic acid. The concentration of the rhodamine-diacetylene Schiff base conjugate is 30 μM, the concentration ratio of the rhodamine-diacetylene Schiff base conjugate to 10,12-tetradecanoic acid is 1:4.5, the volume ratio of ethanol to water is 7:13, the heating and ultrasonication temperature is 60°C, the heating and ultrasonication time is 1 h, the refrigerator temperature is 4°C, and the refrigerator time is 20 h.

[0061] The Cu obtained in step 3b) is photochromic and contains a rhodamine-diacetylene Schiff base conjugate. 2+ A complex and a mixed solution of ethanol and water of 10,12-pentacardiyneic acid, wherein the rhodamine-diaethynyl Schiff base conjugate reacts with Cu 2+ The concentration ratio was 1:15, and the time to place it at room temperature was 8 minutes.

[0062] Example 8 The Cu of the rhodamine-diacetylene Schiff base conjugate described in this invention 2+ The method for photochromism of coordination compounds includes the following steps: 1c) Cu containing both rhodamine-diacetylene Schiff base conjugates 2+ A mixed solution of the complex and 10,12-pentacarbazinoic acid in ethanol and water, after being irradiated with 365 nm ultraviolet light, changed from colorless to purplish-red; when placed in the dark at room temperature, the color of the mixed solution returned to colorless.

[0063] 2c) Cu containing both rhodamine-diacetylene Schiff base conjugates 2+ A mixed solution of the complex and 10,12-tetracarbodiyne in ethanol and water, after being irradiated with 254 nm ultraviolet light, changed from colorless to blue; after being irradiated with 365 nm ultraviolet light, the color of the mixed solution changed from blue to purple; and when placed in the dark at room temperature, the color of the mixed solution returned from purple to blue.

[0064] 3c) Cu containing both rhodamine-diacetylene Schiff base conjugates 2+ A mixed solution of the complex and 10,12-pentacarbazinoic acid in ethanol and water, after being irradiated with 365 nm ultraviolet light, changed from colorless to purplish-red; after being further irradiated with 254 nm ultraviolet light, the color of the mixed solution changed from purplish-red to purple; and when placed in the dark at room temperature, the color of the mixed solution changed from purple to blue.

[0065] In steps 1c), 2c), and 3c), the irradiation time with 365nm ultraviolet light is 5 minutes, the irradiation time with 254nm ultraviolet light is 5 minutes, and the time placed in the dark at room temperature is 10 minutes.

[0066] Example 9 The Cu of the rhodamine-diacetylene Schiff base conjugate described in this invention 2+ The method for photochromism of coordination compounds includes the following steps: 1c) Cu containing both rhodamine-diacetylene Schiff base conjugates 2+A mixed solution of the complex and 10,12-pentacarbazinoic acid in ethanol and water, after being irradiated with 365 nm ultraviolet light, changed from colorless to purplish-red; when placed in the dark at room temperature, the color of the mixed solution returned to colorless.

[0067] 2c) Cu containing both rhodamine-diacetylene Schiff base conjugates 2+ A mixed solution of the complex and 10,12-tetracarbodiyne in ethanol and water, after being irradiated with 254 nm ultraviolet light, changed from colorless to blue; after being irradiated with 365 nm ultraviolet light, the color of the mixed solution changed from blue to purple; and when placed in the dark at room temperature, the color of the mixed solution returned from purple to blue.

[0068] 3c) Cu containing both rhodamine-diacetylene Schiff base conjugates 2+ A mixed solution of the complex and 10,12-pentacarbazinoic acid in ethanol and water, after being irradiated with 365 nm ultraviolet light, changed from colorless to purplish-red; after being further irradiated with 254 nm ultraviolet light, the color of the mixed solution changed from purplish-red to purple; and when placed in the dark at room temperature, the color of the mixed solution changed from purple to blue.

[0069] In steps 1c), 2c), and 3c), the irradiation time with 365nm ultraviolet light is 2 minutes, the irradiation time with 254nm ultraviolet light is 2 minutes, and the time placed in the dark at room temperature is 8 minutes.

[0070] Example 10 The Cu of the rhodamine-diacetylene Schiff base conjugate described in this invention 2+ The method for photochromism of coordination compounds includes the following steps: 1c) Cu containing both rhodamine-diacetylene Schiff base conjugates 2+ A mixed solution of the complex and 10,12-pentacarbazinoic acid in ethanol and water, after being irradiated with 365 nm ultraviolet light, changed from colorless to purplish-red; when placed in the dark at room temperature, the color of the mixed solution returned to colorless.

[0071] 2c) Cu containing both rhodamine-diacetylene Schiff base conjugates 2+ A mixed solution of the complex and 10,12-tetracarbodiyne in ethanol and water, after being irradiated with 254 nm ultraviolet light, changed from colorless to blue; after being irradiated with 365 nm ultraviolet light, the color of the mixed solution changed from blue to purple; and when placed in the dark at room temperature, the color of the mixed solution returned from purple to blue.

[0072] 3c) Cu containing both rhodamine-diacetylene Schiff base conjugates 2+ A mixed solution of the complex and 10,12-pentacarbazinoic acid in ethanol and water, after being irradiated with 365 nm ultraviolet light, changed from colorless to purplish-red; after being further irradiated with 254 nm ultraviolet light, the color of the mixed solution changed from purplish-red to purple; and when placed in the dark at room temperature, the color of the mixed solution changed from purple to blue.

[0073] In steps 1c), 2c), and 3c), the irradiation time with 365nm ultraviolet light is 2 minutes, the irradiation time with 254nm ultraviolet light is 5 minutes, and the time placed in the dark at room temperature is 10 minutes.

[0074] After testing, Figure 1 Following treatments in Examples 4 and 8, 50 μM rhodamine-diaethyne Schiff base conjugate and 150 μM 10,12-tetradecanoic acid were reacted in ethanol and water (v / v, 3 / 7) with the addition of 1 mM Cu 2+ The photos show the images before (left) exposure to 365nm light, after (right) exposure to 365nm light, and after recovery in the dark (left).

[0075] Figure 1 The results show that the addition of Cu to the ethanol and aqueous solutions of rhodamine-diacetylene Schiff base conjugate and 10,12-tetradecanoic acid... 2+ Before irradiation with 365nm ultraviolet light, the mixed solution showed no obvious color change. After irradiation with 365nm ultraviolet light, the mixed solution turned purplish-red; after being placed in the dark for 10 minutes, the color of the mixed solution returned to colorless.

[0076] After testing, Figure 2 Following treatments in Examples 4 and 8, 50 μM rhodamine-diaethyne Schiff base conjugate and 150 μM 10,12-tetradecanoic acid were reacted in ethanol and water (v / v, 3 / 7) with the addition of 1 mM Cu 2+ The UV-Vis absorption spectra were then obtained before, after, and after being exposed to 365nm light and then restored in the dark.

[0077] Figure 2 The results show that the addition of Cu to the ethanol and aqueous solutions of rhodamine-diacetylene Schiff base conjugate and 10,12-tetradecanoic acid... 2+ Before irradiation with 365 nm ultraviolet light, the mixed solution showed virtually no absorption peak in the (400-800) nm range. After irradiation with 365 nm ultraviolet light, the mixed solution exhibited a significant absorption peak at 573 nm, indicating that the presence of Cu metal ions... 2+The presence of 365 nm light can cause the rhodamine structure in the conjugate to open. After being placed in the dark for 10 min, the mixed solution showed almost no absorption peaks in the (400-800) nm range, indicating that the rhodamine structure in the conjugate reverted to a spirocyclic structure under these conditions.

[0078] After testing, Figure 3 Following treatments in Examples 4 and 8, 50 μM rhodamine-diaethyne Schiff base conjugate and 150 μM 10,12-tetradecanoic acid were reacted in ethanol and water (v / v, 3 / 7) with the addition of 1 mM Cu 2+ The photos show the images before (left) illumination, after (middle) illumination, after (right) illumination, and after recovery from darkness (middle).

[0079] Figure 3 The results show that the addition of Cu to the ethanol and aqueous solutions of rhodamine-diacetylene Schiff base conjugate and 10,12-tetradecanoic acid... 2+ Before irradiation with 254nm ultraviolet light, the mixed solution was colorless. After irradiation with 254nm ultraviolet light, the mixed solution turned blue. After further irradiation with 365nm light, the mixed solution changed from blue to purple. After being placed in the dark for 10 minutes, the color of the mixed solution returned to blue from purple.

[0080] After testing, Figure 4 Following treatments in Examples 4 and 8, 50 μM rhodamine-diaethyne Schiff base conjugate and 150 μM 10,12-tetradecanoic acid were reacted in ethanol and water (v / v, 3 / 7) with the addition of 1 mM Cu 2+ The UV-Vis absorption spectra were obtained before, after, and after being exposed to 254nm light, then after being further exposed to 365nm light, and after being restored in the dark.

[0081] Figure 4 The results show that the addition of Cu to the ethanol and aqueous solutions of rhodamine-diacetylene Schiff base conjugate and 10,12-tetradecanoic acid... 2+Before irradiation with 254 nm UV light, the mixed solution showed virtually no absorption peaks in the (400-800) nm range. After irradiation with 254 nm UV light, the mixed solution exhibited a major and significant absorption peak at 663 nm, indicating that the acetylene structure in the mixed solution could undergo polymerization under 254 nm light irradiation. Further irradiation with 365 nm light revealed an absorption peak at 573 nm (after rhodamine ring-opening) and a peak at 655 nm (after acetylene polymerization) in the UV absorption spectrum. The purple color of the sample was attributed to the superposition of the purplish-red color of the rhodamine ring-opening structure and the blue color of the acetylene polymerization structure. After being placed in the dark for 10 minutes, the intensity of the absorption peak at 573 nm significantly decreased, indicating that under these conditions, the rhodamine structure in the conjugate reverted to a spirocyclic structure, and the color of the mixed solution was only the blue color of the acetylene polymerization.

[0082] After testing, Figure 5 Following treatments in Examples 4 and 8, 50 μM rhodamine-diaethyne Schiff base conjugate and 150 μM 10,12-tetradecanoic acid were reacted in ethanol and water (v / v, 3 / 7) with the addition of 1 mM Cu 2+ The images are shown before exposure to 365nm light (from left to right: first centrifuge tube), after exposure to 365nm light (second centrifuge tube), after further exposure to 254nm light (third centrifuge tube), and after recovery in the dark (fourth centrifuge tube).

[0083] Figure 5 The results show that the addition of Cu to the ethanol and aqueous solutions of rhodamine-diacetylene Schiff base conjugate and 10,12-tetradecanoic acid... 2+ Before irradiation with 365nm ultraviolet light, the mixed solution was colorless. After irradiation with 365nm ultraviolet light, the mixed solution turned purplish-red. After further irradiation with 254nm light, the mixed solution changed from purplish-red to purple. After being placed in the dark for 10 minutes, the color of the mixed solution changed from purple to blue.

[0084] After testing, Figure 6 Following treatments in Examples 4 and 8, 50 μM rhodamine-diaethyne Schiff base conjugate and 150 μM 10,12-tetradecanoic acid were reacted in ethanol and water (v / v, 3 / 7) with the addition of 1 mM Cu 2+ The UV-Vis absorption spectra were obtained before, after, and after being exposed to 365nm light, then after being further exposed to 254nm light, and after being restored in the dark.

[0085] Figure 6 The results show that the addition of Cu to the ethanol and aqueous solutions of rhodamine-diacetylene Schiff base conjugate and 10,12-tetradecanoic acid... 2+Before irradiation with 365 nm ultraviolet light, the mixed solution showed virtually no absorption peaks in the (400-800) nm range. After irradiation with 365 nm ultraviolet light, the mixed solution exhibited a significant absorption peak at 573 nm, indicating that the presence of Cu metal ions... 2+ In the presence of 365 nm light, the rhodamine structure in the conjugate undergoes ring-opening. Further irradiation with 254 nm light reveals an absorption peak at 573 nm (after ring-opening of rhodamine) and a peak at 655 nm (after polymerization of acetylene) in the UV absorption spectrum. The purple color of the sample indicates the superposition of the purple-red color of the rhodamine ring-opening structure and the blue color of the acetylene polymerization structure. After being placed in the dark for 10 minutes, the absorption peak intensity at 573 nm in the mixed solution significantly weakens, indicating that under these conditions, the rhodamine structure in the conjugate reverts to a spirocyclic structure, and the color of the mixed solution is only the blue of the acetylene polymerization.

[0086] Other embodiments of the invention will readily occur to those skilled in the art upon consideration of the specification and disclosure of the invention. This application is intended to cover any variations, uses, or adaptations of the invention that follow the general principles of the invention and include common knowledge or customary techniques in the art not disclosed herein. The specification and examples are to be considered exemplary only, and the true scope and spirit of the invention are indicated by the following claims.

[0087] It should be understood that the present invention is not limited to the precise structure described above and shown in the accompanying drawings, and various modifications and changes can be made without departing from its scope. The scope of the invention is limited only by the appended claims.

[0088] The above description is merely a preferred embodiment of the present invention and does not constitute any limitation on the present invention. Any simple modifications, alterations, or equivalent structural changes made to the above embodiments based on the technical essence of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A rhodamine-diacetylene Schiff base conjugate, characterized in that, The chemical structure is: 。 2. A method for preparing the rhodamine-diacetylene Schiff base conjugate according to claim 1, characterized in that, Includes the following steps: 1a) Rhodamine hydrazide and diacetylene-salicylaldehyde conjugate were dissolved in ethanol to obtain a reaction mixture; 2a) The reaction mixture obtained in step 1a) was stirred under heating conditions. After the reaction was completed, it was cooled to room temperature, the solvent was removed, and then eluted by column chromatography to obtain the rhodamine-diacetylene Schiff base conjugate.

3. The method for preparing the rhodamine-diacetylene Schiff base conjugate according to claim 2, characterized in that, In step 1a), the ratio of rhodamine hydrazide, diacetylene-salicylaldehyde conjugate and ethanol in the mixture is 1.8 mmol: (1.5-2.2) mmol: (40-60) mL.

4. The method for preparing the rhodamine-diacetylene Schiff base conjugate according to claim 2, characterized in that, The heating temperature in step 2a) is (50-80)℃; The stirring reaction time in step 2a) is (24-48) h; In step 2a), during the column chromatography elution process, a mixture of petroleum ether and ethyl acetate with a boiling range of (60-90) °C is used as the eluent, wherein the volume ratio of petroleum ether to ethyl acetate is (10:1)-(4:1).

5. A Cu of the rhodamine-diacetylene Schiff base conjugate as described in claim 1 2+ Applications of photochromic compounds.

6. A Cu based on the rhodamine-diacetylene Schiff base conjugate of claim 1 2+ A method for preparing a photochromic solution of a complex, characterized in that, Includes the following steps: 1b) Weigh out rhodamine-diacetylene Schiff base conjugate, 10,12-pentacarbondiyneic acid, tetrahydrofuran, and ethanol. Dissolve the rhodamine-diacetylene Schiff base conjugate and 10,12-pentacarbondiyneic acid in a mixed solvent of tetrahydrofuran and ethanol, respectively, to obtain tetrahydrofuran and ethanol solutions of the rhodamine-diacetylene Schiff base conjugate and 10,12-pentacarbondiyneic acid. The rhodamine-diacetylene Schiff base conjugate is dissolved in tetrahydrofuran and ethanol, respectively. The concentration of the rhodamine-diaethyne Schiff base conjugate in tetrahydrofuran and ethanol solutions was (1-5) mM, and the volume ratio of tetrahydrofuran to ethanol was (1:4)-(1:1); the concentration of 10,12-tetrapentacardiyne acid in tetrahydrofuran and ethanol solutions was (1-5) mM, and the volume ratio of tetrahydrofuran to ethanol was (1:4)-(1:1). 2b) Place the tetrahydrofuran and ethanol solutions of the rhodamine-diethynyl Schiff base conjugate and the tetrahydrofuran and ethanol solutions of 10,12-tetrapentacardiyne acid obtained in step 1b) into centrifuge tubes in sequence, and then add ethanol and water to the centrifuge tubes to obtain a mixed solution containing both the rhodamine-diethynyl Schiff base conjugate and 10,12-tetrapentacardiyne acid in ethanol and water. Then heat and sonicate the solution, cool it to room temperature, and refrigerate it for later use. 3b) The mixed solution of ethanol and water containing rhodamine-diacetylene Schiff base conjugate and 10,12-tetradecanoic acid obtained in step 2b) during low-temperature refrigeration was brought back to room temperature, and metal ions Cu were added to it. 2+ An aqueous solution of Cu, after being left to stand at room temperature, yields a Cu that is photochromic and contains a rhodamine-diacetylene Schiff base conjugate. 2+ A complex and a mixed solution of ethanol and water of 10,12-pentadecanodiyne.

7. The Cu of the rhodamine-diethylamine Schiff base conjugate according to claim 6 2+ A method for preparing a photochromic solution of a complex, characterized in that, Step 2b) contains a mixed solution of ethanol and water containing both rhodamine-diacetylene Schiff base conjugate and 10,12-tetradecanoic acid, wherein the concentration of the rhodamine-diacetylene Schiff base conjugate is (25-50) μM, the concentration ratio of the rhodamine-diacetylene Schiff base conjugate to 10,12-tetradecanoic acid is (1:3)-(1:5), the volume ratio of ethanol to water is (1:9)-(2:3), the temperature of the ultrasonic heating is (50-70) °C, the time of the ultrasonic heating is (0.5-2) h, the temperature of the refrigerator is (0-4) °C, and the time of the refrigerator refrigeration is (12-48) h.

8. The Cu of the rhodamine-diethylamine Schiff base conjugate according to claim 6 2+ A method for preparing a photochromic solution of a complex, characterized in that, The Cu obtained in step 3b) is photochromic and contains a rhodamine-diacetylene Schiff base conjugate. 2+ A complex and a mixed solution of ethanol and water of 10,12-pentacardiyneic acid, wherein the rhodamine-diaethynyl Schiff base conjugate reacts with Cu 2+ The concentration ratio was (1:10)-(1:25), and the time to place it at room temperature was (5-30) min.

9. A Cu of the rhodamine-diacetylene Schiff base conjugate as described in claim 1 2+ The method for photochromism of complexes, characterized in that, Includes the following steps: 1c) Cu containing both rhodamine-diacetylene Schiff base conjugates 2+ A mixed solution of the complex and 10,12-pentacarbazinoic acid in ethanol and water, after being irradiated with 365 nm ultraviolet light, changed from colorless to purplish-red; when placed in the dark at room temperature, the color of the mixed solution returned to colorless. 2c) Cu containing both rhodamine-diacetylene Schiff base conjugates 2+ A mixed solution of the complex and 10,12-tetracarbodiyne in ethanol and water, after being irradiated with 254 nm ultraviolet light, changed from colorless to blue; after being irradiated with 365 nm ultraviolet light, the color of the mixed solution changed from blue to purple; and after being placed in the dark at room temperature, the color of the mixed solution returned from purple to blue. 3c) Cu containing both rhodamine-diacetylene Schiff base conjugates 2+ A mixed solution of the complex and 10,12-pentacarbazinoic acid in ethanol and water, after being irradiated with 365 nm ultraviolet light, changed from colorless to purplish-red; after being further irradiated with 254 nm ultraviolet light, the color of the mixed solution changed from purplish-red to purple; and when placed in the dark at room temperature, the color of the mixed solution changed from purple to blue.

10. The Cu of the rhodamine-diacetylene Schiff base conjugate according to claim 9 2+ The method for photochromism using a complex is characterized in that, In steps 1c), 2c), and 3c), the irradiation time with 365nm ultraviolet light is (2-5) min, the irradiation time with 254nm ultraviolet light is (2-5) min, and the time placed in the dark at room temperature is (5-10) min.

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