CN115975207A - Metal complex with forward and reverse photochromic characteristics, preparation method and application of metal complex in information encryption - Google Patents
Metal complex with forward and reverse photochromic characteristics, preparation method and application of metal complex in information encryption Download PDFInfo
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Abstract
The invention discloses a metal complex with forward and reverse photochromic characteristics, a preparation method and application thereof in information encryption. The invention uses 9-anthracene formic acid as a functional ligand and benzimidazole as an auxiliary ligand, and adopts a solvothermal method to self-assemble with metal zinc to obtain the metal complex with forward and reverse photochromic characteristics. The material has reverse photochromic characteristics caused by a cycloaddition reaction of [4+4] when in a crystalline state, and is accompanied with photoburst behavior; the photochromic material has a positive photochromic characteristic induced by photo-generated free radicals in an amorphous state; exhibiting a mechanochromic behavior during the transition from the crystalline state to the amorphous state; by utilizing the properties, the material can be applied to the field of multiple information encryption. The invention realizes the positive and negative two-way photochromic characteristic in the same substance, and the synthesized metal complex reveals the state-performance correlation, thereby providing a feasible solution for the design and synthesis of the material.
Description
Technical Field
The invention belongs to the technical field of stimulus response type functional materials, and particularly relates to a metal complex with forward and reverse photochromic characteristics, a preparation method and application thereof in information encryption.
Background
The photochromic material is a substance which changes color under the action of light irradiation with certain wavelength and intensity, and shows attractive application prospect in the fields of molecular switch, detection, encryption anti-counterfeiting, molecular machines and the like. Molecular-based photochromic materials are largely divided into two categories, according to the intrinsic mechanism of discoloration: 1) Photochromism resulting from light-induced cis-trans isomerization or a peri-cyclic reaction. Meanwhile, the structural change may drive macroscopic motions of the molecular material, such as photoburst, bending and other behaviors. 2) Intermolecular/internal charge transfer produces photogenerated free radical induced photochromism. Therefore, strategies based on photoisomerization, chemical reactions, and charge transfer mechanisms can be used to construct dynamic photoresponsive materials. Further, photochromic materials are mainly classified into two types, reverse-color-change and forward-color-change, according to color-changing properties (coloring and decoloring). If positive and negative photochromism can be simultaneously integrated in the same molecular material, the multimode regulation and control on the photochromism property can be greatly expanded.
Disclosure of Invention
The invention aims to provide a metal complex with forward and reverse photochromic characteristics, a preparation method and application thereof in information encryption. Provides a new idea and feasible solution for the development of the design and synthesis of novel multi-response functional materials.
The preparation method of the metal complex with forward and reverse photochromic characteristics comprises the following steps: the metal complex with forward and reverse photochromic characteristics is obtained by taking 9-anthracenecarboxylic acid as a functional ligand and benzimidazole as an auxiliary ligand and adopting a solvothermal method to self-assemble with metal zinc.
The preparation method comprises the following specific operation processes: dispersing zinc nitrate, 9-anthracenecarboxylic acid and benzimidazole in deionized water and N, N' -dimethylformamide, dropwise adding concentrated nitric acid, ultrasonically mixing, crystallizing at 80-100 ℃ for 24-72 hours to obtain block light yellow crystals, washing the crystals with ethanol, filtering and drying to obtain the metal complex crystals with forward and reverse photochromic characteristics.
The molar ratio of the zinc nitrate to the 9-anthracenecarboxylic acid to the benzimidazole is 1-3.
The addition amount of the deionized water is 30-60L/mol of 9-anthracenecarboxylic acid.
The addition amount of the N, N' -dimethylformamide is 5-10L/mol of 9-anthracenecarboxylic acid.
The adding amount of the concentrated nitric acid is 0.5-1L/mol of 9-anthracenecarboxylic acid.
The prepared metal complex with forward and reverse photochromic characteristics is applied to information encryption.
The metal complex crystal with the forward and reverse photochromic characteristics is ground to be in an amorphous state and then undergoes fluorescent discoloration, so that information writing is realized.
The metal complex crystal with forward and reverse photochromic characteristics changes from light yellow to white through ultraviolet irradiation and is accompanied with photocracking; the amorphous metal complex with the forward and reverse photochromic characteristics changes from faint yellow to orange by ultraviolet irradiation; the writing and erasing of information and multiple information encryption are realized.
The invention successfully prepares a metal complex with forward and reverse photochromic characteristics by self-assembling 9-anthracenecarboxylic acid, benzimidazole and metal zinc and applies the metal complex to the field of information encryption. The material has reverse photochromic characteristics caused by a [4+4] cycloaddition reaction when in a crystalline state, and is accompanied with photoburst behavior; the photochromic material has a positive photochromic characteristic induced by a photogenerated free radical in an amorphous state; exhibiting a mechanochromic behavior during the transition from the crystalline state to the amorphous state; by utilizing the properties, the material can be applied to the field of multiple information encryption. The invention realizes the positive and negative two-way photochromic characteristic in the same substance, and the synthesized metal complex reveals the state-performance correlation and provides feasible reference for the design and synthesis of the material.
Drawings
FIG. 1: the metal complex with forward and reverse photochromic characteristics prepared by the invention has a face-to-face stacking mode of 9-anthracenecarboxylic acid (a); (b) a stacking view in the c-axis direction.
FIG. 2 is a schematic diagram: reverse photochromic pattern of crystalline material under uv lamp in example 1.
FIG. 3: positive photochromic pattern of amorphous material under uv lamp in example 1.
FIG. 4: the information encryption application is shown in the figure.
Detailed Description
Example 1
Zinc nitrate (0.20mmol, 0.062g), 9-anthracenecarboxylic acid (0.10mmol, 0.022g), benzimidazole (0.10mmol, 0.012g), deionized water (4 mL), N' -dimethylformamide (0.5 mL) and concentrated nitric acid (0.05 mL) are sealed in a 15mL high-temperature resistant glass reaction bottle, and after ultrasonic dispersion, the reaction product is placed in an oven at 93 ℃ for 24 hours to obtain light yellow blocky crystals. And then taking out the glass bottle, cooling to room temperature, washing the obtained single crystal with ethanol, filtering, separating, and drying at room temperature to obtain the target product crystal.
The product was characterized:
the single crystal X-ray diffraction data show that the target product crystallizes on
The space group belongs to a triclinic system, 9-anthracenecarboxylic acid and benzimidazole are used as terminal group ligands to be coordinated with metal zinc to form a flexible zero-dimensional structure, and adjacent 9-anthracenecarboxylic acid is in a face-to-face stacking mode, as shown in figure 1.
Crystalline materials at different illumination times showed a change in color from yellowish to white with increasing illumination time, showing reverse photochromic behavior and concomitant photoburst behavior (fig. 2).
The nuclear magnetic resonance spectrum shows that the anthracene unit generates [4+4] cycloaddition reaction in the reverse photochromic process.
Powder X-ray diffraction data indicate that the complex changed from the crystalline to the amorphous state after milling.
The amorphous material with different illumination time shows that the color of the material changes from light yellow to orange with the increase of the illumination time, and the material shows positive photochromic characteristic, as shown in figure 3.
The electron spin resonance spectrum shows that photo-generated radicals are generated in the forward photochromic process.
Example 2
Zinc nitrate (0.20mmol, 0.062g), 9-anthracenecarboxylic acid (0.10mmol, 0.022g), benzimidazole (0.10mmol, 0.012g), deionized water (5 mL), N' -dimethylformamide (0.5 mL) and concentrated nitric acid (0.05 mL) are sealed in a 15mL high-temperature resistant glass reaction bottle, and after ultrasonic dispersion, the reaction product is placed in an oven at 93 ℃ for 72 hours to obtain light yellow blocky crystals. And then taking out the glass bottle, cooling to room temperature, washing the obtained single crystal with ethanol, filtering, separating, and drying at room temperature to obtain the target product crystal.
The product was characterized: single crystal X-ray diffraction data show that this example is the same material as example 1.
Application example
Rapid writing of information can be achieved by using the fluorescence difference (force induced fluorescence discoloration) between the crystalline complex prepared in example 1 and the amorphous complex obtained by grinding, as shown in fig. 4 a; the complex crystal prepared in example 1 changes color from light yellow to white (reverse photochromic) by ultraviolet irradiation and is accompanied with photocracking behavior, the amorphous complex obtained by grinding in example 1 changes color from light yellow to orange (forward photochromic) by ultraviolet irradiation, and the complex shows various colors which can be distinguished by naked eyes by utilizing the similarity of the color of the complex crystalline complex and the amorphous complex under a fluorescent lamp and the difference under the ultraviolet lamp and the forward and reverse photochromic characteristics of the complex crystalline complex and the amorphous complex, so that multiple information encryption is realized, as shown in fig. 4 b; rapid writing and erasing of information can be achieved using the forward and reverse photochromic properties of the complex prepared in example 1, as shown in fig. 4 c.
Claims (9)
1. A preparation method of a metal complex with forward and reverse photochromic characteristics is characterized by comprising the following steps: the metal complex with forward and reverse photochromic characteristics is obtained by taking 9-anthracenecarboxylic acid as a functional ligand and benzimidazole as an auxiliary ligand and adopting a solvothermal method to self-assemble with metal zinc.
2. The preparation method according to claim 1, characterized in that the specific operation process of the preparation method is as follows: dispersing zinc nitrate, 9-anthracenecarboxylic acid and benzimidazole in deionized water and N, N' -dimethylformamide, dropwise adding concentrated nitric acid, ultrasonically mixing, crystallizing at 80-100 ℃ for 24-72 hours to obtain block-shaped light yellow crystals, washing the crystals with ethanol, filtering and drying to obtain the metal complex crystals with forward and reverse photochromic characteristics.
3. The preparation method according to claim 2, wherein the molar ratio of zinc nitrate, 9-anthracenecarboxylic acid and benzimidazole is 1-3.
4. The method according to claim 2, wherein the deionized water is added in an amount of 30 to 60L/mol of 9-anthracenecarboxylic acid.
5. The method according to claim 2, wherein the N, N' -dimethylformamide is added in an amount of 5 to 10L/mol of 9-anthracenecarboxylic acid.
6. The method according to claim 2, wherein the concentrated nitric acid is added in an amount of 0.5 to 1L/mol of 9-anthracenecarboxylic acid.
7. Use of a metal complex having positive and negative photochromic properties prepared by the process according to any one of claims 1 to 6 in encryption of information.
8. The use of claim 7, wherein the metal complex crystal with forward and reverse photochromic characteristics is ground to an amorphous state and then undergoes fluorescent discoloration to realize information writing.
9. The use of claim 7, wherein the metal complex crystal with forward and reverse photochromic characteristics changes from light yellow to white by ultraviolet irradiation and is accompanied with photocracking behavior; the amorphous state of the metal complex with the forward and reverse photochromic characteristics is changed from light yellow to orange by ultraviolet irradiation; the writing and erasing of information and multiple information encryption are realized.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007038422A1 (en) * | 2007-08-14 | 2009-02-19 | Heinz Prof. Dr. Langhals | New anthracene dicarboxylic acid imide compounds useful e.g. as photodimerisation product for treating tumors, vat dye, dihydroanthercenebisimde compound and bisanthracene dicarboxylic acid imide compounds |
| WO2017180898A1 (en) * | 2016-04-13 | 2017-10-19 | Segan Industries, Inc. | Optical evanescent color change compositions and methods of making and using the same |
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- 2022-12-27 CN CN202211686699.2A patent/CN115975207A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007038422A1 (en) * | 2007-08-14 | 2009-02-19 | Heinz Prof. Dr. Langhals | New anthracene dicarboxylic acid imide compounds useful e.g. as photodimerisation product for treating tumors, vat dye, dihydroanthercenebisimde compound and bisanthracene dicarboxylic acid imide compounds |
| WO2017180898A1 (en) * | 2016-04-13 | 2017-10-19 | Segan Industries, Inc. | Optical evanescent color change compositions and methods of making and using the same |
Non-Patent Citations (1)
| Title |
|---|
| YU-JUAN MA, 等: "Leveraging Crystalline and Amorphous States of a Metal-Organic Complex for Transformation of the Photosalient Effect and Positive-Negative Photochromism", ANGEW. CHEM. INT. ED., vol. 62, pages 202217054 * |
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