An organic photochromic material and its preparation method and application

Abstract

The present invention relates to an organic photochromic material and a preparation method and application thereof. The general structural formula of the material is: #imgabs0# wherein X is selected from halogen, hydrogen, C1-C 12 Alkyl or phenyl, the halogen includes chlorine, bromine or iodine; the preparation method is specifically: adding substituted diarylethene-based monoaldehyde compounds, methyl coumarin and organic solvents in sequence, heating and refluxing, cooling and filtering, using silica gel column chromatography on the obtained solid, and drying to obtain an organic photochromic material. Compared with the prior art, it does not have photochromic properties by itself, but under the action of ions, it can specifically make the material produce color changes or fluorescence changes under the illumination environment, that is, the material obtains photochromic properties under the action of ions.

Description

Technical Field

[0001] The invention belongs to the technical field of organic photofunctional materials and relates to an organic photochromic material and a preparation method and application thereof. Background Art

[0002] With the rapid development of social production and science and technology, advanced intelligent materials that can respond to external stimuli have important application value in the fields of information storage, sensor devices, targeted medical treatment, anti-counterfeiting and military industry. Among them, organic photochromic materials, as an important type of optical functional materials, have a place in the field of intelligent materials. Organic photochromic compounds can achieve precise regulation at the molecular scale. After being irradiated with a certain wavelength of light, the molecules undergo a specific chemical reaction to generate photoisomers, and the absorption spectrum and the color of the substance change significantly; under the irradiation of another wavelength of light or the action of heat, a reversible reaction occurs to restore the original molecular structure. This kind of material that undergoes a reversible reaction under the action of light and is accompanied by a color change is called a photochromic material. As a readily available clean energy, light provides broad prospects for the design, construction and application of photochromic materials due to its rapid response and renewable characteristics.

[0003] At present, the main organic photochromic compounds include azobenzene, fulgide, spiropyran, spirooxazine and diarylethene. Among them, diarylethene photochromic materials have become star molecules in optoelectronic fields such as molecular logic gates, fluorescence sensors, fluorescence imaging, and single-molecule devices due to their excellent thermal stability, high conversion rate, fast response speed, and good fatigue resistance. In order to achieve practical applications in the optoelectronic field, people have designed and synthesized a series of functional materials using diarylethene compounds. These materials have the advantages of strong designability, low price, and easy synthesis. Although great progress has been made in the research on the photochromic properties of diarylethene compounds, there are still some problems that need to be solved to meet the needs of practical applications. One of the problems is to regulate the spectral performance of molecular switches by ions, which is essential in the fields of molecular logic gates and sensors. There are still few reports on regulating the performance of molecular switches by ion complexation (XGHu, et al. Dyes and Pigments, 2020, 172, 107869-107875; R. Wang, et al. Dyes and Pigments, 2017, 146, 445-454; S. Wang, et al. Journal of Materials Chemistry C, 2017, 5, 282-289). Compared with chemical reactions or heating (Masahiro Irie, et al. J. Am. Chem. Soc., 1994, 116, 9894-9900; F. Nourmohammadian, et al. Chem Commun, 2011, 47, 10954-10956), ion complexation has broader application prospects.

[0004] Patent CN110423607A discloses an organic photochromic material and its preparation method and application. The preparation method includes: reacting a monoaldehyde compound based on diarylethene with photochromic properties with 3-hydroxy-2-naphthoic acid hydrazine at a temperature of 20-120°C for about 1-24h. After the reaction stops, a precipitate is generated in the solution. The precipitate is filtered, washed, and purified to obtain a novel photochromic compound of Schiff base based on diarylethene. Patent CN112142722A discloses a novel organic photochromic material and its preparation method and application. The preparation method includes: reacting a monoaldehyde compound based on diarylethene with photochromic properties with 2-pyridinecarboxylic acid hydrazide at a temperature of 20-120°C for about 1-24h. After the reaction stops, a precipitate is generated in the solution. The precipitate is filtered, washed, and purified to obtain a novel photochromic compound of Schiff base based on diarylethene. However, the above patent has photochromic reaction activity without ion action, and the photochromic reaction activity can only be suppressed after adding ions. Summary of the invention

[0005] The purpose of the present invention is to provide an organic photochromic material and its preparation method and application in order to overcome the defects of the above-mentioned prior art. The present invention has no photochromic activity in the absence of ions, the photochromic activity of the molecule can be activated by silver ions, has gating properties, and has ion-regulated molecular switch spectral properties and ion recognition properties.

[0006] The purpose of the present invention can be achieved by the following technical solutions:

[0007] One of the technical solutions of the present invention is to provide an organic photochromic material, the general structural formula of which is:

[0008]

[0009] Wherein, X includes halogen, hydrogen, C 1 ~C 12 Alkyl or phenyl.

[0010] Furthermore, the X is a halogen, and the halogen includes chlorine, bromine or iodine.

[0011] As a preferred technical solution, the X is chlorine.

[0012] One of the technical solutions of the present invention is to provide a method for preparing an organic photochromic material. The preparation method is specifically as follows: a substituted diarylethene-based monoaldehyde compound, methyl coumarin and an organic solvent are sequentially added to a reaction system, heated under reflux for reaction, cooled and filtered, and the obtained solid is subjected to silica gel column chromatography, and dried to obtain an organic photochromic material. The reaction equation is as follows:

[0013]

[0014] Furthermore, the organic solvent includes toluene, methanol, ethanol or tetrahydrofuran.

[0015] Furthermore, the catalyst for the heating reflux reaction is sodium p-toluenesulfonate.

[0016] Furthermore, the ratio of the added amounts of the substituted diarylethene-based monoaldehyde compound, methyl coumarin, organic solvent and catalyst is (1.0-3.0 mmol):(1.0-3.0 mmol):(15-60 mL):(0.16-0.48 mmol).

[0017] Furthermore, the heating reflux reaction is carried out at a temperature of 65-110° C. and for a time of 1-24 h.

[0018] As a preferred technical solution, ethanol is used to wash the filter cake.

[0019] One of the technical solutions of the present invention is to provide an application of an organic photochromic material in ion-regulated molecular switch spectral performance. The material has photochromic properties when it interacts with ions, that is, the solution produces color or fluorescence changes under ultraviolet or visible light irradiation, and has no photochromic properties in the absence of ion action, that is, the solution cannot produce color or fluorescence changes in a light environment.

[0020] One of the technical solutions of the present invention is to provide an application of an organic photochromic material in ion recognition performance, wherein the material reacts with silver ions in a pure organic solution with high selectivity, and the color of the solution changes after the reaction, thereby achieving a specific response to the silver ions.

[0021] Furthermore, the solvent of the pure organic solution includes tetrahydrofuran, methanol, ethanol, acetonitrile, dimethyl sulfoxide or dichloromethane.

[0022] As a preferred technical solution, a use of an organic photochromic material in the preparation of an optoelectronic information element is provided.

[0023] As a preferred technical solution, the photoelectric information element includes a multi-addressable photoelectric molecular switch, a molecular wire element or a photochromic light-emitting device.

[0024] The present invention obtains an organic photochromic material by condensing an ion recognition group methyl coumarin with an amino group with a parent diarylethene through aldehyde amine. The sulfur atoms, nitrogen atoms and oxygen atoms in the organic photochromic molecules work together to coordinate with silver ions, giving the organic photochromic material photochromic properties and realizing gated switching.

[0025] Compared with the prior art, the present invention has the following advantages:

[0026] (1) The present invention uses a monoaldehyde compound based on diarylethene and methylcoumarin to form a Schiff base compound, the synthesis method is simple, the synthesis steps are few, the raw material cost is low, the process is easy to industrialize, and the product purification is efficient and convenient;

[0027] (2) The organic photochromic material with ion-regulated molecular switch spectral performance prepared by the present invention has high light conversion efficiency, fast light response ability, good thermal stability and excellent fatigue resistance, and can be used as a smart material in the optoelectronic field;

[0028] (3) The present invention itself does not have photochromic properties, but the complex solution formed with silver ions can achieve color change response to ultraviolet and visible light, that is, it obtains basic photochromic properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1This is an absorption spectrum diagram of the methanol solution of the organic photochromic material under different illumination times in an embodiment of the present invention;

[0030] Figure 2 This is an absorption spectrum diagram of the methanol solution of the organic photochromic material after adding silver ions of different concentrations in the embodiment of the present invention;

[0031] Figure 3 This is an absorption spectrum diagram of the methanol solution of the organic photochromic material under different illumination times after adding silver ions to the embodiment of the present invention. DETAILED DESCRIPTION

[0032] The present invention is described in detail below in conjunction with specific embodiments. This embodiment is implemented based on the technical solution of the present invention, and provides a detailed implementation method and a specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

[0033] Unless otherwise specified, the equipment used in the following examples are all conventional equipment in the art; the reagents used are all commercially available products or prepared by conventional methods in the art unless otherwise specified. Anything not described in detail in the following examples can be achieved by conventional experimental means in the art.

[0034] The room temperature described in the following examples is 25-28°C.

[0035] Embodiment 1:

[0036] An organic photochromic material and a preparation method thereof, wherein the reaction equation is as follows:

[0037]

[0038] The preparation method of 1-(5-chloro-2-methyl-3-thienyl)-2-(5-formyl-2-methyl-3-thienyl)cyclopentene (Compound 1) can be found in the literature (H. Tian, ​​et al. Tetrahedron, 2011, 67, 915-921). Methyl coumarin (Compound 2) is a commercial product.

[0039] The preparation method comprises the following steps:

[0040] In a light-proof environment, compound 1 (0.322 g, 1 mmol), methyl coumarin (0.191 g, 1 mmol) and catalyst sodium p-toluenesulfonate (0.032 g, 0.16 mmol) were added to a 50 mL reaction tube, and 20 mL of anhydrous toluene was added under nitrogen protection, and the mixture was stirred evenly. The mixture was heated to 110 ° C and refluxed for 12 h. After the reaction was completed, the mixture was cooled to room temperature and filtered. The solid residue was chromatographed on a silica gel column with an eluent of petroleum ether: dichloromethane = 1:1 to obtain 0.074 g of a brown solid product with a yield of 15% for the organic photochromic material (compound P1).

[0041] The NMR spectrum data of compound C1 are as follows:

[0042] 1 H NMR (600 MHz, DMSO-d 6 )δ7.40(d,J=7.8Hz,1H),7.04(d,J=7.8Hz,1H),6.83(d,J=8.5Hz,2H),6.69(m, 2H),6.04(s,1H),2.55(t,J=2.0Hz,3H),2.32(m,4H),2.27(s,6H),2.22(s,2H). 13 C NMR (151 MHz, DMSO-d 6 )δ159.71,153.51,146.82,140.66,137.11,127.47,124.91,122.89,111. 86,111.75,110.64,109.37,20.18,17.62.HRMS(ESI+,m / z):[M+H]calcd.C 26 H 22 ClNO 3 S 2 For 495.0730; found 496.0809.

[0043] A photochromic performance test of an organic photochromic material, the performance test comprising the following steps:

[0044] Dissolve compound P1 in methanol to prepare 10 μmol·L -1 Methanol solution. 2.5 mL of the test solution was added to a 1 cm × 1 cm × 4 cm quartz cuvette with stirring, and the test solution was irradiated with a 365 nm monochromatic light source at different illumination times (1 min, 2 min, 3 min, 4 min, 6 min, 8 min, 10 min, 12 min, 14 min and 16 min), and the absorption spectrum was measured with a UV-visible spectrophotometer.

[0045] like Figure 1 As shown, under 365nm ultraviolet light irradiation, the absorption spectrum in the ultraviolet and visible light regions does not change basically, and the color of the solution does not change either.

[0046] A method for regulating the spectral performance of an organic photochromic material, the performance regulation comprising the following steps:

[0047] Compound P1 was dissolved in methanol to a concentration of 10 μmol·L -1 Add 2.5 mL of the test solution to a 1 cm × 1 cm × 4 cm quartz cuvette with stirring, and then use a micro-syringe to add different concentrations of silver ions (the concentration of silver nitrate aqueous solution is 10 μmol·L -1 , 20μmol·L -1 , 30μmol·L -1 , 40μmol·L -1 , 50μmol·L -1 , 60μmol·L -1 , 70μmol·L -1 , 80μmol·L -1 , 90μmol·L -1 and 100 μmol·L -1 ) and then uniformly mixed for 10 min, and the absorption spectrum was measured.

[0048] like Figure 2 As shown, with the continuous addition of silver ions, the absorption peak at 323 nm in the absorption spectrum gradually weakened and blue-shifted, and the color of the solution did not change.

[0049] Add 2.5 mL of the test solution to a 1 cm × 1 cm × 4 cm quartz cuvette with stirring, and then use a microsyringe to add 100 μmol·L -1 The silver ions were irradiated with a 365nm monochromatic light source for different illumination durations (1min, 2min, 3min, 4min, 6min, 8min, 10min, 12min, 14min and 16min), and the absorption spectrum was measured with a UV-visible spectrophotometer.

[0050] like Figure 3 As shown, a new absorption band appears at 410 nm in the absorption spectrum and gradually increases with the extension of illumination time. The color of the solution changes from colorless to yellow, indicating that the spectral properties of compound P1 can be regulated by silver ions.

[0051] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.

Claims

1. An organic photochromic material, characterized in that: The general structural formula of this material is: ， Wherein, X is halogen or hydrogen.

2. The organic photochromic material according to claim 1, characterized in that: Said X is halogen.

3. A method for preparing an organic photochromic material as claimed in claim 1, characterized in that: The preparation method is specifically as follows: a substituted diarylethene-based monoaldehyde compound, methyl coumarin and an organic solvent are sequentially added to a reaction system, heated under reflux for reaction, cooled and filtered, and the obtained solid is subjected to silica gel column chromatography, and dried to obtain an organic photochromic material. The reaction equation is as follows: 。 4. The method for preparing an organic photochromic material according to claim 3, characterized in that: The organic solvent is selected from toluene, methanol, ethanol or tetrahydrofuran.

5. The method for preparing an organic photochromic material according to claim 3, characterized in that: The catalyst for the heating reflux reaction is sodium p-toluenesulfonate.

6. The method for preparing an organic photochromic material according to claim 5, characterized in that: The ratio of the added amounts of the substituted diarylethene-based monoaldehyde compound, methyl coumarin, organic solvent and catalyst is (1.0-3.0 mmol):(1.0-3.0 mmol):(15-60 mL):(0.16-0.48 mmol).

7. The method for preparing an organic photochromic material according to claim 3, characterized in that: The heating reflux reaction temperature is 65-110°C and the time is 1-24 h.

8. An application of the organic photochromic material according to any one of claims 3 to 7 for non-diagnostic and non-therapeutic purposes in ion-modulated molecular switch spectral properties, characterized in that: The material has photochromic properties when reacting with silver ions, but has no photochromic properties when there are no ions.

9. An application of the organic photochromic material according to any one of claims 3 to 7 for non-diagnostic and non-therapeutic purposes in ion recognition performance, characterized in that: The material reacts with silver ions in a pure organic solution with high selectivity, and the color of the solution changes after the reaction, thereby achieving a specific response to the silver ions.

10. The use of an organic photochromic material for non-diagnostic and non-therapeutic purposes in ion recognition performance according to claim 9, characterized in that: The solvent of the pure organic solution is selected from tetrahydrofuran, methanol, ethanol, acetonitrile, dimethyl sulfoxide or dichloromethane.

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