固态光致变色螺吡喃类化合物的研究进展

doi:10.6023/cjoc202312017

摘要/Abstract

近年来, 有机光致变色材料持续引起人们的研究兴趣, 因为此类化合物在分子开关、防伪及生物荧光成像等领域都展现出了广泛的应用价值. 螺吡喃(SP)类化合物具有制备方法简单、容易修饰和光学性能较好等优点, 能在光、热、电、酸碱及外力等多种外部刺激下发生结构和性能的改变, 因而可被应用于多个领域. 无基质的固态螺吡喃类化合物因为分子堆积紧密, 缺少空间自由体积, 难以发生光致变色反应. 开发固态下具有光致变色的螺吡喃是新材料领域的一个重要发展趋势. 以分子结构与性质之间的关系为重点, 全面总结了固态光致变色螺吡喃材料的研究进展.

关键词: 螺吡喃, 固态, 光致变色

In recent years, organic photochromic materials have drawn continuous interest due to their wide application value in fields such as molecular switches, anti-counterfeiting and biological fluorescence imaging. Spiropyran (SP) compounds have the advantages of simple preparation, easy modification and good optical properties. They can undergo structural and performance changes under various external stimuli such as light, heat, electricity, acid-base, and external forces. Therefore, they can be applied in multiple fields. Solid spiropyran compounds without a matrix are difficult to undergo photochromic reactions due to their tightly packed molecules and lack of spatial free volume. Development of photochromic SP in the solid state is a significant trend in new materials. The research progress on photochromic spiropyrans in the solid state is summarized with the relationship between molecular structures and properties as an emphasis.

Key words: spiropyran, solid state, photochromism

引用此文

杨素华, 刘箫音, 邹丽飞, 韩杰. 固态光致变色螺吡喃类化合物的研究进展[J]. 有机化学, 2024, 44(6): 1719-1732.

Suhua Yang, Xiaoyin Liu, Lifei Zou, Jie Han. Research Progress on Photochromic Spiropyrans in the Solid State[J]. Chinese Journal of Organic Chemistry, 2024, 44(6): 1719-1732.

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图/表 15

图式1. 萘并吡喃化合物的光致变色机理

Scheme 1. Photochromic mechanism of spiropyran compounds

图式2. 化合物1和2的光致变色机理

Scheme 2. Photochromic mechanism of 1 and 2

图1. 晶体2的颜色变化

Figure 1. Color change of crystal 2 (a) Before irradiation, (b) after UV irradiation at room temperature, and (c) after UV irradiation at 90 K. Reproduced from Ref. [21] by permission of John Wiley & Sons Ltd.

图2. 8a~8c(SP4, SP8和SP12)在室温下的光致变色性能

图3. 化合物12(闭环体TPEA-SP和开环体TPEA-MC)粉末在紫外光和可见光交替照射下的荧光和可见光图像

Figure 3. Fluorescent and visible images of 12 (the closed form TPEA-SP and open mwrocyanine form TPEA-MC) powders under the alternating UV and visible light treatment Reproduced from Ref. [31] with permission. Copyright 2021 American Chemical Society.

图4. 化合物13的粉末和薄膜的颜色和荧光图片

图5. 化合物19的粉末在自然光(A)和365 nm紫外线下(B)的照片以及19的粉末经紫外线照射后在自然光(C)和365 nm紫外线下(D)的照片

Figure 5. Photographs of the 19 powder under natural light (A) and 365 nm UV light (B) and photographs of 19 powder after UV irradiation under natural light (C) and 365 nm UV light (D) Reproduced from Ref. [36] by permission of John Wiley & Sons Ltd.

图6. 化合物20的晶体在紫外光照射前后的颜色改变(上排)以及21a (a)和21a' (b)紫外光照射前后的颜色变化(下排)

Figure 6. Color change of 20 crystal before and after UV irradiation (top) and color changes of 21a (a) and 21a' (b) before and after UV irradiation (bottom) Reproduced from Ref. [37]. Copyright 2018, with the permission from the Royal Society of Chemistry.

图7. 化合物36在粉末状态下紫外光和可见光照射后的表观颜色

图8. 化合物(a) 42、(b) 48a ([PSP]NO3)、(c) 48b ([PSP]SCN)及(d) 48c ([PSP]BPh4)在365 nm照射5 min前(上排)和后(下排)的光致变色晶体照片(A)[54]以及化合物49 ([6'-SP]PF6)的单晶经紫外光照射5 min前后的照片(B)[55]

Figure 8. Photographs of photochromic crystals of (a) 42, (b) 48a, (c) 48b, and (d) 48c before (top) and after (bottom) irradiation of 365 nm for 5 min (A)[54] and photographs of the single crystal of 49 ([6'-SP]PF6) before and after UV light irradiation for 5 min (B)[55] Reproduced from Ref. [54] with permission. Copyright 2019 American Chemical Society. Reproduced from Ref. [55] with permission. Copyright 2020 American Chemical Society.

图式3. 化合物54和55的合成路线

Scheme 3. Schematic synthesis of 54 and 55

图9. (a) 58的粉末在365 nm紫外线照射不同时间后的照片及(b)紫外线(365 nm)照射0、0.166、0.5、1、1.5、2、3、4、5、8、15和30 min后58的吸收光谱的变化

Figure 9. (a) Photographs of powders of 58 after 365 nm UV irradiation for different times and (b) evolution of the photogenerated absorption of 58 after 0, 0.166, 0.5, 1, 1.5, 2, 3, 4, 5, 8, 15 and 30 min of UV irradiation (365 nm) Reproduced from Refs. [64] with permission. Copyright 2013 American Chemical Society.

图10. 化合物63薄膜在紫外光照射前后紫外-可见吸收光谱(插图是笼型化合物63在固态状态下的SP和MC形态的数码照片)

Figure 10. UV-Vis absorption spectra of a thin film of 63 recorded under ultraviolet irradiation (The inset shows digital photographs of SP and MC forms of the cage 63 in the solid state) Reproduced from Refs. [76] with permission. Copyright 2017 American Chemical Society.

图11. 化合物64暴露于低强度紫外线后的可视化变化

图12. 固体化合物67光照前后的颜色和荧光照片

Figure 12. Color and fluorescent images of solid compound 67 before and after illumination Reproduced from Ref. [79] by permission of John Wiley & Sons Ltd.

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