Synthesis of Novel Photochromic Films by Oxidation Polymerization of Diarylethenes Containing Phenol Groups
Synthesis of Novel Photochromic Films by Oxidation Polymerization of Diarylethenes Containing Phenol Groups
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含酚基二芳基乙烯氧化聚合合成新型光致变色薄膜
DOI：
10.1002/adfm.200304369
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发表时间：
2003
影响因子：
19
通讯作者：
M. Irie
中科院分区：
文献类型：
--
作者：
K. Uchida;A. Takata;M. Saito;A. Murakami;Shinichiro Nakamura;M. Irie
本文报道了一些附着于苯酚基团的二亚乙烯衍生物的合成，它们表现出显著的光致变色反应。根据Hay的方法，在邻酚基团（1,2 -二[2,4 -二甲基- 5 - （o -羟基苯基）- 3 -噻吩基]六氟环戊烯）上聚合了一个二乙烯基；所得薄膜不溶于任何溶剂，在红外光谱中不显示OH基团的吸收带。在相同的氧化条件下，与间酚和对酚基团相连的异构体二乙烯不会形成薄膜，而是通过与4,4′-二羟基苯基醚共聚形成薄膜。在紫外和可见光交替照射下，均聚膜和共聚物膜均表现出可逆的光致变色反应，但显色效果不显著。二乙烯的闭环异构体聚合不会产生预聚体，而是分解，而与邻酚部分（1,2 -二[2 -甲基- 6 - （o -羟基苯基）- 1 -苯并噻吩- 3 -基]六氟环戊烯）相连的双苯并噻吩衍生物的闭环异构体通过相同的过程形成聚合物膜。该聚合物薄膜表现出明显的光致变色反应，表明光反应构象固定在聚合物基体上，X射线衍射测量表明薄膜处于非晶相。光致变色反应也可以通过红外光谱监测，使其适用于非破坏性读出记录薄膜。
We report the synthesis of some diarylethene derivatives attached to phenol moieties, which show remarkable photochromic reactions. A dithienylethene group attached to the o‐phenol moiety (1,2‐bis[2,4‐dimethyl‐5‐(o‐hydroxyphenyl)‐3‐thienyl]hexafluorocyclopentene) was polymerized according to Hay's method; the resulting film was insoluble to any solvents, and showed no absorption band attributable OH group in its IR spectrum. Isomeric dithienylethenes attached to m‐ and p‐phenol moieties did not form films under the same oxidation conditions, but instead formed films by copolymerization with 4,4′‐dihydroxyphenyl ether. Although the homopolymer film and copolymer films showed reversible photochromic reactions by alternate irradiation with UV and visible light, the coloration was not remarkable. Polymerization of closed‐ring isomers of the dithienylethenes did not give pre‐polymers and instead decomposed, while the closed‐ring isomer of a bisbenzothienylethene derivative attached to the o‐phenol moiety (1,2‐bis[2‐methyl‐6‐(o‐hydroxyphenyl)‐1‐benzothiophen‐3‐yl]hexafluorocyclopentene) formed a polymer film by the same procedure. This polymer film showed a remarkable photochromic reaction, indicating the photo‐reactive conformation was fixed in polymer matrix, and X‐ray diffraction measurements show that the film is in the amorphous phase. The photochromic reaction can also be monitored by IR spectroscopy, making it applicable for non‐destructive read‐out recording films.