螺噁嗪类光致变色化合物的合成研究进展

光致变色螺噁嗪;双光致变色螺噁嗪;螺噁嗪聚合物;合成;微波合成     

螺噁嗪光致变色反应机理研究进展

20世纪80年代中期以来, 关于螺噁嗪在光致变色过程中的光化学和光物理现象的研究非常活跃. 综述了近20年来对溶液中的螺噁嗪、晶体螺噁嗪以及固体介质中的螺噁嗪的光致变色机理研究结果, 同时介绍了实验研究方法和理论研究方法在螺噁嗪光致变色过程研究中的应用, 分析了取代基对光致变色性质的影响. 阐述了机理研究对新型螺噁嗪设计合成的重要指导意义.     

Synthesis, characterization and photochromic studies in film of heterocycle-containing spirooxazines

A series of novel heterocycle-containing spirooxazines have been designed and synthesized, and their photochromic properties were investigated under flash photolysis and continuous irradiation in particular regard to the fatigue resistance, the lifetime of the colored merocyanine form in various solutions and polymers. Especially, the characteristics of two UV-sensitive spirooxazines dispersed polymethylmethacrylate thin-films were extensively studied. Detailed studies showed that general significant shifts in the λ_max of the absorption spectra of the open forms, interesting fatigue resistances and emission fluorescene properties were observed.     

Electrical properties of photochromic organic systems (review)

The results of studying the electrical properties of organic photochromic systems based on diarylethenes, spiropyrans, spirooxazines, and azo compounds have been analyzed. It has been shown that diarylethenes have promise for use in photoswitches of various types that reversibly and simultaneously change the spectral and electrical properties when exposed to light.     

Synthesis of Green Colored Photochromic 6′-Arylamino Spiro [2H]Naphth[1,2-b]oxazines

The published route to a series of 6′-arylamino substituted photochromic spirooxazines has been investigated with improvements made to perform the synthesis in satisfactory yield. The route has been exemplified with several novel derivatives prepared (including hydroxyl functionalised). Additionally, a one-pot procedure for the conversion of suitably functionalized 1,2-naphthoquinones into the photochromic compounds is reported.     

Synthesis and photochromism of photochromic spiro compounds having a reactive pendant group

The photochromic spiropyrans and spirooxazines having a reactive pendant group, including carboxyl, halide, succinimidyl ester and isothiocyanate, were synthesized. Their photochromic behaviors in solution and solid state were studied.     

Factors Influencing Photochromism of Spiro-Compounds Within Polymeric Matrices

Abstract

Photochromic polymeric materials have been commercialized in ophthalmic lenses, however, there are many other potential uses for this technology. The photochromic transitions are extremely sensitive to environmental conditions, thus offering the potential for modifying the kinetics to suit different applications. There are a significant number of photochromic molecular families, with different characteristics. The spiro-compounds, both spirooxazines and spiropyrans, have received the most attention as they have good coloration properties and spirooxazines also display good fatigue resistance. Consequently this review focuses on the inclusion of these compounds into polymer matrices. In addition we discuss decoloration and coloration behaviors, solvatochromism, mechanism of fatigue, and unusual synthetic approaches.     

Photochromic fulgides and spirooxazines: mechanism and substituent effect on photoreactions

Molecular design, synthesis and photochromic properties of spirooxazines and fulgides are described. In the case of fulgides, the change of the substituents may lead to different photochromic properties and different photoreactions of the kind of compounds. In photochromic process of pyrryl-substituted fulgides, the excited singlet state is the mam species, but the excited triplet state is also involved. However, no excited triplet state has been observed in cyclization of aryl-substituted fulgides. In the case of spirooxazines, the substituents at 2'-position have great effect on the formation of photoproduct and on the mechanism of photoreaction. The increase of steric hindrance of the 2'-position substituent gives rise to the decrease of the quantum yield for the formation of photochromic merocyanine (PMC) and the increase of the relative quantum yield for the charge separated twist intermediate (CT).     

Synthesis of photochromic optically transparent polycarbonate glasses and study of their properties

Procedure was developed for surface dyeing of polycarbonate glass with photochromic thermally relaxing compounds from the classes of spiropyrans, spirooxazines, and chromenes via diffusion of photochromic molecules from solutions in cyclohexanone. It was shown that the highest diffusion efficiency of photochromic compounds without loss of the optical surface quality of polycarbonate glass is reached at a temperature of 80°C. Samples of photochromic polycarbonate glasses were obtained and their photochromic properties were studied.     

Photochromic,Thermochromic, and Fluorescent Spirooxazines and Naphthopyrans: A Spectrokinetic and Thermodynamic Study

The photochromic and thermochromic behavior of four commercially available Reversacol dyes are presented. The compounds studied belong to the class of spirooxazines and naphthopyrans, which are typically thermoreversible photochromic molecules. On stimulation with UV light, these compounds become colored and exhibit spectra which extend over the whole visible region. Increasing the temperature causes spontaneous coloration (thermochromism). Herein, absorption and fluorescence spectra, molar absorption coefficients of the colorless and colored forms, fluorescence and photochemical quantum yields, and kinetic parameters of thermal bleaching (rate constant, frequency factor, and activation energy) are determined in acetonitrile solution. The thermal ground‐state reaction is exhaustively described in terms of thermodynamic parameters (equilibrium constant, free energy, enthalpy, and entropy). Temperature effects on photochemical and thermal colorabilities are evaluated. The results indicate that the two spirooxazines are good photochromes below room temperature, whereas they are efficient thermochromic compounds above room temperature. Naphthopyrans are better photochromes but worse thermochromic compounds than spirooxazines.     

光致变色聚合物研究进展

本文主要介绍了9类光致变色聚合物的研究状况,包括光致变色螺吡喃聚合物、螺嗪聚合物、二芳基乙烯光致变色聚合物、偶氮苯类光致变色聚合物、苯氧基萘并萘醌光致变色聚合物、俘精酰亚胺光致变色共聚物、硫靛光致变色共聚物、双硫腙光致变色聚合物以及二氢吲嗪光致变色聚合物等。讨论了聚合物的合成、光致变色性质、影响聚合物性质的因素,并对光致变色聚合物未来的研究重点和方向作了展望。     

有机光致变色材料的最新成就与机遇

综述了近年来在有机光致变色领域所取得的成就,主要包括螺恶嗪类化合物、吡喃类化合物、俘精酸酐及其衍生物、新型二芳基乙烯和质子转移体系共五大类光致变色体系。     

Photochromic Transformations of Spiro Compounds: 1. A New Approach to Determining the Photocoloration Quantum Yield

A new approach to determining a photocoloration quantum yield for photochromic compounds was considered. This approach is based on comparison between the calculated and experimental values of maximum absorbance A ^B _maxof a photocolored form upon monochromatic irradiation. Using spirooxazines as an example, the quantum yield of photocoloration was determined, and A ^B _maxwas examined as a function of a number of parameters that characterize the photocolored form (the quantum yields of photocoloring and photobleaching and the lifetime of the colored form). It was found that A ^B _maxnonlinearly increased with decreasing rate constant (<0.2 s^–1) of the thermal bleaching of spirooxazines.     

新型双螺噁嗪分子的合成及性能

设计合成了3个双螺噁嗪化合物, 采用核磁共振谱、红外光谱和高分辨质谱对这些化合物进行了表征. 测试了光照前后化合物在不同溶剂中的紫外吸收光谱、荧光光谱以及在高分子薄膜中的消色动力学曲线. 结果表明, 目标化合物均具有良好的光致变色性能和耐疲劳度, 在材料、分子开光及生物探针领域有潜在的应用前景.     

Synthesis of Thiophene-Substituted Spiropyrans and Spirooxazines,Precursors of Photochromic Polymers

The synthesis of spiropyrans 11 and 12 and spirooxazines 13–17 containing a thiophene moiety is described. Two different synthetic approaches were used. The spectrokinetic properties of these new compounds are reported.     

Searching for photochromic liquid crystals Spironaphthoxazine substituted with a mesogenic group

A number of photochromic spiropyrans and spirooxazines containing mesogenic groups were synthesized. Only one of them, spiro-indoline-naphthoxazine with mesogenic substituent, 4-(4-heptylbenzoyloxy)benzoyloxy in 5-position, revealed mesomorphic properties. Its phase behaviour, photochromism and alignment in the electric field was investigated. A structure of the mesophase is discussed.     

Spiropyrans and spirooxazines. 1. Synthesis and photochromic properties of 9"-hydroxy- and 9"-alkoxy-substituted spironaphthooxazines

A procedure was developed for phase-transfer catalyzed alkylation of 5-hydroxyindolenine and 9"-hydroxy-substituted spiro[indoline-2,3"-naphtho[2,1-b]oxazines] by alkyl halides. New 9"-hydroxy- and 9"-alkoxy-substituted spironaphthooxazines, spirooxazinyloxyacetic acids, and their esters containing substituents with different length of the carbon chain in the indoline moiety were synthesized. The influence of the substituents on the spectroscopic properties of the starting and colored forms and the kinetic characteristics of photochromic transformations of 9"-substituted spironaphthooxazines in solutions and polymeric films was investigated. The bipolar merocyanine forms of spirooxazines were found to produce H-aggregates.     

几种取代螺吲哚啉萘并噁嗪的合成

螺吲哚啉-2,3'-[3H]萘并[2,1-b][1,4]噁嗪(简称螺噁嗪)是一类耐光疲劳性能优于螺吡喃的光致变色物^[1]。Fox以及Ono先期合成了这类化合物^[2],最近Pottier等考察了取代基对性能的影响^[3,4]。但所涉及的取代基(CH₃、CH₃O、Cl、NO₂)多在母体结构中吲哚环的5( 6)位,且N-烷基碳链较短,蔡环上有取代基的情形较少见^[5]。     

Novel synthesis and characterisation of 3,3-dimethyl-5′-(2-benzothiazolyl)-spironaphth(indoline-2,3′-[3H]naphth[2,1-b] [1,4]oxazine) derivatives

Novel modified spirooxazines (SOs) with additional chelating groups were synthesised and the crystal structure of one of these was determined. UV-vis spectroscopic characterization of the photoisomerization of the SO derivatives shows that the photochromic behaviour is altered with Zn²⁺ coordination. In particular, addition of a group as in carboxylic acid 5 to the indole section of the SO increases the lifetime of the merocyanine Zn ²⁺ complex by 20-fold compared to the methylated indole 6.     

Spiropyrans and spirooxazines 9. Photochromism of novel cationic spirooxazines

Novel photochromic spirooxazinoquinolines, their cationic derivatives, and cationic spirooxazine containing pyridinium cation in the aliphatic side chain of the oxazine moiety of the molecule were synthesized. Quaternization of the quinoline fragment leads to a substantial increase in the thermal stability of the merocyanine isomers of cationic spirooxazines and a decrease in the efficiency of photocoloration. Pyridinium cation in the aliphatic side chain of the spirooxazine does not exert a substantial effect on the kinetics of photocoloration and thermal bleaching.