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.     

光致变色微胶囊的制备与性能

以蜜胺树脂为壁材、光致变色材料为芯材,采用原位聚合法制备了具有光致变色性能的微胶囊.研究了三聚氰胺/甲醛摩尔比、壁材与芯材的用量比、乳化剂浓度等因素对微胶囊形貌及性能的影响.在最佳工艺条件下制备的变色微胶囊,在日光和紫外光下具有快速、可逆的光致变色性能.     

2-芳氧基-1,8-邻苯二甲酰基萘的合成及光致变色性

合成了3种2-芳氧基-1,8-邻苯二甲酰基萘类光致变色化合物,通过核磁共振谱、红外光谱、质谱和元素分析确定了结构.对产物进行了荧光光谱测定,3种光致变色化合物的荧光强度和Stoke位移都较大.用紫外-可见分光光度计对其在丙酮溶液中的光致变色行为进行了测定,3种光致变色化合物在300-600 nm范围内都具有一定的光致变色性能和较大的吸光系数.     

聚乙二醇支载的螺吡喃类光致变色化合物的合成及其逆光致变色性质

采用DCC缩合的方法,将吲哚啉螺苯并吡喃的衍生物和聚乙二醇相缩合,以聚乙二醇末端的羟基和吲哚啉螺苯并吡喃衍生物的羧基为反应活性基团,实现了带有羧基的螺吡喃类光致变色化合物支载到了聚乙二醇两端.通过引入亲水基团得到了水溶性较好的螺环类光致变色化合物.通过对产物的紫外-可见光谱的研究发现,产物具有良好的光致变色性质,在乙醇、丙酮和乙酸乙酯中皆具有良好的光致生色现象;产物可溶于水,在紫外光(波长365nm)照射时产生了光消色现象,具有明显的逆光致变色性质.该方法原料易得,反应条件容易控制,为光致变色新材料的研究和开发提供了新方法.     

Syntheses, characterization, and photochromic studies of spirooxazine-containing 2,2'-bipyridine ligands and their zinc(II) thiolate complexes

A series of photochromic spirooxazine-containing zinc(II) diimine bis-thiolate complexes were successfully synthesized, and their photophysical and photochromic properties were studied. The X-ray crystal structure of complex 1a has also been determined. Upon excitation by UV light at 330 nm, all the ligands and complexes exhibit photochromic behavior. The thermal bleaching kinetics of the ligands and the complexes were studied in dimethylformamide at various temperatures. The photochemical quantum yields for the photochromic reactions of the ligands and complexes were also determined.     

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.     

吲哚啉苯并螺呲喃类化合物的合成和应用

吲(口朶)啉苯并螺吡喃类化合物具有明显的光致变色性能。我们合成了6′-碘-1,3,3-三甲基吲(口朶)啉-2-螺环-2′-苯并吡喃及一些不同取代的吲(口朶)啉苯并螺吡喃化合物并对其色变性能进行了初步探讨。用这些化合物与光致抗蚀干膜G11胶制成了一种新型光致变色抗蚀干膜。将底片覆盖在此膜上,经紫外线照射后呈现出明显的色差,显示出的图象可保留24小时以上。     

Synthesis and properties of photochromic liquid-crystalline polyacrylates containing a spirooxazine group

The novel photochromic liquid-crystalline polyacrylates containing a spirooxazine group were synthesized. The photochromic polymer containing (4-penta- methyleneoxy)biphenylene moiety at the 5-position of spironaphthoxazine showed nematic phase from 122.9 to 133.8°C. The photochromic polymer containing undeca- methylene instead of pentamethylene showed smectic phase from 93.1 to 169.7°C. On the other hand, the photochromic polymer containing both undecamethylene as a spacer and spironaphthoxazine-bound biphenylene moiety at 9′-position did not show any liquid crystallinity. All spirooxazine-containing liquid-crystalline polymers showed photochromism in the solid state at room temperature. Because the shape of the absorption spectra of the photochromic quenched liquid-crystalline polymer films was almost the same as those of the photochromic amorphous polymer films, the photochromic properties did not depend on the mesophase in the polymers examined. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3513–3522, 1999     

Synthesis and photochromic properties of coumarin-based dithienylethenes

Two photochromic coumarin-based dithienylethenes were synthesized by one-pot nucleophilic addition reaction of alkyne and phenol. Both diarylethenes exhibited reversible photochromism, but their conformation played an important role in their photochromic properties. The derivative with high conjugation degree showed switchable fluorescence, providing a valuable reference for design of novel photochromic diarylethenes.     

Synthesis and properties of photochromic liquid‐crystalline copolymers containing both spironaphthoxazine and cholesteryl groups

Photochromic liquid‐crystalline copolymers consisting of a photochromic monomeric unit containing both a spironaphthoxazine group and an undecamethylene spacer, and a liquid‐crystalline monomeric unit containing both a cholesteryl group and a decamethylene spacer were prepared to investigate the effect of the thermal properties of the photochromic monomeric unit on the mesomorphic order of the side chain of the related copolymers. The photochromic liquid‐crystalline copolymers containing a photochromic liquid‐crystalline monomeric unit showed only a smectic phase. On the other hand, the photochromic liquid‐crystalline copolymers containing a photochromic non‐liquid‐crystalline monomeric unit showed a chiral nematic phase (cholesteric phase). The photochromic chiral nematic liquid‐crystalline copolymer containing 14 mol % photochromic monomeric unit reflected visible light around 104 °C. To lower the temperature range of reflection of visible light, cholesteryl oleyl carbonate was used as a chiral nematic plasticizer for the photochromic chiral liquid‐crystalline polymer systems. Photo‐induced pitch change of the mixture by means of UV irradiation was investigated and it was concluded that the pitch change observed under UV irradiation was mainly induced by thermal effect in the case of our system. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 887–894, 2000     

Liquid crystal polymers containing permanent dipole azobenzene chromophores

Three photochromic monomers containing a permanent dipole photochromic azobenzene group spaced from the methacryloyl moiety by a polymethylene segment were synthesized in three steps starting from 4-cyanoaniline. The monomers were homopolymerized and copolymerized with an optically active monomer, (-)-menthyl methacrylate, in the presence of AIBN as a radical initiator. Structurally similar amphiphilic polymers were obtained by homopolymerization of analogous methacrylates in which oligo(oxyethylene) segments replaced the polymethylene spacers. The polymeric materials, having a molar content of photochromic units between 5 and 100% and molecular weights of about 15,000, were characterized by thermal analysis, X-ray diffraction, 1D and 2D NMR. Mobility and photochromic properties in solution were also investigated.     

A new photochromic 8pi-system based on an azaheptatriene-tetrahydroazepinoisoquinoline electrocyclization

A new photochromic family of tetrahydroazepinoisoquinolines (THAI) 4a-i has been prepared. It undergoes light-induced ring opening from spiro compounds 4 to betaines 3 that decolorize in a very fast cyclizing reaction. Depending on substitution of the precursors 1 and 6, the photochromic styryltetrahydroindolizines (THI) 5k-q are formed in a periselective way. The conformation and configuration of the new photochromic THAI 4 and THI 5 were investigated by NMR and the structure of both compounds was proven by X-ray analysis. The photochromic properties were studied by laser flash photolysis, which afforded the lifetime of the colored form 3 and 3' in the micro- or nanosecond range.     

Preparation and Photochromic Behavior of Ormosil Containing Encapsulated AgTCNQ Molecules

Preparation and photochromic behavior of ormosil containing encapsulated AgTCNQ molecules were studied in this paper. The ormosil resulted from hydrolysis and polycondensation of glycidoxypropyltrimethoxysilane, dimethyldimethoxysilane and methyltrimethoxysilane. The time to add AgNO₃ water solution into the resultant sol was a key factor to synthesize AgTCNQ molecules inside ormosil matrix. AgTCNQ molecules encapsulated in the ormosil showed different photochromic behavior compared with pure AgTCNQ film: normal photochromic reaction can be realized, while reverse photochromic reaction can not. The “cage” model was used to explain this phenomenon.     

光致变色全氟环戊烯类二芳烯化合物的合成及其性质研究

合成了两种新的二芳基乙烯类光致变色化合物1,2 双(2 甲基5 (4 乙氧基苯基)噻吩3 基)全氟环戊烯(1a)和1,2 双(2 甲基5 (对氟苯基)噻吩3 基)全氟环戊烯(2a),并且研究了其在不同溶剂和浓度中的UV Vis光谱、荧光性质和光致变色反应动力学特征.实验结果表明,化合物1a和2a具有良好的光致变色性质和较强的荧光;光致变色闭环反应为零级反应,开环反应为一级反应.     

Synthesis and photochromic properties of spiro (benzindoline-naphthoxazines)

A new photochromic compound belonging to the class of spiro(indoline-naphthoxazines) was synthesized. Nitration of this compound was carried out and the structures of two photochromic nitro-substituted products were determined. The photochromic properties of the products were studied in solvents of different polarity.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 732–736, April, 1995.     

有机光致变色材料

有机光致变色材料作为一种新型功能材料,已应用在高科技领域和民用领域.本文简单介绍它的光致变色机理、主要的光致变色体系和有机光致变色材料在各种领域的应用.     

光致变色液晶材料研究进展

本文介绍了液晶相态和光致变色的基本原理,液晶材料在光学领域中的应用,光致变色化合物的光异构化反应对液晶光学性质的影响,以及光致变色液晶材料制备的进展。参考文献53篇。     

Synthesis and spectral-kinetic investigation of fulgimide-based photochromic autocomplexes of the dinitroquinoline series

Two new hybrid compounds, which belong to autocomplexes of the dinitroquinoline series and contain an NH spacer and fragments of photochromic fulgimides as donor components, were synthesized. These autocomplexes were used as ligands in the synthesis of cobalt-containing metal chelates. The spectral-kinetic study revealed that these compounds exhibit photochromism. The introduction of photochromic fulgimide moieties into the autocomplexes has no substantial effect on the spectral properties of the latter but influences the kinetics of photochromic transformations by decreasing their efficiency. Chelate complexes of the hybrid compounds with cobalt ions are characterized by the lowest efficiency of photochromic transformations due to a decrease in the intensity of activating radiation as a result of its absorption by the dinitroquinoline moieties, which are not conjugated with fragments of photochromic compounds. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1409–1416, July, 2008.     

Synthesis and study of photochromic properties of copolymers based on functionalized chromenes

Chromenes functionalized with methacryl groups were synthesized and involved into the radical polymerization to obtain copolymers with ethyl acrylate. Comparison of spectral kinetic characteristics of poly(methyl methacrylate) glasses containing chromenes and photochromic copolymers as additives led to a conclusion that incorporation of a photochromic compound as a part of a copolymer into the polymeric glass increases efficiency of photocoloration of photochromic compounds in the polymeric layer.     

一些带二硫腙汞的光致变色共聚物

合成了一些对(甲基丙烯酰胺基)苯基汞二硫腙络合物的共聚物。测试了这些共聚物在光照下变色和在黑暗中恢复的光致变色性能。讨论了它们的化学组成对光致变色性能的影响。