Photochromism of spirofluorenylindolizines

The decoloration kinetics of three spirofluorenylindolizines have been followed in solution and in polymer matrix. They are the 5′-methyl-spiro[9H-fluorene-9.1′(1′H)-indolizine]-2′-3′-bis-methoxycarbonyl ( I ), its methacryloyl oxymethyl ( II ) derivative, and the copolymers of ( II ) with ethyl acrylate. In solution the reactions follow first-order kinetics and show pronounced negative solvatochromism. In solid polymer film, the incorporation of the photochrome as side group of polyethylacrylate affects strongly the decoloration below T_g of the film. Above T_g the decoloration was interpreted on the basis of the WLF equation.     

光致变色与光子器件

本文概述了光致变色和光子器件领域的发展现状和机遇。总结了他们在基础和应用方面获得的结果。通过激光光解技术、时问分辨光谱和反应中问体的衰减动力学深入研究了光致变色机理。     

光致变色高分子体系

对光致变色功能高分子作了概括性综述，介绍了各类体系的光致变色机理，制备方法，应用研究等方面的进展情况。     

Photochromism of Anabaena sensory rhodopsin

Protein-controlled photochemical reactions often mediate biological light-signal and light-energy conversions. Microbial rhodopsins possess all-trans or 13-cis retinal as the chromophore in the dark, and in the light-driven proton pump, bacteriorhodopsin (BR), the stable photoproduct at the end of the functional cycle of the all-trans form is 100% all-trans. In contrast, a microbial rhodopsin discovered in Anabaena PCC7120 is believed to function as a photochromic sensor. For Anabaena sensory rhodopsin (ASR), the photoreaction is expected to be not cyclic, but photochromic. The present low-temperature UV-visible spectroscopy of ASR indeed revealed that the stable photoproduct of the all-trans form in ASR is 100% 13-cis, and that of the 13-cis form is 100% all-trans. The complete photocycle for the proton pump in BR and the complete photochromism for the chromatic sensor of ASR are highly advantageous for their functions. Thus, the microbial rhodopsins have acquired unique photoreactions, in spite of their similar structures, during evolution.     

光(热)致变色现象

在光照或加热的情况下,某些物质的颜色会发生可逆性的变化,称之为光（热）致变色现象。此类物质的种类不同,其变色机理不同,所呈现的颜色也不同。此现象首先发现于无机物,并已有130余年的历史。但不论是在合成与理论研究上,还是在实际应用上的迅速发展,却是在近30余年来更显得卓有成效。光（热）致变色物质目前已在图像显示、光记录材料、彩色录像、照像、印刷照排、化妆品、染料、装饰品、油漆、玩具、护目镜等方面得到了不同程度的应用。     

萘氧基萘并萘醌的合成和光致变色性质

萘氧基萘并萘醌的合成和光致变色性质方政，杨志范，王淑芝，徐素贤，方天如，王佛松（吉林工学院化工系长春）（中国科学院长春应用化学研究所长春１３００２２）关键词萘氧基萘并萘醌，合成，光致变色苯氧基萘并萘醌类光致变色材料具有耐疲劳，室温下几乎无热消失反应，...     

六芳基二咪唑类化合物的合成及光致变色性能

六芳基咪唑;六芳基二咪唑类化合物的合成及光致变色性能     

Photochromism in CaS:Sm

CaSfREhasbeenknownforalongtimeasanexcellentphosphor'.ThephotochronismofSinScrystal'hasbeenfound.Yasuski'repoFtedthatSin' ionstrapedelectronsandchangedintoSin' intheinfraredstimulablephosphorCaScontainingEuandSinions,butphotochromismhasnotbeenobserved.Inthepresentletter,thephotochromismwasobservedinCaS:Sm.Activatedcarbon,calciumsulfate,sodiumsulfateandSin(NO,),weremixedandground,andthen,themixturewasputintoanalumiacrucibleandheatedat950"Cfor3--4hours.Thesampleswereanalyzedbyx-raydiffrac…     

Reversible Multicolor Photochromism of Dihydroazulene Crystals

The photochemical conversion of 1,8a-dihydroazulene-1,1-dicarbonitrile (DHA) to vinylheptafulvene (VHF) is a positive T-type photoswitch that is well understood in solution, but has not been explored in the solid state. Upon excitation with UV light, DHA is converted into VHF in the solid state, with a distinct color change from yellow to deep-red, and retention of crystallinity. The structure of the ring-opened product was assigned to syn-VHF using variable-temperature infrared spectroscopy, and determined by X-ray photodiffraction in a crystal enriched with the product by two-photon excitation. A radical pathway becomes an observable photoreaction channel at low temperatures, and includes a strongly colored, short-lived diradical intermediate.     

苯氧基萘并萘醌衍生物的合成与光致变色性能研究

设计合成了16个新的具有不同迁移基团、不同取代基及双苯氧基萘的苯氧基并萘醌化合物; 通过红外光谱、核磁共振、质谱等方法对其结构进行了表征; 利用紫外-可见光谱研究化合物的光致变色性, 结果表明, 化合物的结构影响其变色性能, 当迁移基团为芳香基时, 其变色性较好; 主链醌环上有取代基时, 化合物成色体最大吸收波长红移; 双苯氧基萘并萘醌化合物较相应的单化合物有较大的摩尔吸光系数; 随着苯基上取代基增大, 其成色速率常数变小.     

Photochromism in the arylaroylaziridine system

Photochromism of a number of arylaroylaziridines has been observed in the solid state or in the rigid matrix. The photochromic behavior is dependent on the intensity of the incident radiation, the reaction medium, the wavelength of light used and on the relationship of the substituents on the three-membered ring. From the visible absorption spectra it is clear that cis-arylaroylaziridines give different colored species than do the trans isomers. These results suggest that the coloration is due to an extensive electrical interaction between the bent bonds of the aziridine ring and the π orbitals of the benzoyl and phenyl groups. Attempts to trap the colored species by co-irradiation with substrates containing a multiple bond failed. A reaction has been found to occur upon heating various arylaroylaziridines with dimethylacetylene dicarboxylate in inert solvents.     

二氧化钛溶胶凝胶的光致变色

通过钛酸丁酯在酸性醇溶液中的水解制备二氧化钛溶胶和凝胶。在中压汞灯的照射下,溶胶和凝胶由浅黄色变成蓝紫色。电子自旋共振谱(ESR)表明,变色的原因是由于…Ti－O－Ti－O…网络中Ti^4^+离子被还原成Ti^3^+离子。Ti^3^+离子又会被空气中的氧所氧化成Ti^4^+离子,个人成分吏家产凝胶由蓝紫色褪为浅黄色。和变色溶胶的吸收光谱不同,在变色凝胶的吸收光谱上出现了四个明显的吸收峰,这些吸收峰是由于处于一定结构中的Ti^3^+离子的3d轨道上电子的跃迁所引起。     

Photochromism of Hexatungstic Acid in DMF

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Photochromism of organometallic compounds with structural rearrangement

This article introduces photochromic properties together with structures of organometallic compounds that undergo photo-induced structural rearrangement. The aim of this review is to survey the research on photochromism by using organometallics which possess by their own nature the properties responsible for the photochromism such as bonding and structural fluxionality, electronic state fluctuation, and photochemically active characteristic in both solution and the solid state. Therefore, the organometallics which include the well-characterized organic photochromic moieties, considered to be derivatives of such kinds of organic photochromic compounds, are excluded in this article. Mono-, di-, and poly-nuclear organometallic compounds are presented based on the reaction types such as linkage isomerization, haptotropic rearrangement, and reorganization of metal–ligand and/or metal–metal bonds. Very recently, the crystalline-state photochromism is becoming an attractive field of photochromic chemistry. As a demonstrative example, the photochromism of organometallic rhodium dinuclear complexes having a dithionite ligand (μ-O₂SSO₂), which shows 100% reversible interconversion in the crystalline-state and have been developed in the authors’ laboratory, will be discussed.     

Photochromism of single crystals of arylhydrazide derivatives

Photochromic transformations in single crystals of hydrazides due to trans—cis-isomerization were found. The presence of the hydroxyl group in the ortho-position of the benzylidene fragment completely precludes photoinduced isomerization in the crystalline state.     

Photochromism and the spectral properties of bispiroanthro-bis-oxazine

The spectral and photochromic properties of bispiroanthro-bis-oxazine (bis-SAO) in toluene, DMF, and polystyrene films were investigated in the 77–300 K interval. It is shown that the long-wave part of the absorption spectrum of the starting form of the molecule is formed by three-electron transitions localized in the anthro-bis-oxazine fragment. The directions of the oscillators of these transitions relative to the nuclear. backbone of the molecule are proposed on the basis of luminescence polarization data. It is proposed that the photochromic properties of the solutions are determined by the existence of bis-SAO molecules in dimer form.N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow. Institute of Solid State and Semiconductor Physics, Academy of Sciences of Belarus, 210023 Vitebsk. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 12, pp. 2718–2725, December, 1992.     

Photochromism of 36-Armed Liquid Crystalline Dendrimer

The photochromism of a 36-armed liquid crystalline dendrimer D6 was briefly described in this paper. The molar absorption coefficient, photoisomerization and photo back-isomerization of D6 in solution were investigated by UV/Vis absorption spectra. The results indicate that the photochromism and photo back-isomerization of D6 in chloroform （CHC13） and tetrahydrofuran （THF） solutions are in accordance with the ftrst order kinetics. The photochromism rate constants of D6 are 101 sI, it is 107 times larger than that of side-chain liquid crystalline polymers containing the same azobenzene moieties.     

萘并萘醌酚醛树脂的合成和光致变色性质

通过6-氯-5,12-萘并萘醌(1)与酚醛树脂经亲棱取代,一步合成制备具有光致变色性的酚醛树脂(3)。在苯溶液中,光致变色聚合物(3)与光致变色化合物6-{4-[2-(4-羟基苯基)异丙基]苯氧基}-5,12-萘并萘醌(2)有相似的光致变色行为。但是,在聚合物(3)中,由于苯基处于聚合物骨架中不易迁移,使聚合物(3)的变色速度较化合物(2)明显减慢,化合物(2)的光异构化速度常数是聚合物(3)的3倍。同时发现溶剂对聚合物(3)的光诱导trans-ana异构化反应速度有明显影响,在氯仿中的反应速度常数约为在苯中的2倍。