Synthesis and photochromic properties of 4-[2-(anthracen-9-yl)-5-methyloxazolyl] fulgide

New photochromic fulgide, viz., 4-{1-[2-(anthracen-9-yl)-5-methyloxazol-4-yl]ethylidene}-3-isopropylidenetetrahydrofuran-2,5-dione, with fluorescent properties was synthesized. Studies by electronic, IR, and ¹H NMR spectroscopy and X-ray diffraction demonstrated that this fulgide exists in the Z form. Light irradiation of its solutions at a wavelength of 365 nm causes Z/E isomerization giving rise to the thermally stable cyclic form. The latter is transformed into the starting E isomer under light irradiation at λ = 436 nm. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 97–101, January, 2006.     

Synthesis and applications of photochromic fulgides in optical information storages

A pyrryl substituted photocbromic fulgide, (1-p-methoxyphenyl-2-methyl-5-phenyl)-3-pyrryl-ethylidene (isopropylidene) succinic anhydride, was synthesized. Its chemical structure was identified by IR, 1H NMR MS and elemental analysis. The title compound was used to prepare the optical disks by the spin coating method and the vacuum evaporation method. The results of the static state examination show that the optical disks prepared with this kind of molecules possess excellent thermal stability and fatigue resistance, i.e. over 450 writing-erasing recycles, the relative contrast between writing state and erasing state remains at 40%.     

吡咯俘精酸酐的图像光存储特性

对一种新型可用于可擦重写光存储的有机光致变色材料——吡咯俘精酸酐，测定了它的光致变色双稳态吸收光谱，呈色态的吸收峰在635nm，无色态的吸收峰在385nm。利用其双稳态特性，在吡咯俘精酸酐／PMMA薄膜上实现了图像光存储。所存储的图像对比度高，用普通相机在自然光下即可直接读出。在膜上存储的图像在室温下暗处保存6个月未见消退，估计此条件下保存期可以年计。     

2-(1-苄基-3-甲基-2-吲哚亚甲基)-3-亚异丙基丁二酸酐的合成及其光致变色性能研究

在氢化钠和甲苯存在下, 1-苄基-3-甲基吲哚-2-甲醛与亚异丙基丁二酸二乙酯发生Stobbe缩合反应, 经过碱性水解和酸化得到二酸化合物, 接着在乙酰氯存在下脱水, 合成2-(1-苄基-3-甲基-2-吲哚亚甲基)-3-亚异丙基丁二酸酐. 研究了该俘精酸酐在不同溶剂中的光致变色性能.     

CNDO/2-FPP Polarizabilities

Polarization functions have been added to the CNDO/2 basis set to reproduce a minimal set of experimental polarizability tensors for 13 model molecules containing H, C, N, O, F, P, S, Cl, Se, and Br without affecting occupied molecular orbital energies or atom-in-molecule charges. The resulting CNDO/2-FPP program yields excellent molecular and atom-in-molecule polarizability tensors for almost any molecule containing these elements.     

吲哚俘精酰胺的偏振全息图像光存储实验研究

在吲哚俘精酰胺/PMMA薄膜上记录了同偏振全息和正交偏振全息图，获得了它们的再现衍射像.实验结果表明：吲哚俘精酰胺具有光致各向异性，可以进行正交偏振全息记录.在偏振全息中，衍射光的偏振方向依赖于物光和再现光的偏振方向，衍射像的噪声主要来源于再现光照射到样品上引起的散射.正交偏振全息可以得到比同偏振全息更高信噪比的衍射像.存储于样品上的全息图在室温下黑暗处至少可以保存五个月而衍射效率无明显下降.结果表明，吲哚俘精酰胺是一种可用于偏振全息的可擦重写记录介质. 关键词： 偏振全息 光致各向异性 俘精酸酐 光致变色     

Chiral,Thermally Irreversible and Quasi-Stealth Photochromic Dopant to Control Selective Reflection Wavelength of Cholesteric Liquid Crystal

A chiral and thermally irreversible photochromic fulgide derivative incorporating an (R)-binaphthol unit in its acid anhydride moiety was used for the photoswitching of the pitch length of cholesteric liquid crystals. Since the absorption maximum wavelengths of both thermally stable photoisomers are nearly in the UV region (quasi-stealth photochromism), it can be exposed to visible light without inducing photochromic reactions. Therefore, when the photoswitching molecule is added to a permanent cholesteric liquid crystal whose reflection light wavelength is in the visible region, the UV light-induced photochromic reaction of the photoswitching molecule changes the wavelength of the reflection light in the visible light region. We have succeeded in regulating the color of cholesteric liquid crystalline cells between red and blue upon UV light irradiation. Attempts to introduce this system in polymer dispersed cholesteric liquid crystals are also described.     

Synthesis, structures, and photochromic properties of 2-methylthieno[3,2-b][1]benzothiophen-3-ylfulgide

The novel heterocyclic fulgide, 3-(1-methylethylidene)-4-[1-(2-methylthieno[3,2-b]-[1]benzothiophen-3-yl)ethylidene]dihydrofuran-2,5-dione, was obtained and isolated as a Z-isomer. Its structure was confirmed by electronic absorption spectroscopy, ¹H NMR spectroscopy, and X-ray diffraction analysis. The novel thienothiophene fulgide is photochromic in both solutions and the crystalline state. Its colored cyclic form resists photodegradation and is thermally stable. When benzothiophene is annulated with the thienyl fragment, the long-wavelength absorption peak of the cyclic isomer of the novel fulgide experiences a bathochromic shift compared to the earlier described 3-thienylfulgide. The TD B3LYP/6-311G**-calculated spectroscopic characteristics of the fulgide isomers suggest the formation of their photostationary mixture under irradiation with λ = 365 nm. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2318–2324, December, 2007.     

Photochromic and fluorescence properties of coumarin fulgimides

Four new fulgimides possessing a fluorescent coumarin unit were synthesized from the corresponding fulgides, and their photochromic as well as fluorescence properties were investigated. The open-ring forms of coumarin fulgimides were found to exhibit fluorescence in the visible region. Upon exposure to UV light, the fulgimides were transformed into the nonfluorescent closed-ring forms, which can be reverted to the initial fluorescent open-ring forms on exposure to visible light. The efficiency of quenching of fluorescence was as high as 95% at the photostationary state of UV irradiation.     

双色俘精酸酐薄膜的双波长图像光存储

采用两种光致变色俘精酸酐体系化合物[1,2,4-三甲基-5-苯基-3-吡咯甲叉(异丙叉)俘精酸酐和对-N,N-二甲基苯基-2-甲基-3-恶唑甲叉(异丙叉)俘精酸酐]制备了单层双色聚甲基丙烯酸甲酯(PMMA)复合薄膜感光记录材料。采用双波长(650nm和488nm)图像存储和读出光路,实现了用两种波长在双色复合薄膜的同一位置同时记录两幅图像。当分别用各自对应的波长读出时,两幅图像各自获得了高衬比度,且二者之间的串扰很小,证明了在双色光致变色俘精酸酐材料上进行双波长复用图像光存储的可行性。