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.     

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 application on parallel image storage of bisfurylfulgide

The synthesis of photochromic compounds has received a great deal of attention because of their potential application in various areas such as optical information storage[1—5], photoswitches and molecular recognition[6—8]. One of the most important researches in this field is the synthesis of a variety of photochromic fulgides to establish basic correlation between their molecular structures and photochromic properties. Since 1978, Heller[9] firstly reported the synthesis of the heterocyclic…     

Photochromic reactions of pyrryl substituted fulgides and fulgimides

Photochromic behaviour of six pyrryl substituted fulgides and one fulgimide has been examined. The substituents have significant effects on their photochromic processes. The results of steady state kinetics show that the photodecoloration of the colored form, 7,7a-dihydroindole derivatives (II) follows the first-order kinetics. The substituents have certain effects on the rate constant of the photodecoloration. As for the colored form (II), compounds with the substituent at 2- or 3-position have larger rate constants of the decoloration than those of non-substituted ones. The photocoloration reactions are more complicated and do not fit the simple kinetics. Introduction of the electron donating substituent into the 2- or 3-position leads to bathochromic shift of the maximum of absorption (λmax) of 7,7a-dihydroindole derivatives. For example, the λmax of compound II 7 is 720 nm in acetonitrile. The increasing of the polarity of the solvent caused a remarkable bathochromic shift of λmax of the colored     

光致变色冠醚部花菁染料的合成及其逆光致变色性

作者用含冠醚结构单元的2-甲基-苯并噻唑季铵盐与取代水物醛缩合得到了五个光致变色冠醚部化菁化合物。这些新的冠醚化合物具有逆光致变色性质, 较稳定的结构是开环部花菁式。     

Synthesis, structures, and photochromic properties of N-aryl-3-indolylfulgides

New 3-indolylfulgides, viz., 3-[1-(1-aryl-5-methoxy-2-methyl-1H-indol-3-yl)ethylidene]-4-(1-methylethylidene)tetrahydro-2,5-furandiones, were synthesized. These compounds were obtained as E-isomers, as demonstrated by X-ray diffraction, electronic spectroscopy, and ¹H NMR spectroscopy. Fulgides exhibit photochromic properties in solution. The cyclic dihydrocarbazole photoisomers of indolylfulgides show fluorescence properties and are characterized by high thermal stability. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1417–1423, July, 2008.     

Synthesis of polymerizable photochromic spironaphthoxazines

Hydrogenatjon of 8-nitrospironaphthoxazine (1) resulted in the corresponding amine (2). Acylation of compound 2 yielded the N-methacryloyl derivative (3). Radical polymerization of the latter resulted in its copolymers with styrene, which possess photochromic properties.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1243–1245, May, 1996.     

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.     

吡咯取代的杂环俘精酸酐的合成及溶剂对其吸收光谱的影响

合成了五个新的3-乙酰基吡咯衍生物,以它们为原料,进一步合成了五个新的吡咯取代的俘精酸酐。研究了五个俘精酸酐化合物在不同溶剂中的光致变色性能,考察了溶剂极性对俘精酸酐及其光致变色反应产物(7,7a-二氢吲哚衍生物)吸收光谱的影响,结果表明,随溶剂极性的增加吸收光谱发生红移。对7,7a-二氢吲哚衍生物的影响远比对俘精酸酐本身的影响显著的多。     

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 and properties of a novel photochromic luminophore

A photochemically bifunctional compound was obtained. Its molecule includes the spironaphthoxazine and dansylamino fragments. This compound exhibits both photochromic and luminescent properties. Its spectroscopic characteristics were studied in different solvents. The electronic systems of two constituent fragments do not interact with each other. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2802–2805, December, 2005.     

Side-chain liquid crystalline polyesters for optical information storage

Azobenzene side-chain liquid crystalline polyester structures suitable for permanent optical storage are described. The synthesis and characterization of the polyesters together with differential scanning calorimetry and X-ray investigations are discussed. Optical anisotropic investigations and holographic storage in one particular polyester are described in detail and polarized Fourier transform infrared spectroscopic data complementing the optical data are presented. Optical and atomic force microscope investigations point to a laser-induced aggregation as responsible for permanent optical storage.     

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.     

超声波辐射下光致变色螺噁嗪类化合物的快速合成

在超声波辐射条件下,以Fischer碱、1-亚硝基-2,7-二羟基萘为原料,无水乙醇为溶剂快速合成了三个螺嗪类光致变色化合物,通过1 H NMR、IR对目标产物的结构进行了表征,讨论了超声辐射时间对合成产率的影响,利用超声波法合成螺噁嗪类光致变色化合物反应速率快、产率有所提高.     

冠醚螺吡喃化合物的合成和光致变色性质

合成了四个新的6位带不同取代基的含冠醚结构单元吲哚啉螺苯并吡喃化合物(5a-5d),研究了其光致变色性质和离子诱导光致变色作用及取代基的影响。结果表明冠醚能稳定螺吡喃开环形式,碱金属离子对冠醚螺吡喃的生色有诱导作用;6位为吸电子基团时,螺吡喃开环形式的稳定性增加,而6位为推电子基团时,螺吡喃开环形式的稳定性降低。另外,就稳定螺吡喃开环体的作用来说,吲哚啉环上的取代基效应和苯并吡喃环上的正好相反。     

Synthesis and spectral kinetic investigation of solutions of photochromic thienylfulgimides

A convenient method has been developed for the synthesis of previously unknown photochromic 1-amino-3-[1-(2,5-dimethyl-3-thienyl)ethylidene]-4-(1-methylethylidene)pyrrolidine-2,5-dione, from which photochromic Schiff’s bases were obtained. A spectral kinetic investigation of the photochromism of the thienylfulgimides obtained has been carried out. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1170–1175, August, 2006.     

Preparation of a spirooxazine grafted PMMA and its photochromic properties

A novel spirooxazine (SO) compound was designed and synthesized. Macromolecular materials, called SO-g-hPMMAs (where the g means grafting and the h means partial hydrolysis), were prepared using PMMA (polymethylmethacrylate) with different degrees of hydrolysis. SO-g-5%hPMMA was prepared by reacting SO-containing active C-Br bonds with 5% partially hydrolyzed PMMA. The SO was characterized using ¹H NMR and infrared. Beyond that, photochromic properties were studied in detail. We discuss the effects of hydrochloric acids and hPMMAs of different hydrolysis degrees on photochromic properties of SO-g-hPMMA. Additionally, mechanical properties of the material were studied. Results indicate that the colored ring-opening form (PMC) of SO-g-hPMMA exhibits a good performance in terms of thermal stability, in contrast to the homologous SO. Experiments additionally demonstrate that hydrochloric acid improves the PMC’s thermal stability. SO-g-9%hPMMA demonstrated a good performance of photochromic properties compared to those with different degrees of hydrolysis.     

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.     

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.