Studies on elucidation of isomerization reaction of Schiff bases crystals and construction of novel proton flux. supramolecular systems

席夫碱晶体异构化反应的阐明及新型质子通量的构建研究。

• 批准号: 14540498
• 负责人: KAWATO Toshio
• 金额: $ 2.24万
• 依托单位: Kyushu University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14540498/
• 关键词: Photochromism; Photoisomerization; Organic crystals; Salicylideneamines; Schiff bases; Solid state reaction; Proton transfer; X-Ray crystallography; 包接化合物; 光学異性体; デオキシコール酸

Experimantal finding of a cis-keto photoproduct derived from N-salicylideneaniline crystal.Deuterium isotope kinetic effect in the solid state was observed by using thermal fading reaction of photo-coloured species derived from N-salicylideneaniline deuterohydroxyl derivative : thus, the existence of a cis-keto form in the photocoloured Schiff base crystals was suggested experimentally along with 6-methyl-substitution effect on the stability of the photoproduct.Advantage of 2,6-dialkyl substituents of aniline for preparation of photochromic Schiff base crystals.N-(3,5-Dihalosalicylidene)-2,6-dialkylaniline derivatives were prepared and their structure and photochromic properties were investigated. From the X-ray crystallography, it was revealed that steric repulsion between the azomethine hydrogen atom and the alkyl groups at the 2,6-positions of the aniline ring lead to a non-planar molecular structure, which was effective for the crystals to exhibit photochromism. The relationship between photochromicity and crystal packing of N-(3,5-dichlorosalicylidene)-2,6-dialkylanilines series was also discussed. The 2,6-dialkylaniline method was suggested to be applicable to the preparation of photochromic Schiff bases with various substituents in the salicylidene rings.Photochromism of polymorphic 4,4'-methylenebis(N-salicylidene-2,6-diisopropylaniline) crystals.4,4'-Methylenebis(N-salicylidene-2,6-dialkylaniline) derivatives were prepared and their structures were determined by ^1H NMR,IR,DSC and X-ray crystallographic analyses. The 2,6-diisopropylaniline derivative yielded definite polymorphic crystals : the space groups of the crystals were C2/c and P2_1/n, respectively. It was found that both polymorphs were similarly photochromic but the thermal stability of the photochrome was different due to the variance of the shape of molecule and cavity in each crystal.

实验发现源自N-水杨基苯胺晶体的顺式酮光产物。通过利用源自N-水杨基苯胺氘羟基衍生物的光致变色物质的热褪色反应观察到固态氘同位素动力学效应：因此，表明光致着色希夫碱晶体中存在顺式酮形式 研究了苯胺的2,6-二烷基取代基在制备光致变色希夫碱晶体中的优势。制备了N-(3,5-二卤代水杨基)-2,6-二烷基苯胺衍生物，并研究了其结构和光致变色性能。 X射线晶体学表明，偶氮甲碱氢原子与苯胺环2,6位烷基之间的空间排斥导致非平面分子结构，这对于晶体表现出光致变色是有效的。还讨论了N-(3,5-二氯水杨基)-2,6-二烷基苯胺系列的光致变色性与晶体堆积之间的关系。 2,6-二烷基苯胺法适用于水杨环上具有多种取代基的光致变色席夫碱的制备。多晶型4,4'-亚甲基双(N-水杨基-2,6-二异丙基苯胺)的光致变色 制备了4,4'-亚甲基双(N-水杨基-2,6-二烷基苯胺)衍生物，并通过1H NMR、IR、DSC和X射线晶体分析确定了其结构。 2,6-二异丙基苯胺衍生物得到了明确的多晶型晶体：晶体的空间群分别为C2/c和P2_1/n。结果发现，两种多晶型物具有相似的光致变色性，但由于每个晶体中分子形状和空腔的变化，光致变色的热稳定性不同。

项目成果

Hisatane Fukuda, Toshio Kawato 他: "Crystalline photochromism of N-salicylidene-2,6-dialkylanilines : advantage of 2,6-dialkyl substituents of aniline for preparation of photochromic Schiff base crystals"Organic & Biomolecular Chemistry. 1. 1578-1583 (2003

Hisatane Fukuda、Toshio Kawato 等人：“N-水杨基-2,6-二烷基苯胺的晶体光致变色：苯胺的 2,6-二烷基取代基用于制备光致变色希夫碱晶体的优势”有机与生物分子化学 1。1578-。 1583 ( 2003 年

Photochromism of polymorphic 4,4'-mcthylcncbis-(N-salicylidenc-2,6-diisopropylanilinc crystals

多晶型 4,4-甲基苯胺双-(N-水杨基-2,6-二异丙基苯胺晶体)的光致变色

• 发表时间: 2004
• 期刊: Organic and Biomolecular Chemistry 2
• 作者: Masatsugu Tancda;Toshio Kawato et al.
• 通讯作者: Toshio Kawato et al.

Hiroshi Sekiya, Toshio Kawato他: "Excited-state intramolecular proton transfer in photochromic jet-cooled N-salicylideneaniline"J.Photochem.Photobiol., Chemistry. 154. 33-39 (2002)

Hiroshi Sekiya、Toshio Kawato 等人：“光致变色喷射冷却 N-水杨基苯胺中的激发态分子内质子转移”J.Photochem.Photobiol.，Chemistry 154. 33-39 (2002)。

Excited-state intramolecular proton transfer in photochromic jet-cooled N-salicylideneaniline

• DOI: 10.1016/s1010-6030(02)00306-4
• 发表时间: 2002-12
• 期刊: Journal of Photochemistry and Photobiology A-chemistry
• 影响因子: 4.3
• 作者: Nobuto Otsubo;C. Okabe;H. Mori;Kenji Sakota;Kiichi Amimoto;T. Kawato;H. Sekiya

N-サリチリデンアニリン類結晶のフォトクロミズム

N-水杨基苯胺晶体的光致变色

• 发表时间: 2003
• 期刊: 光化学 34・1
• 作者: 網木貴一;川東利男
• 通讯作者: 川東利男