超分子結晶中でのシッフ塩基類の異性化機構の解明と新規プロトン移動系の構築

阐明超分子晶体中席夫碱的异构化机理并构建新型质子转移体系

• 批准号: 11640538
• 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: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11640538/
• 关键词: photochromism; photoisomerization; solid-state reaction; inclusion crystals; supramolecula chemistry; N-salicylideneamline; Schiff base; deoxycholic acid; 光学異性体

N-{3,5-bis(1-methyl-1-phenylethyl)salicylidene}-4-trityl-aniline and its clathrate crystals with methanol and acetone were prepared. The yielded crystals were photochromic; each photo-colored species was obtained by irradiating crystalline powder with 365 nm light. The large substituents on both aromatic rings were found not to disturb the occurrence of photochromism of salicylideneaniline. The degrees of the spectral changes after UV irradiation for the solvent clathrate compounds were much smaller than that of pure host Schiff base crystals. The maximum changes in optical density were observed at 481 nm for the parent Schiff base and 499 nm for both solvent adducts. Thermal stability of the photochrome depended on the solvent included. Thus, solvent effects were observed on the solid-phase photoisomerization of the Schiff base. Definite clathrate crystals of deoxycholic acid and its amide and alcohol derivatives as host molecules with N-salicylideneaniline as a guest molecule were pr … More epared to investigate their photochromic properties. All these clathrate crystals exhibited photochromism by irradiating the crystal powder with 365 nm light. Rate constants of the thermal fading of the photochromes were measured to be distinct in the different clathrate environments. From the sharp difference in the first-order rate constants of the thermal bleaching of the photochromes, it was found that the thermal unimolecular motion of photo-colored species was strongly influenced by the neighboring environments in the crystal state. These results demonstrate that the photochromic process of Schiff bases is delicate and a small change of supramolecular environment influences strongly the photochromic properties in the crystal state.In order to develop a new series of supramolecular systems, we prepared a series of 2,6-bis(2,2'-dicarbalkoxyethyl)pyridine ligands and their Pd(ll)-complexes. A couple of the ligands linked by a trans-PdCl2 unit were found toextract alkali metal ions from an aqueous media into a chloroform media, while a single pyridine ligand did not work as an extractive reagent. In general, acyclic host molecules have the advantage of easy synthesis and high versatility of the structure. Thus, 2,6-difunctionalized pyridines and related derivatives are expected to develop into a new type of supramolecular systems to pick up selected chemical species by the aid of trans-metal complexation which grips the coupled host molecules in the right way. Of the potential variations on our general strategy, a study on the inclusion of a neutral molecule into such a Pd(ll) complex with condensed-ring subunits is now under investigation. Less

合成了N-{3，5-二（1-甲基-1-苯乙基）亚水杨基}-4-三苯甲基苯胺及其与甲醇、丙酮的包合物晶体。所产生的晶体是光致变色的;通过用365 nm的光照射结晶粉末来获得各光致变色物质。发现两个芳环上的大取代基不会干扰水杨醛苯胺光致变色的发生。溶剂包合物在紫外光照射后光谱的变化程度远小于纯主体席夫碱晶体。母体席夫碱在481 nm处观察到光密度的最大变化，两种溶剂加合物在499 nm处观察到光密度的最大变化。光致变色剂的热稳定性取决于所包括的溶剂。因此，溶剂效应上观察到的席夫碱的固相光异构化。以脱氧胆酸及其酰胺、醇衍生物为主体分子，N-水杨醛苯胺为客体分子，制备了明确的笼形晶体 ...更多信息 研究了它们的光致变色性能。通过用365 nm的光照射晶体粉末，所有这些笼形晶体都表现出光致变色。在不同的包合物环境中，光致变色化合物的热褪色速率常数是不同的。从光致变色物质热漂白的一级速率常数的急剧差异，发现光致变色物质的热单分子运动强烈地受晶体状态下的邻近环境的影响。为了开发一系列新的超分子体系，我们合成了一系列2，6-双（2，2 ′-二烷氧乙基）吡啶配体及其Pd（II）配合物。发现由trans-PdCl_2单元连接的一对配体可以从水介质中萃取碱金属离子到氯仿介质中，而单个吡啶配体不能作为萃取剂。一般来说，无环主体分子具有易于合成和结构通用性高的优点。因此，2，6-二官能化吡啶及其衍生物有望发展成为一种新型的超分子体系，通过反式金属络合作用以正确的方式抓住偶联的主体分子，从而获得选定的化学物种。在我们的一般策略的潜在变化中，关于将中性分子包含到具有稠环亚基的Pd（II）络合物中的研究现在正在调查中。少

项目成果

Toshio Kawato, Hajime Kanatomi, Kiichi Amimoto, Hiroyuki Koyama, and Hideki Shigemizu: "Enclathrated Solvent Effects on the Photochromic Process of N-Salicylideneaniline in the Crystal State"Chemistry Letters. No.1. 47-48 (1999)

Toshio Kawato、Hajime Kanatomi、Kiichi Amimoto、Hiroyuki Koyama 和 Hideki Shigemizu：“包合溶剂对晶态 N-水杨基苯胺光致变色过程的影响”化学快报。

Toshio Kawato, Kiichi Amimoto, Hiroshi Maeda, Hiroyuki Koyama, and Hajime Kanatomi: "Photochromism of Guest N-Salicylideneaniline in the Rooms of Host Bile Acid Derivatives"Molecular Crystal and Liquid Crystal. Vol.345. 57-62 (2000)

Toshio Kawato、Kiichi Amimoto、Hiroshi Maeda、Hiroyuki Koyama 和 Hajime Kanatomi：“客体 N-水杨基苯胺在宿主胆汁酸衍生物房间中的光致变色”分子晶体和液晶。

Toshio Kawato 他: "Photochromism of Guest N-Salicylideneaniline in the Rooms of Host Bile Acid Derivatives."Molecular Crystals and Liquid Crystals. 345巻. 57-62 (2000)

Toshio Kawato 等人：“宿主胆汁酸衍生物房间中客体 N-水杨基苯胺的光致变色”。《分子晶体和液晶》卷 345. 57-62 (2000)。

Toshio Kawato et al.: "Photochromism of Guest N-Salicylideneaniline in the Rooms of Host Bile Acid Derivatives"Molecular Crystals and Liquid Crystals. Vol.345. 57-62 (2000)

Toshio Kawato 等人：“客体 N-水杨基苯胺在宿主胆汁酸衍生物房间中的光致变色”分子晶体和液晶。

Tomoko Mutou, Kiichi Amimoto, Hiroyuki Koyama, Hajime Kanatomi, and Toshio Kawato: "Palladium(II)-induced Alkali Metal Ion Incorporation of 2,6-Disubstituted Pyridines with Bis(alkoxyethyl) Malonate Subunits"Chemistry Letters. No.11. 1231-1232 (1999)

Tomoko Mutou、Kiichi Amimoto、Hiroyuki Koyama、Hajime Kanatomi 和 Toshio Kawato：“钯 (II) 诱导的碱金属离子与双（烷氧基乙基）丙二酸亚基的 2,6-二取代吡啶的结合”化学快报。