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

实验发现N-亚水杨基苯胺晶体中的顺式-酮基光产物，利用N-亚水杨基苯胺氘代羟基衍生物的光致变色物种的热褪色反应，观察到固态下氘同位素动力学效应：因此，在本发明中，实验表明，在光致变色的席夫碱晶体中存在顺式-酮形式，合成了N-（3，5-二卤代水杨醛）-2，6-二烷基苯胺衍生物，并对其结构和光致变色性能进行了研究。X射线晶体学研究表明，甲亚胺氢原子与苯胺环2，6-位烷基之间的空间排斥导致了非平面分子结构，这对晶体表现出光致变色性是有效的。讨论了N-（3，5-二氯亚水杨基）-2，6-二烷基苯胺系列化合物的光致变色性与晶体堆积的关系。采用2，6-二烷基苯胺法合成了4，4 '-亚甲基双（N-亚水杨基-2，6-二异丙基苯胺）衍生物，并对其结构进行了表征. 2，6-二异丙基苯胺衍生物具有明确的多晶型，空间群分别为C2/c和P2_1/n。结果表明，这两种多晶型物具有相似的光致变色性质，但由于晶体中分子的形状和空腔的不同，光致变色物的热稳定性不同。

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.