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

用甲醇和丙酮制备了N-{3,5-二（1-甲基-1-苯乙基）水杨基}-4-三烷基苯胺及其笼形物晶体。所得晶体为光致变色晶体；每个光色物种都是通过365 nm光照射结晶粉末获得的。两个芳香环上的大取代基对水杨基苯胺光致变色的发生没有影响。溶剂包合物在紫外照射后的光谱变化程度远小于纯寄主席夫碱晶体。母席夫碱的光密度变化在481 nm处最大，溶剂加合物的光密度变化在499 nm处最大。光色素的热稳定性与所含溶剂有关。因此，溶剂效应在席夫碱的固相光异构化中被观察到。以n -水杨基苯胺为客体分子，制备了脱氧胆酸及其酰胺和醇衍生物的包合物晶体，进一步研究了它们的光致变色性质。在365 nm光照射下，这些包合物晶体均表现出光致变色。测定了光致变色剂在不同笼形物环境下的热衰减速率常数。从光致变色一阶速率常数的显著差异可以看出，在晶体状态下，光致变色物质的热单分子运动受到邻近环境的强烈影响。这些结果表明，希夫碱的光致变色过程是微妙的，超分子环境的微小变化会强烈地影响晶体状态下的光致变色性能。为了开发一系列新的超分子体系，我们制备了一系列2,6-二（2,2'-二碳氧乙基）吡啶配体及其Pd（ll）配合物。一对由反式pdcl2单元连接的配体被发现可以将碱金属离子从水介质中提取到氯仿介质中，而单个吡啶配体不能作为提取试剂。一般来说，无环宿主分子具有易于合成和结构通用性强的优点。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，通过反金属络合作用，以正确的方式吸附偶联的宿主分子，从而吸附选定的化学物质。在我们的一般策略的潜在变化中，目前正在研究将中性分子包含到具有凝聚环亚基的Pd（ll）配合物中。少

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