Sgncheses of slimulus responsible complexes and their structure, properties and reactivities

本文研究了过渡金属配合物的各种变色体系。(1)为了实现溶剂化变色和热变色，合成了多种含有手性β-二酮（dike，如三氟乙酰基樟脑酸）和手性二胺（N-烷基化-1，2-二氨基-丙烷，diam）的混合配体配合物（Ni（II）和Cu（II））：通式，M（diam）（dike）X。本研究的另一个有趣的点是由于含有这些类型的手性配体的手性混合配体络合物的有机配体的手性歧视。以乙酰樟脑衍生物为配体的配合物不具有很强的手性识别能力，而手性二胺则表现出较强的手性识别能力，其研究正在进行中。(2)化合物Ni（环二胺）（dike）X的溶剂化变色体系，其中环二胺= N-甲基-1，4-二氮杂环庚烷，dike =各种dike，X =配位或非配位单阴离子。与非配位阴离子形成的混配配合物呈正方形平面结构，与配位阴离子形成的混配配合物呈八面体结构，这就是所谓的“阴离子结构调控效应”。(3)合成了大体积双齿二亚胺配体的Cu（II）配合物，并测定了它们的晶体结构，这对阐明配合物催化体系的中间体是重要的工作。(4)最后，我们得到了两个“电致变色”的例子，它们在Mn（II）和Mn（III）含1，4，7-三氮杂环壬烷-1，4，7-三羧酸盐的氧化还原体系中显示可逆的颜色变化（深红< = >无色）。

We have studied various kinds of chromotropic systems of the transition metal omplexes. (1) For the Solvatochromism and Thermochromism, many kinds of mixed ligand complexes (Ni(II) and Cu(II)) containing a chirai β-diketonate(dike, such as trifluoro-acetyl-camphororate) and the chiral diamine (N-alkylated-1, 2-diamino-propane, diam) synthesized : general formula, M(diam)(dike)X. Another interesting point of this study is chiral discrimination of the organic ligand due to the chiral mixed ligand complexes containing these types of chiral ligands. The complexes with the ligand of acethylcamphor derivatives could not have a strong power of chiral discrimination, on the other hand, the chiral diamine shows more effective power for the chiral discrimination whose study is now in progress. (2) Solvatochromic systems of the compounds, Ni(cvclic-diamine)(dike)X, where cyclic-diamine = N-methyl-1, 4-diazacycloheptane, dike = various kinds of dike, X = coordinating or non-coordinating monoanion. These mixed ligand complexes with non-coordinating anion, show square planar and those with coordinating anion are octahedral This is called as "Anion effect of structural regulation". (3) Cu(II) complexes with bulky bidentate di-imine ligand synthesized and their crystal structure were determined, which is important work to clarify the intermediate substance of the catalytic complex system. (4) Finally, we obtained two examples of "Electrochromism", which shows reversible color change(deep red < = > colorless) with the redox system of Mn(II) and Mn(III) containing 1,4,7-triazacycIononane-1,4,7-tricarboxylate.