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

粘液负责复合物及其结构、性质和反应性的概要

基本信息

批准号：
11304046
负责人：
FUKUDA Yutaka
金额：
$ 23.82万
依托单位：
OCHANOMIZU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2002
项目状态：
已结题

项目摘要

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.

我们研究了各种过渡金属配合物的显色体系。(1)对于溶剂致色性和热致色性，合成了多种含有手性β-二酮酸酯（如三氟乙酰-樟脑酸酯）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配合物对有机配体的手性识别。与乙基樟脑衍生物配体配合物的手性辨别能力不强，而手性二胺的手性辨别能力更强，目前研究还在进行中。(2)化合物Ni（环二胺）（dike）X的溶剂致变色体系，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。这些非配位阴离子混合配合物呈方形平面，配位阴离子混合配合物呈八面体，称为“阴离子结构调节效应”。(3)合成了具有大体积双齿二亚胺配体的Cu（II）配合物并测定了其晶体结构，这是阐明催化配合物体系中间物质的重要工作。(4)最后，我们得到了两个“电致变色”的例子，当Mn（II）和Mn（III）的氧化还原体系含有1,4,7-三氮杂环ionononone -1,4,7-三羧酸盐时，呈现出可逆的颜色变化（深红色< = >无色）。