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Studies on Molecular Building and Characterization of 1-st Dimensional Polynuclear Metal Complexes Comprised by Stacking Binuclear Units

双核单元堆叠组成的一维多核金属配合物的分子构建及表征研究

基本信息

批准号：
08454212
负责人：
TOKII Tadashi
金额：
$ 4.99万
依托单位：
SAGA University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1996
资助国家：
日本
起止时间：
1996 至 1997
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08454212/
关键词：
Stacking Compoud Polynuclear Metal Complex Polymer Complex 二核金属錯体

项目摘要

A new polynucleating ligand (1), which derived from dinucleating ligand 2-hyfeoxy-4,6-dimethyl-isophtalic acid, was synthesized. However, synthetic yield is quite low (<10%) in spite of our efforts of improvement. It is necessary that the synthetic and purifying methods are established. In relation to this ligand, tow more ligands, which have eta-butylen (2) or rho-xylen (3) as bridging unit, respectively, were prepared as references. These ligands gave higher yield compared with 1 because they had a small steric repulsion.Next step was valuation for ability of the dinucleating unit. A green complex was obtained by the reaction of the dinucleating unit with copper(II) acetate, and a violet complex was obtained from copper (II) bromide. The green complex was assigned as stacking polymeric complex. On the other hand, the violet one was supposed as the mu_4-oxo bridged tetranuclear copper (II) complex. According to these results, the dinucleating ligand generates the pi-stacking effect on its complexation tnder the other ligand absence. Finally, the polymer complexes were synthesized by the reaction of copper (II) acetate with the ligands 1,2 and 3, respectively. Each complex has I : 2 mole ratio about the ligand and copper iorns. Magnetic moments at room temperature were in range I.4-I.6 B.M., which show existence of antiferromagnetic interaction. Ab initio computer calculation was applied to understand the structure of these complexes. As the results, it was suggested that the optimized structure for 1 was p-stacked structure but those of 2 and 3 were linear-Chain structures.

合成了一种新的多成核配体（1），它是由双核配体2-羟基-4，6-二甲基间苯二甲酸衍生而来的。然而，尽管我们努力改进，合成产率仍然很低（<10%）。因此，有必要建立其合成和纯化方法.在此基础上，又合成了两个分别以正丁烯（2）和对二甲苯（3）为桥连单元的配体作为参考。这些配体由于空间位阻小，产率比1高。下一步是评价双核单元的能力。双核单元与醋酸铜反应生成绿色配合物，溴化铜反应生成紫色配合物。将该绿色配合物归属为堆积聚合物配合物。另一方面，紫色的配合物被认为是μ_4-氧代桥联的四核铜（II）配合物。根据这些结果，双核配体在另一配体不存在的情况下对其络合作用产生π堆积效应。最后，通过醋酸铜（II）与配体1，2，3的反应，合成了高分子配合物。配体与铜离子的摩尔比为1：2。室温下的磁矩范围为1.4 - 1.6 B.M.，这表明存在反铁磁相互作用。应用从头算计算机计算来了解这些配合物的结构。结果表明，1的优化结构为p-堆叠结构，而2和3的优化结构为直链结构。