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

以二核配体2-羟基-4,6-二甲基异苯二酸为基础，合成了一种新的多核配体(1)。然而，尽管我们努力改进，合成收率仍然很低（<10%）。有必要建立其合成和纯化方法。在此基础上，制备了以邻丁烯(2)或邻二甲苯(3)为桥接单元的两种配体作为参考。这些配体与1相比产率更高，因为它们有较小的空间斥力。下一步是评估双核单位的能力。二核化单元与醋酸铜（II）反应得到绿色配合物，溴化铜（II）反应得到紫色配合物。绿色配合物被指定为堆叠聚合物配合物。另一方面，紫色的被认为是mu_4-氧桥接的四核铜（II）配合物。根据这些结果，在其他配体缺失的情况下，双核配体对其络合产生pi堆叠效应。最后，以乙酸铜（II）为配体，分别与配体1、2和3反应合成了聚合物配合物。每个配合物的配体和铜铁的摩尔比都是1:2。室温下的磁矩在i - i - 6范围内b.m.，证明了反铁磁相互作用的存在。用计算机从头算法计算了这些配合物的结构。结果表明，1的优化结构为p-堆叠结构，2和3的优化结构为线性链结构。

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.