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

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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.