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含双酰腙四齿配体和1,10-菲咯啉的混合配体及聚合双核过渡金属配合物的合成与光谱研究

Synthesis and spectroscopic studies of mixed-ligand and polymeric dinuclear transition metal complexes with bis-acylhydrazone tetradentate ligands and 1,10-phenanthroline.

作者信息

Gup Ramazan, Kirkan Bülent

机构信息

Department of Chemistry, Mugla University, Kampus-Kotekli, 48000 Mugla, Turkey.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2006 Jun;64(3):809-15. doi: 10.1016/j.saa.2005.08.008. Epub 2006 Feb 2.

Abstract

Two types of dinuclear copper(II) and nickel(II) complexes with two tetradentate N2O2 donor ligands 1,4-bis(1-anthranoylhydrazonoethyl)benzene (L1), 1,4-bis(1-salicyloylhydrazonoethyl)benzene (L2) and N,N'-bidentate heterocyclic base [1,10-phenonthroline (phen)] have been synthesized and characterized by elemental analysis, infrared spectra, UV-vis electronic absorption spectra and magnetic susceptibility measurements. The reaction of metal(II) acetates with the solution containing ligand and 1,10-phenonthroline in methanol gives mixed-ligand dinuclear metal(II) complexes with general formula [M2L(phen)2]Cl2 (L=L1 or L2), whereas, the ligands react with metal(II) acetates to form polymeric dinuclear complexes with general formula [(M2L2)n] (L=L1 or L2). In the complexes, the ligands act as dianionic tetradentate and coordination takes place in the enol tautomeric form with the enolic oxygen and azomethine nitrogen atoms while the phenolic hydroxyl and amino groups of aroylhydrazone moiety do not participate in coordination. The effect of varying pH and solvent on the absorption behavior of both ligands and complexes has been investigated.

摘要

合成了两种双核铜(II)和镍(II)配合物,它们含有两个四齿N2O2供体配体1,4-双(1-邻氨基苯甲酰腙基乙基)苯(L1)、1,4-双(1-水杨酰腙基乙基)苯(L2)以及N,N'-双齿杂环碱[1,10-菲咯啉(phen)],并通过元素分析、红外光谱、紫外可见电子吸收光谱和磁化率测量对其进行了表征。金属(II)乙酸盐与含有配体和1,10-菲咯啉的甲醇溶液反应,得到通式为[M2L(phen)2]Cl2(L = L1或L2)的混合配体双核金属(II)配合物,而配体与金属(II)乙酸盐反应形成通式为[(M2L2)n](L = L1或L2)的聚合双核配合物。在这些配合物中,配体作为双阴离子四齿配体,以烯醇互变异构形式通过烯醇式氧原子和偶氮甲碱氮原子进行配位,而芳酰腙部分的酚羟基和氨基不参与配位。研究了pH值和溶剂变化对配体和配合物吸收行为的影响。

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