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一些含乙酰乙酰苯胺和异恶唑腙配体的新型双核过渡金属(II)配合物的光谱和热学研究

Spectroscopic, and thermal studies of some new binuclear transition metal(II) complexes with hydrazone ligands containing acetoacetanilide and isoxazole.

作者信息

Chen Zhimin, Wu Yiqun, Gu Donghong, Gan Fuxi

机构信息

Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai, PR China.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2007 Nov;68(3):918-26. doi: 10.1016/j.saa.2007.01.006. Epub 2007 Jan 19.

Abstract

A new chelating ligand, 2-(2-(5-tert-butylisoxazol-3-yl)hydrazono)-N-(2,4-dimethylphenyl)-3-oxobutanamide (HL), and its four binuclear transition metal complexes, M(2)(L)(2) (micro-OCH(3))(2) [M=Ni(II), Co(II), Cu(II), Zn(II)], were synthesized using the procedure of diazotization, coupling and metallization. Their structures were postulated based on elemental analysis, (1)H NMR, MALDI-MS, FT-IR spectra and UV-vis electronic absorption spectra. Smooth films of these complexes on K9 glass substrates were prepared using the spin-coating method and their absorption properties were evaluated. The thermal properties of the metal(II) complexes were investigated by thermogravimetry (TG) and differential scanning calorimetry (DSC). Different thermodynamic and kinetic parameters namely activation energy (E*), enthalpy of activation (DeltaH*), entropy of activation (DeltaS*) and free energy change of activation (DeltaG*) are calculated using Coats-Redfern (CR) equation.

摘要

一种新型螯合配体,2-(2-(5-叔丁基异恶唑-3-基)肼基)-N-(2,4-二甲基苯基)-3-氧代丁酰胺(HL)及其四种双核过渡金属配合物M₂(L)₂(μ-OCH₃)₂[M = Ni(II)、Co(II)、Cu(II)、Zn(II)],采用重氮化、偶联和金属化步骤合成。基于元素分析、¹H NMR、基质辅助激光解吸电离质谱(MALDI-MS)、傅里叶变换红外光谱(FT-IR)和紫外可见电子吸收光谱推测了它们的结构。使用旋涂法在K9玻璃基板上制备了这些配合物的光滑薄膜,并评估了它们的吸收特性。通过热重分析(TG)和差示扫描量热法(DSC)研究了金属(II)配合物的热性质。使用Coats-Redfern(CR)方程计算了不同的热力学和动力学参数,即活化能(E*)、活化焓(ΔH*)、活化熵(ΔS*)和活化自由能变化(ΔG*)。

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