两种甲氧基苯基咔咯铜配合物的合成及光谱性质(英文)

Synthesis and Spectral Properties of Two Copper Methoxyphenylcorrole Complexes

合成了两个中位苯基上具有甲氧基取代基的铜咔咯配合物(Tp-OCH3PC)Cu和(To,p-(OCH3)2PC)Cu,通过紫外-可见、红外光谱、元素分析、核磁共振及质谱对它们进行了表征。研究了配合物在非水溶剂中的电子顺磁共振、电化学和光谱电化学性质,结果表明无论在固体状态还是在非水溶剂中,配合物的中心金属离子均为三价铜Cu(Ⅲ),在给定的溶剂中Cu(Ⅲ)可以发生可逆的还原反应生成Cu(Ⅱ),也可以被可逆氧化为Cu(Ⅲ)的阳离子自由基。探讨了甲氧基取代基以及溶剂对配合物的紫外-可见光谱和氧化还原电位的影响。

Two copper methoxyphenylcorrole complexes were synthesized and characterized by UV-Vis,FTIR,1H NMR,MS and ESR spectroscopies.The investigated corroles are represented as（Tp-OCH3PC）Cu and（To,p-（OCH3）2PC）Cu,where Tp-OCH3PC and To,p-（OCH3）2PC are the trianion of the 5,10,15-tri（4-methoxyphenyl）corrole and 5,10,15-tri（2,4-dimethoxyphenyl）corrole,respectively.Neutral copper complexes expected to contain the low spin d8 Cu（Ⅲ） central ions exhibit no ESR signal in the solid state and in CH2Cl2 or DMF solutions,thin-layer UV-Visible spectroelectrochemistry result indicates that the first reduction of Cu（Ⅲ） corroles leads to formation of a Cu（Ⅱ） species in non-aqueous media while the first oxidation of the same compound is corrole ring-centered to give a Cu（Ⅲ） π-cation radical under the same solution conditions.Effects of the electron-donating OCH3 substituents and the solvent on the UV-Vis spectra and redox potentials of the copper corrole were discussed.