两种甲氧基苯基咔咯铜配合物的合成及光谱性质

摘要

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.