Synthesis and Electrochemistry of Aryl-Substituted Tripyrrinone Copper Complexes. Comparison of Redox Properties to Structurally Related Porphyrins and Corroles  

作　　者：Wenda Wang Zhongping Ou Lina Ye Yuanyuan Fang Songlin Xue Yang Song Karl M. Kadish 

机构地区：[1]School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, China [2]Department of Chemistry, University of Houston, Houston, TX 77204-5003, USA

出　　处：《Chinese Journal of Chemistry》2016年第10期962-968,共7页中国化学（英文版）

基　　金：Support from the National Natural Science Foundation of China （Nos. 21501070, 21071067）, Jiangsu University Foundation （Nos. 05JDG051, 15JDG131） and the Robert A. Welch Foundation （K.M.K., E-680） are gratefully acknowledged.

摘　　要：Four awl-substituted tripyrrinone copper（II） complexes were synthesized and characterized as to their electro- chemical and spectroelectrochemical properties. The examined compounds are represented as （YPh）3TPO2Cu, where TPO2 is a dianion of the tripyrrinone and Y is a CH3O, CH3, H or CI substituent on the para-position of each phenyl ring of the compound. The neutral compounds are ESR active and show a typical d9 Cu（II） signal in frozen CH2C12 solution. Each Cu（II） compound undergoes three reductions between -0.61 and -1.90 V and two oxidations between 1.00 and 1.24 V in CH2Cl2 containing 0.1 mol/L tetra-n-butylammonium perchlorate. The potentials for oxidation are similar to those of copper tetraarylporphyrins but the reduction potentials are positively shifted as compared to the corresponding tetraarylporphyrins. Thus, the potential difference between the first one-electron oxidation and first one-electron reduction （the HOMO-LUMO gap） of （YPh）3TPO2Cu, which ranges from 1.68 to 1.75 V, is similar to that of copper corroles （1.73-1.85 V）, but smaller than the separation of 2.30-2.37 V for the copper tetraarylporphyrins under the same solution conditions.Four awl-substituted tripyrrinone copper（II） complexes were synthesized and characterized as to their electro- chemical and spectroelectrochemical properties. The examined compounds are represented as （YPh）3TPO2Cu, where TPO2 is a dianion of the tripyrrinone and Y is a CH3O, CH3, H or CI substituent on the para-position of each phenyl ring of the compound. The neutral compounds are ESR active and show a typical d9 Cu（II） signal in frozen CH2C12 solution. Each Cu（II） compound undergoes three reductions between -0.61 and -1.90 V and two oxidations between 1.00 and 1.24 V in CH2Cl2 containing 0.1 mol/L tetra-n-butylammonium perchlorate. The potentials for oxidation are similar to those of copper tetraarylporphyrins but the reduction potentials are positively shifted as compared to the corresponding tetraarylporphyrins. Thus, the potential difference between the first one-electron oxidation and first one-electron reduction （the HOMO-LUMO gap） of （YPh）3TPO2Cu, which ranges from 1.68 to 1.75 V, is similar to that of copper corroles （1.73-1.85 V）, but smaller than the separation of 2.30-2.37 V for the copper tetraarylporphyrins under the same solution conditions.

关 键 词：SYNTHESIS PORPHYRINOIDS ELECTROCHEMISTRY copper tripyrrinones substituent effect 

分 类 号：O641.4[理学—物理化学] TG139.7[理学—化学]