取代卟啉锌与含氮碱轴向配位反应的光谱性质及平衡常数  

Spectral Properties and Equilibrium Constants of Axial Coordination Reactions between Substituted Zinc Porphyrins and Nitrogenous Bases

作　　者：侯月平 王丽萍 房媛媛[2] 欧忠平[2] Hou Yueping;Wang Liping;Fang Yuanyuan;Ou Zhongping(Department of Chemical Engineering,Zhenjicutg Vocational,Technical College,Zhenjiang,Jiangsu 212003,China;School of Chemistry and Chemical Engineering,Jiangsu University,Zhenjiang,Jiangsu 212013,China)

机构地区：[1]镇江高等职业技术学校化工系,江苏镇江212003 [2]江苏大学化学化工学院,江苏镇江212013

出　　处：《化学世界》2020年第12期805-810,共6页Chemical World

基　　金：国家自然科学基金(No.21501070);江苏大学高级人才基金(No.15JDG131);中国博士后科学基金(No.2019M661735)资助项目。

摘　　要：采用光谱法研究了5,10,15,20-四-(2,6-二甲氧苯基)卟啉锌[(TDMPP)Zn]和2,3,7,8,12,13,17,18-八溴-5,10,15,20-四-(2,6-二甲氧基-4-溴苯基)卟啉锌[(OBTDMBPP)Zn]在二氯甲烷溶剂中,与3-氯吡啶(3-CPy)、3-乙酰基吡啶(3-APy)、吡啶(Py)、4-甲基吡啶(4-Pic)、哌啶(Pip)和2-甲基吡啶(2-Pic)等6种含氮碱发生轴向配位反应的光谱性质,并测定了反应的平衡常数。实验结果表明,每种取代卟啉锌均可以与不同的含氮碱发生轴向配位反应导致卟啉的光谱吸收峰发生较大的红移。卟啉锌大环上的取代基以及含氮碱的结构和性质对轴向配位反应有较大的影响。与(TDMPP)Zn相比,大环上具有强吸电子溴取代基的(OBTDMBPP)Zn具有较强的配位能力和较大的平衡常数。6种含氮碱的配位反应能力为:Pip>4-Pic>Py>3-APy>3-CPy>2-Pic。The spectral properties of axial coordination reactions of 5,10,15,20-tetra(2,6-dimethoxyphenyl)porphyrin zinc[(TDMPP)Zn]and 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetra(2,6-dimethoxy-4-bromophenyl)porphyrin zinc[(OBTDMBPP)Zn]with 6 nitrogenous bases,such as 3-chloropyridine(3-CPy),3-acetylpyridine(3-APy),pyridine(Py),4-picoline(4-Pic),piperidine(Pip)and 2-picoline(2-Pic)in CH2Cl2 were examined by spectral method and the equilibrium constant was determined.The results showed that each substituted porphyrin zinc can react with nitrogenous base to form a five-coordinate derivative,resulting in a red-shift of Soret and Q bands.The substituents on the porphyrin macrocycle as well as the structure and properties of nitrogenous base have a significant effect on the axial coordination reactions.In comparison with(TDMPP)Zn,(OBTDMBPP)Zn containing strong electron-withdrawing Br groups has a strong reactivity with a large equilibrium constant.The coordinate reaction abilities of 6 nitrogenous bases follow the order of Pip>4-Pic>Py>3-APy>3-CPy>2-Pic.

关 键 词：取代卟啉锌 含氮碱 轴向配位反应 光谱性质 平衡常数 

分 类 号：O657.3[理学—分析化学]