金属卟啉－甲基紫精二连体配合物的合成及其光化学行为

PREPARATION AND PHOTOCHEMICAL BEHAVIOR OF COVALENTLY LINKED METALLOPORPHYRIN METHYL VIOLOGEN COMPLEXES

本文合成了四（对－氯代甲基）苯基－甲基紫精卟啉及其Ｚｎ、Ｃｏ、Ｍｎ配合物，用元素分析、红外光谱和紫外可见光谱进行了表征．研究了它们的光化学性质．结果表明．在ＴＥＯＡ中光照使Ｍ·ＴＣＭＰＰ—ｍｖ￣２＋发生了分子内从卟啉到甲基紫精的电子迁移反应．在ＺｎＴＣＭＰＰ－ｍｖ￣２＋／ＴＥＯＡ／ＤＭＳＯ—Ｈ２Ｏ体系中可发生光敏化还原ｍｖ２＋反应，生成较稳定的ｍｖ＋．在Ｍｎ（Ⅲ）ＴＣＭＰＰ－ｍｖ２＋／ＣＨ３ＯＨ／Ｈ２Ｏ体系中可发生光助氧化甲醇反应，并检出了氧化产物甲醛．

The covalently linked 5, 10, 15, 20-tetra(p-chloromcthyl) phenyl porphyrinmethylviologen zinc, manganese and cobalt complexes(abb:MTCMPP-mv2+) were synthesizedand characterized by clemental analysis,UV absorphon spectra and IR spectra.Thephotochemical behavior of MTCMPP-mv2+ was steadied.In deaceratcd solution containingtriethanolaminc(TEOA),the intramelocular electron transfer from porphyrin to viofogen takesplace under steady state irradiation.In the deaerated soluhon of MTCMPP-mv2+/TEOA / DMSO-H2O system photosensitized reduchon takes place and reduced methylviologen was formed. In deaerated solution of M(Ⅲ)TCMPP-mv2+/ CH3OH / H2O systemphotooxidation reaction of methanol takes place with a product methanal formed.