系列二肽链键联的卟啉-蒽醌及其金属配合物的微波合成及电子转移性质  

Microwave Synthesis and Electron Transfer Properties of a Series of New Porphyrin-anthraquinone Hybrids with Dipeptide Link and Their Metal Complexes

作　　者：陈年友[1] 赵胜芳 董甲庆[3] 田又平 李早英[3] 

机构地区：[1]黄冈师范学院化学工程学院 [2]化学与生命科学学院,黄冈438000 [3]武汉大学化学与分子科学学院,武汉430072

出　　处：《高等学校化学学报》2011年第7期1466-1471,共6页Chemical Journal of Chinese Universities

基　　金：湖北省自然科学基金面上项目(批准号:2007ABA064);湖北省教育厅重大项目(批准号:Z200727001)资助

摘　　要：利用微波技术合成了系列二肽链键联的卟啉-蒽醌及其金属配合物,并通过UV-Vis,IR,1H NMR及元素分析确证了化合物的结构,用荧光光谱法探讨了目标化合物分子内电子转移性质(IETP)和结构对IETP的影响.实验结果显示:柔性的二肽链使卟啉环和蒽醌环有可能形成面-面重叠构象,利于卟啉环的激发态π电子直接向蒽醌转移,发生荧光猝灭;过渡金属配合物中Zn2+的d轨道的重原子效应所引起电子自旋-轨函偶合作用,增大了系间窜跃几率,导致卟啉-蒽醌(P-AQ)的荧光猝灭;中位苯环对位上连有不同取代基R(a.R=H,b.R=Cl,c.R=OCH3)时最大荧光发射波长顺序为λc>λb>λa,荧光发射强度顺序为Ic>Ia>Ib.This paper reports the microwave synthesis of a series of new porphyrin-anthraquinone hybrids with dipeptide link and their metal complexes.The new compounds were confirmed by 1H NMR,IR,UV-Vis spectra and elementa1 analysis.The intramolecule electron transfer property（IETP） and the influence of structure for IETP of these compounds were studied by fluorescence spectra.The results show that the flexible dipeptide linker may make the porphyrin ring and anthraquinone ring form face to face overlapping,which is good for the electron transfer in excitation state from the porphyrin ring to anthraquinone ring so the fluorescence quench occurred,heavy atom effect in transition state complex causes spin-orbit coupling effect,which can increae the intersystem crossing rate,so the fluorescence of porphyrin-anthraquinone（P-AQ） decreased.When the phenyl ring has different substitute groups on the p-postion（a.R=H,b.R=Cl,c.R=OCH3）,the excitation wavelength and the strength are in the orders： λcλbλa,I cIaIb,respectively.

关 键 词：卟啉-蒽醌 二肽键联 金属卟啉 微波合成 分子内电子转移 

分 类 号：O614[理学—无机化学]