新型卟啉-酞菁二元分子内光物理过程的研究  

The Photophysical Process of A New Kind of Porohyrin-Phthalocyanine Heterodimer

作　　者：李希友[1] 田宏健[1] 周庆复[1] 许慧君[1] 

机构地区：[1]中国科学院感光化学研究所,北京100101

出　　处：《物理化学学报》1997年第1期11-15,共5页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金

摘　　要：合成了以哌嗪连接的含卟啉-酞菁的双发色团分子，测定了它的吸收光谱，荧光光谱和荧光寿命．并计算了在不同溶剂中两发色团之间的能量传递效率EnT和电子转移效率ET．结果表明：在非极性溶剂苯中，两发色团之间的光物理过程以激发态单线态能基传递为主（EnT80％）．而在极性溶剂DMF中，则以电子转移为主（ET69.8％）该二元化合物在DMF中的电子转移效率明显高于我们以前合成的以氧或柔性链连接的二元化合物．这可能是由于在DMF中，哌嗪以船式构象存在，两个发包团呈较固定的，相互平行的面对面构象．从CPK分子模型可以算出卟啉环和酞菁环中心至中心的距离为3.56A.Intramolecular energy-transfer and electron-transfer of porphyrin-phthalocyanine heterodimer, linked by piperazine, were investigated by absorption and fluorescencc spectroscopy.The efficiency of energy transfer(EnT) and electron transfer (ET) were calculated. The results indicate that: In benzene, the main photophysical process is excited singlet-singlet energy transfer, while in DMF photoinduced electron transfer Predominant. The ET of this heterodimer in DMF is bigge1i than that of porphyrin-phthalocyanine heterodimers linked by oxygen or flexible chains. This Inay be ascribed to the 'boat-form' conformation of piperazine, According to the CPK molecular model, porphyrin and phthalocyanine are held together in a face to face way, and the center to center distance between two macrorings is about 3.56A. It is suggested that, conformational changes from 'chair form' to 'boat form' occurred subsequent to optical excitation in DMF.

关 键 词：二元化合物 能量传递 光诱导电子转移 卟啉 酞菁 

分 类 号：O626.13[理学—有机化学]