双卟啉的超共轭效应对其光谱行为的影响  

The Influence of Double-porphyrin Hyperconjugation on Luminescent Spectrum

作　　者：朱磊[1] 蒋宛莉[2] 倪媛[1] 王筱梅[1] 

机构地区：[1]苏州大学材料与化学学部,苏州215021 [2]山东大学晶体材料国家重点实验室,济南250100

出　　处：《信息记录材料》2009年第3期3-8,共6页Information Recording Materials

摘　　要：合成了2个双卟啉化合物(简称为(TPP)2p和(TPP)2n)和一个单卟啉化合物(简称TPPa),并进行了核磁共振表征。研究了卟啉环之间的超共轭效应对分子的单、双光子吸收行为的影响,经吸收光谱和荧光光谱证实,发现双卟啉(TPP)2p和(TPP)2n由于存在pπ共轭效应和σπ超共轭效应,使得双卟啉的吸收和荧光强度均比单卟啉TPPa要强得多。并计算三种卟啉在不同溶剂种光物理性质参数。Two new porphyrin derivatives, named （TPP） 2 - P and （TPP）2 - n, respectively, have been synthesized and characterized by 1^H NMR measurement. And their absorption and luminescent spectra have been measured in comparison with the reference, TPP-a. The hyperconjugation effects existing in （TPP）2-P and（TPP）2-n were found to affect absorption and fluorescence behaviors, resulting in their molar absorbance and emission intensity of（TPP）2-P and （TPP）2-n are twice more than the reference, TPP-a. In addition, the hyperconjugation has contribution to intermolecular charge-transfer and resulting increases the molecular transition moment from the excited- to the ground-state. Thus, （TPP）2 P and （TPP）2-n show larger molar absorbance （ε） and higher fluorescence intensity （I） than the reference, TPP-a, however, the fluorescence quantum yields of（TPP）2-P and（TPP）a-n are reduced. Since （TPP）2 P and （TPP）2-n possess symmetric conformation, relative to the reference （TPP-a）, their dipole moment differences （ge） between the excited,state and the ground-state show smaller, which confirms by Lippert equation.

关 键 词：卟啉衍生物 共轭效应 超共轭效应 

分 类 号：O64[理学—物理化学]