卟啉多枝分子合成与分子内能量转移、双光子吸收性能研究  

Synthesis of Multibranched Porphyrins with Two-photon Absorption and Intramolecular Energy Transfer

作　　者：王保柱[1] 王筱梅[1] 蒋宛莉[2] 王正平[2] 杨平[1] 胡大伟[2] 闫永莉[3] 钱世雄[3] 

机构地区：[1]苏州大学材料科学与工程学院化学化工学院,苏州215021 [2]山东大学晶体材料国家重点实验室,济南250100 [3]复旦大学物理系,上海200433

出　　处：《化学学报》2007年第10期887-893,共7页Acta Chimica Sinica

基　　金：国家自然科学基金(Nos.50273024;50673070;20543001);全国优秀博士论文作者专项基金(Nos.FANEDD;GrantNo.200333)资助项目.

摘　　要：以三苯胺或硝基苯为端基,合成了三个卟啉多枝分子:5-(4-硝基苯甲酰氧基)苯基-10,15,20-三-(4-溴苯基)卟啉(TPP-NO2)、5-(4-硝基苯甲酰氧基)苯基-10,15,20-三-(4-二苯胺基-1-苯乙烯基)苯基卟啉(TPP-X3)和5,10,15,20-四-(4-二苯胺基-1-苯乙烯基)苯基卟啉(TPP-X4),进行了红外光谱、核磁共振光谱和质谱表征.比较研究了分子“枝”、“核”不同键合方式与不同对称结构对分子的线性光谱、非线性光谱以及分子内能量转移行为的影响.在钛宝石激光器(800nm)和Nd∶YAG倍频光(532nm)泵浦下,样品溶液均发出卟啉环特有的红色荧光——前者系双光子吸收机制“上转换”荧光,后者则为双光子吸收与分子内能量转移机制“下转换”荧光.飞秒Z-scan技术测得样品双光子吸收截面最大可达130GM,与四苯基卟啉(TPP)同等测试条件下的双光子吸收截面相比增大了两个数量级.Three new multibranched porphyrins： 5-（4-nitrobenzoxy）-phenyl-10,15,20-tris-（4-bromo- phenyl）-porphyrin （TPP-NO2）, 5-（4-nitrobenzoxy）-phenyl- 10,15,20-tris-（4-N,N-diphenylamino-styryl）- phenyl-porphyrin （TPP-X3） and 5,10,15,20-tetra-（4-N,N-diphenylamino-styryl）-phenyl-porphyrin （TPP-X4） were synthesized and characterized by IR, 1H NMR and MS measurements, respectively. Pumped by 800 nm and 532 nm laser pulses, respectively, the sample solution could emit strong up- and down-conversion fluorescence, wherein the former cound be interpreted by two-photon absorption （TPA） mechanism and the latter was attributed to two-photon absorption and intramolecular energy transfer. TPA cross-section was measured by femtosecond Z-scan technique at 800 nm Ti ＂ sapphire laser. It was found that TPA cross-section of multibranched porphyrins was enhanced by larger dipole moment difference between the ground- and the excited-state, that is, I6｜△μge｜ value, and stronger conjugation effect, that is, π-π conjugation, between porphyrin ＂core＂ and branches linked to the porphyrin periphery.

关 键 词：卟啉多枝分子 双光子吸收 双光子荧光 分子内能量转移 

分 类 号：O626[理学—有机化学]