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化学学报
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化学学报 ›› 2007, Vol. 65 ›› Issue (10): 887-893. 上一篇    下一篇

研究论文

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

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   

  1. (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)
  • 投稿日期:2006-10-09 修回日期:2007-01-08 发布日期:2007-05-28
  • 通讯作者: 王筱梅

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

WANG Bao-Zhu1; WANG Xiao-Mei*,1; JIANG Wan-Li2; WANG Zheng-Ping2; YANG Ping1; HU Da-Wei2; YAN Yong-Li3; QIAN Shi-Xiong3   

  1. (1 Institute of Material Engineering, Department of Chemistry, Suzhou University, Suzhou 215021)
    (2 State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100)
    (3 Department of Physics, Fudan University, Shanghai 200433)
  • Received:2006-10-09 Revised:2007-01-08 Published:2007-05-28
  • Contact: WANG Xiao-Mei

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被引次数

20 | 1

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(800 nm)和Nd∶YAG倍频光(532 nm)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130 GM, 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.

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

Three new multibranched porphyrins: 5-(4-nitrobenzoxy)-phenyl-10,15,20-tris-(4-bromophenyl)-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, |Δμge| value, and stronger conjugation effect, that is, π-π conjugation, between porphyrin “core” and branches linked to the porphyrin periphery.

Key words: multibranched porphyrin, two-photon absorption, two-photon fluorescence, intramolecular energy transfer