物理化学学报 >> 2010, Vol. 26 >> Issue (03): 701-706.doi: 10.3866/PKU.WHXB20100306

光化学与光谱 上一篇    下一篇

咪唑修饰的卟啉及其锌、铜配合物的合成和非线性光学性质

张晓红, 矫志, 闫伟伟, 阮文娟, 朱志昂   

  1. 南开大学化学学院, 天津 300071
  • 收稿日期:2009-11-06 修回日期:2009-12-23 发布日期:2010-03-03
  • 通讯作者: 阮文娟 E-mail:wjruan@nankai.edu.cn

Synthesis and Nonlinear Optical Properties of Porphyrin Modified by Imidazole and Its Zinc, Copper Complexes

ZHANG Xiao-Hong,  JIAO Zhi, YAN Wei-Wei, RUAN Wen-Juan, ZHU Zhi-Ang   

  1. College of Chemistry, Nankai University, Tianjin 300071, P. R. China
  • Received:2009-11-06 Revised:2009-12-23 Published:2010-03-03
  • Contact: RUAN Wen-Juan E-mail:wjruan@nankai.edu.cn

摘要:

合成了一种新型咪唑修饰的卟啉(1)及其锌、铜配合物(2、3). 通过核磁共振氢谱(1H NMR)、紫外-可见(UV-Vis)光谱、傅里叶变换红外(FT-IR)光谱、电喷雾质谱(ESI-MS)及元素分析等多种谱学方法对其结构进行表征. 卟啉环流效应对侧链咪唑芳环的影响导致咪唑环上三个氢原子的化学位移向高场移动, 且卟啉的紫外-可见光谱的Soret带发生裂分. 采用分子模拟方法得到的自由卟啉最低能量构象与光谱分析结果一致, 即侧链咪唑环位于卟啉环上方. 同时, 利用Z-扫描技术对卟啉及其锌、铜配合物的三阶非线性光学性质进行了研究, 结果表明: 卟啉及其锌、铜配合物均具有很强的反饱和吸收性质, 且铜卟啉的非线性光学性质强于锌卟啉的.

关键词: 光谱性质, Z-扫描技术, 金属卟啉, 非线性光学性质

Abstract:

A novel porphyrin (1) and its zinc, copper complexes (2, 3) were synthesized and characterized by proton nuclear magnetic resonance (1H NMR), ultraviolet-visible (UV-Vis) spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, electron spray ionization mass spectrometry (ESI-MS), and elemental analysis. The circumfluent effect of the porphyrin was exerted on the imidazole, which resulted in the chemical shifts of three hydrogen atoms moving upfield. The Soret band in the UV-Vis spectrum of the porphyrin was split because of this effect. The lowest energy conformation of the porphyrin obtained by simulated annealing coincided with the analysis of the spectrum where the imidazole was above the porphyrin. We also studied the third-order nonlinear optical properties of the porphyrin and its zinc, copper complexes using Z-scan techniques. We found that the porphyrin and its zinc, copper complexes all gave rise to a strong reverse saturable absorption and that the nonlinear optical property of the copper complex was stronger than that of the zinc complex.

Key words: Spectral property, Z-scan technique, Metalloporphyrin, Nonlinear optical property

MSC2000: 

  • O644