物理化学学报 >> 1996, Vol. 12 >> Issue (06): 491-495.doi: 10.3866/PKU.WHXB19960603

研究论文 上一篇    下一篇

空心酞菁光物理性质的取代基效应

刘剑波,赵福群,赵瑜,张复实,唐应武,宋心琦,周福添   

  1. 清华大学化学系,北京 100084|香港理工大学应用生物及化学科技学系
  • 收稿日期:1995-09-24 修回日期:1996-01-22 发布日期:1996-06-15
  • 通讯作者: 刘剑波

Substituent Dependence of Photophysical Properties for Free-base Phthalocyanines

Liu Jian-Bo,Zhao Fu-Qun,Zhao Yu,Zhang Fu-Shi,Tang Ying-Wu,Song Xin-Qi,Chau Footim   

  1. Department of Chemistry,Tsinghua University,Beijing 100084|Department of Applied Biology and Chemical Technology,Hong Kong Polytechnic University,Hong Kong
  • Received:1995-09-24 Revised:1996-01-22 Published:1996-06-15
  • Contact: Liu Jian-Bo

摘要:

合成了一系列可溶性的2,9,16,23-四取代的空心酞菁,并研究了其光物理性质,实验表明,烷基、烷氧基、芳氧基取代空心酞菁的最低电子跃迁能和最低激发单重态能量与Hammett间位取代基常数线性相关.而强吸电子基如硝基和强给电子基如氨基取代则会诱导分子内电荷转移和使酞菁聚集,导致吸收光谱畸变和激发态量子产率下降.但取代基对酞菁的振动能级没有影响.

关键词: 酞菁, 电荷转移, 聚集体, Hammett相关性

Abstract:

 A series of soluble 2,9,16,23-tetrasubstituted free-base phthalocyanines were synthesized and studied spectroscopically. The lowest electronic transition energy and the lowest excited singlet state energy of the phthalocyanines substituted with alkyl, alkoxy and aryloxy groups can be correlated well with the Hammett's meta-directing group effect. While the strong electron-withdrawing group (nitro) and the strong electron-donating group (amino) may induce intense intramolecular charge-transfer which results in the formation of aggregates, marked distortion of the absorption spectra and quenching of the excited states. However, all the substituents have less influence on the vibrational level.

Key words: Phthalocyanine, Charge-transfer, Aggregate, Hammett correlation