物理化学学报 >> 1996, Vol. 12 >> Issue (01): 44-48.doi: 10.3866/PKU.WHXB19960110

研究论文 上一篇    下一篇

酞菁-卟啉超分子的形成及光致电子转移过程

田宏健,周庆复,沈淑引,许慧君   

  1. 中国科学院感光化学研究所,北京 100101
  • 收稿日期:1994-12-02 修回日期:1995-07-06 发布日期:1996-01-15
  • 通讯作者: 田宏健

The Studies of the Supramolecular System of Porphyrin-Phthalocyanine Formed by Molecular Self-assembly and Its Photoinduced Electron Transfer Processes

Tian Hong-Jian,Zhou Qing-Fu,Shen Shu-Yin,Xu Hui-Jun   

  1. Institute of Photographic Chemistry,Chinese Academy of Sciences,P.O.Box,Beijing 100101
  • Received:1994-12-02 Revised:1995-07-06 Published:1996-01-15
  • Contact: Tian Hong-Jian

摘要:

用吸收光谱的方法研究了溶液中四-[(4′-N,N,N-三甲基)-苯氧基]-酞菁季铵碘盐及它的锌络合物与四-(4′-磺酸基苯基)卟啉及它的锌络合物通过分子间自组装形成的新一类超分子排列的杂聚体,用Job氏光度滴定的方法确定了它们的组成,为面对面的杂二聚体或三明治式的杂三聚体超分子排列.证实卟啉和酞菁的中心络合金属与溶剂分子之间的轴向配位是决定了卟啉-酞菁杂聚体的组成.发现在超分子体系中卟啉与酞菁能互相猝灭各自的荧光,用纳秒级的激光闪光光解技术观察到卟啉的正离子在600-650nm和酞菁负离子自由基在550-600nm的瞬态吸收光谱.结果表明在超分子体系中存在分子间的光诱导电子转移过程.

关键词: 超分子体系, 分子自组装, 酞菁, 卟啉, 光致电子转移

Abstract:

The supramolecular assemblies consisting of metal-free tetra(N-trimethylaminobenoxy) phthalocyanate (H2TAPc) and its zinc complex (ZnTAPc) as well as metal-free tetra (4-sulfonatophyenyl) porphyrin (H2TSPP) and its zinc complex (ZnTSPP) in solution were studied by absorption spectroscopy. The stoichiometries of the hetero-aggregates were ascertained by Job’s photometric titration plots, indicating that the aggregates were either face to face heterodimers or sandwich structure heterotrimers. The composition of the hetero-aggregates are controlled by the affinity of the central metal ion of each chromophore for axially bound coordinating solvent molecules. The fluorescence of porphyrin and phthalocyanine in the supramolecular system are quenched by each other. The transient absorption spetra of cationic porphyrin radical (around 600-650nm region) and anionic phthalocyanine radical(around 550-600nm) were observed by nanosecond laser photolysis. The results indicated that intermolecular photoinduced electron transfer process from excited triplet state between the porphyrin and the phthalocyanine occured in the supramolecular system.

Key words: Supramolecular system, Molecular self-assembly, Phthalocyanine, Porphyrin, Photoinduced electron transfer