金属萘酞菁配合物的光敏反应及机理

Twelve metal naphthalocyanine（MNc）complexes are synthesized by Templet-Reaction Method at the present of 1,8-diazabicyclo[5,4,0]undec-7-ene). Including three kinds: no substituent kind: ZnNc, Nc=C48H20N8; homo-substituent kind: ZnNcBr4, ZnNcS4 (S: -SO3H), CoNcS2 and 5,9,14,28,23,27,32,36-octaalkoxy metal naphthalocyanines MNc(OR)8, including M=Zn: R=C4H9, C8H17, C12H25, and M=Zn, Ni, Cu, Co, R=C4H9; mixed substituent kind: ZnNc(OC8H17)8S4 and ZnNc(OC12H25)8S6. And characterized by IR, UV¤Vis, MNR, XPS, MS, ICP and elemental analysis. The thermal analysis for the three kinds of complexes is done systematically with TG, TG-DTA and TG-IR, the thermal decomposition mechanisms are proposed. The excited-singlet-state photophysical parameters of the different kinds of metal naphthalocyanines are determined, those are the excited singlet state's lifetime and dynamic decay parameter. And fluorescent photon yield and fluorescent decay parameter are also determined. The effect of central metal ions, substituents, solvents and temperature on the photophysical parameters above-mentioned is learned as well. The excited-triplet-state lifetime, triplet-triplet three-dimensional time resolved absorption spectra of the series of metal naphthalocyanines are obtained by laser flash photolysis. The influence of the central ions and substituents of the complexes on the properties of the excited-triplet-state is investigated. The results indicated that the substituents play an important role in increasing the triplet-triplet absorption intensity of zinc naphthalocyanines. The abilities of a series metal naphthalocyanines for photo-generating singlet oxygen (1O2) are studied. The influence of central ions, substituents, and the equilibrium between monomer and aggregate on the abilities of photo-generating 1O2 is investigated. The mechanism of photosensitive reaction is discussed. And it is proposed that the energy transfers not only from the first excited triplet state to ground state oxygen, which is ordinarily known, but also from higher excited triplet state to ground state oxygen in the photosensitive reaction of producing 1O2 of zinc naphthalocyanines.

拟通过模板反应合成一系列组成确定的金属萘酞菁新物种，研究其光敏反应及其机理，包括稳态与非稳态谱学性质、在一定波光激发下三重态寿期、量子产额及光敏化产生单重态１Ｏ２或超氧负离子Ｏ１２能力和其它光学性质等，从而揭示组成、结构与光敏性的关系。这即可以丰富金属萘酞菁配合物的静、动态光化学内容，又可为开拓其应用奠定基础。