四取代酞菁金属配合物的紫外-可见吸收光谱和荧光发射光谱研究

报道了16种含哌嗪或含哌啶四取代酞菁金属配合物{R4PcM，R=2-4-(2-磺基乙基)哌嗪-1-基]乙氧基(SPEO—)、2-(哌啶-1-基)乙氧基(PEO—);取代位置分别在α位和β位;M=Zn(Ⅱ)，Ni(Ⅱ)，Co(Ⅱ)， Cu(Ⅱ)}的UV-Vis吸收光谱和荧光发射光谱的测定，探讨了中心金属离子、取代基种类及其取代位置、溶剂等因素对酞菁金属配合物UV-Vis吸收光谱和荧光发射光谱性质的影响。结果表明:R4PcM的Q带λ_max落在681～718 nm范围内，与相同中心金属离子的无取代酞菁金属配合物(669～671 nm)比较都发生了不同程度的红移，荧光发射光谱与UV-Vis吸收光谱呈镜像关系，特别的是两种β位取代中心金属离子为Zn(Ⅱ)的酞菁金属配合物β-(SPEO)₄PcZn，β-(PEO)₄PcZn]具有极高的摩尔消光系数、较大的荧光量子产率和较长的荧光寿命，有望开发成新型的光动力诊疗用光敏剂。

Study on UV-Vis Absorption Spectra and Fluorescence Emission Spectra of Sixteen Tetra-Substituted Metallophthalocyanine Complexes

The UV-Visible absorption spectra and the fluorescence emission spectra of sixteen tetra-substituted metallo-phthalocyanine complexes {R4PcM, where R=2-［4-(2-sulfonic ethyl)piperazin-1-］ ethoxyl (SPEO—), 2-(piperidin-1-yl)ethoxyl (PEO—); substitution position at α-position and β-position of phthalocyanine ring; M=Zn(Ⅱ), Ni(Ⅱ), Co(Ⅱ)and Cu(Ⅱ)} were measured. The influence of different central ion, substituted group and its position, as well as different solvent on the Q-band of phthalocyanine complex in its UV-Vis absorption spectra was investigated. The influence of different central ion, substituted group and its position on the fluorescence emission spectra was discussed. Some properties of the UV-Vis absorption spectra such as the maximum absorption wavelength (λmax)of Q-band and its molar extinction coefficient (ε), and those of the fluorescence emission spectra such as fluorescence quantum yield (ΦF), fluorescence lifetime (τ) and excited state energy (Es)were studied. The results showed that the λmax of Q-band of all complexes were located at 681-718 nm, which had a distinct red shift in contrast with unsubstituted metallophthalocyanines (669-671 nm). All complexes of R4PcM possessed a very high molar extinction coefficient up to 105 L·mol－1·cm-1. And the UV-Vis absorption spectra and the fluorescence emission spectra of all complexes exhibited mirror shape concurrently. Two β-substituted zinc phthalocyanine complexes with formula β-(SPEO)4PcZn and β-(PEO)4PcZn possessed very high molar extinction coefficient, fluorescence quantum yield and fluorescence lifetime specially. Therefore, it is hoped that these two would be developing to be new photosensitizers for photodynamic therapy (PDT)and photodynamic diagnosis (PDD).