Abstract
Phenanthroline-fused unsymmetrical phthalocyanine (2-H) and its zinc complex (2-Zn) were treated with Re(CO)5Cl to give rhenium(I) tricarbonyl chloride chelates 1-H and 1-Zn respectively, which represent the first example of phthalocyanines with peripherally appended rhenium(I) complex units. The molecular structure of 1-Zn was determined by single crystal X-ray diffraction analysis. The electronic absorption, magnetic circular dichroism, and steady-state and time-resolved fluorescence spectra and the singlet oxygen (1O2) generation efficiencies of 1-H and 1-Zn were measured and compared with those of phenanthroline-fused unsymmetrical phthalocyanines 2-H and 2-Zn, and the corresponding symmetrical phthalocyanines 3-H and 3-Zn as well. The electrochemical properties of 1-H and 1-Zn were also studied by cyclic voltammetry and compared with those of 2-H and 2-Zn. The effects of unsymmetrical phenanthroline fusing and rhenium(I) chelating on the photophysical and electrochemical behaviors of phthalocyanines were highlighted based on the above investigations.
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