四(α-萘基)四苯并卟啉钴配合物的光谱电化学性质

Spectroelectrochemical Characteristics of Tetra ( α naphythyl) Tetrabenzoporphyrin Cobalt Complex

Ｋｅｌｅｔ等［１］研究ＣｏＴＭＡＰＩ催化水制取氢气的反应时指出，活性中心是一价钴卟啉．曹锡章等［２］研究钴卟啉催化ＣＯ２电化学还原时指出，活性中心也是一价钴卟啉．然而，不稳定价态的金属卟啉配合物的制备和性质研究较为困难．光谱电化学的迅速发展为不稳定价...

The electrochemical and spectroelectrochemical behaviour of tetra ( α naphythyl) tetrabenzoporphyrin cobalt complex, TNTBPCo, was studied by cyclic voltammetry, in situ FTIR and in situ UV Vis spectroelectrochemistry. The different oxidation states of the complex were obtained by controlling potential electrolysis at different potentials, and this electronic spectra and molecular vibration spectra were studied. The first and second redox processes of TNTBPCo(Ⅱ) correspond to the centre metal cobalt(Ⅱ) to form TNTBPCo(Ⅲ) + or TNTBPCo(Ⅰ) -. The third reduction step is the addition of one electron to the porphyrin ring. The Soret band of TNTBPCo moves to low wavelength as the oxidation state of the complex decreases. The oxidation state sensitive bands of TNTBPCo were found to be in the 1 660, 1 476, 1 142, 924 and 998 cm -1 and these bands shift to low frequency as the oxidation state of the centre metal decreases.