Effects of an Axial Ligand on the Reduction Potential, Proton Dissociation, and Fluorescence Quantum Yield of Hydroxo(porphyrinato)antimony(V) Complexes
Effects of an Axial Ligand on the Reduction Potential, Proton Dissociation, and Fluorescence Quantum Yield of Hydroxo(porphyrinato)antimony(V) Complexes
复制标题
轴向配体对羟基(卟啉)锑(V)络合物还原电位、质子解离和荧光量子产率的影响
DOI：
10.1246/bcsj.75.1577
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发表时间：
2002
影响因子：
4
通讯作者：
M. Yasuda
中科院分区：
文献类型：
--
作者：
T. Shiragami;Y. Andou;Yuichiro Hamasuna;Futoshi Yamaguchi;K. Shima;M. Yasuda
研究了取代基对芳氧（羟基）四芳基卟啉锑（V）配合物的还原电位（E1/2 red）、氢氧配体的质子离解常数（Ka）和荧光量子产率（Φ）的影响。轴向芳氧配体上的取代基对E1/2 red和Ka值有影响，而卟啉环上的取代基对E1/2 red和Ka值影响不大。由于四芳基卟啉锑（V）配合物的E1/2 red比其它金属卟啉配合物的E1/2 red高，推测金属轨道对配合物的LUMO能级有很大贡献，这可能与配合物的E1/2 red和Ka值有关.因此，轴向芳氧基配体对配合物E1/2 red和Ka值的取代基效应是由于锑离子的电子密度影响了配合物的LUMO能级.此外，卟啉部分的Φ取决于轴向芳氧基配体的氧化电位和所用溶剂的极性。荧光...
The substituent effects on the reduction potentials (E1/2red), the proton dissociation constants of a hydroxo ligand (Ka), and the fluorescence quantum yields (Φ) in aryloxo(hydroxo)tetraarylporphyrinatoantimony(V) complexes were investigated. The E1/2red and Ka values were affected by substituents in the axial aryloxo ligand but, little affected by substituents in the porphyrin ring. Since E1/2red of tetraarylporphyrinatoantimony(V) complexes were higher than those of other metal-porphyrin complexes, it was suggested that the metal orbital greatly contributed to the LUMO level of the complex which can be related to the E1/2red and Ka values. Therefore, the substituent effects of the axial aryloxo ligand on the E1/2red and Ka values were attributed to the electron density of the antimony ion, which affected the LUMO level of the complexes. Moreover, the Φ of the porphyrin moiety depended on both the oxidation potential of the axial aryloxo ligands and the polarity of the solvent used. The fluorescences of...