Synthesis and Photochemistry of Amido-Linked, Peripherally-Molybdenated Tetraphenylporphyrins

Autor: Natalie M. Rowley, Godfrey S. Beddard, T. A. Hamor, Jon A. McCleverty, Peter R. Ashton, Neil Spencer, Eric J. L. McInnes, Stefan S. Kurek, Lesley J. Yellowlees, Nigel T. H. White, Chris Jones, Timothy M. Feehan, Nicholas N. Payne
Rok vydání: 1996
Předmět:
Zdroj: Inorganic Chemistry. 35:7526-7534
ISSN: 1520-510X
0020-1669
DOI: 10.1021/ic9509342
Popis: The para, meta, and ortho peripherally-molybdenated tetraphenylporphyrin complexes [5-{[Mo(NO)Tp*Cl]NHC6H4}-10,15,20-Ph3porphH2] [1−3, respectively; Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate; Ph3porphH2 = triphenylporphyrin] have been prepared by reaction of the corresponding 5-(aminophenyl)-10,15,20-triphenylporphyrin derivative with [Mo(NO)Tp*Cl2]. Cyclic voltammetry shows that most of these complexes undergo two oxidation processes (associated with the porphyrin) and three reduction processes (two associated with the porphyrin, and one with the molybdenum fragment). The redox potentials of the molybdenum fragment are little influenced by the presence of the macrocyclic ring, and vice versa. The ΔG° values for charge separation in 1−3 are close to 0 eV. Photochemical measurements have been made on 1−3, and they were all found to undergo photoinduced intramolecular electron transfer from the excited singlet state of the porphyrin macrocycle to the molybdenum moiety, yielding charge-separated states...
Databáze: OpenAIRE