Analytical Sciences
Online ISSN : 1348-2246
Print ISSN : 0910-6340
ISSN-L : 0910-6340
Original Papers
Electronic Structure Analysis of Iron(III)-Porphyrin Complexes by X-ray Absorption Spectra at the C, N and Fe K-Edges
Hisao YAMASHIGEShuji MATSUOTsutomu KURISAKIRupert C. C. PERERAHisanobu WAKITA
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2005 年 21 巻 3 号 p. 309-314

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X-ray absorption near edge structure (XANES) measurements at the C, N, and Fe K absorption edges were performed for iron(III)-tetraphenylporphyrin (FeTPP), iron(III)-tetrakis(p-carboxyphenyl)porphyrin (FeTCPP), and iron(III)-tetrakis(p-sulfonatophenyl)porphyrin (FeTSPP). The spectral shapes differ in the Fe K XANES, but not in C and N K XANES among FeTPP, FeTCPP, and FeTSPP. Crosschecks of XANES data for C, N, and Fe K absorption edges in combination with discrete variational (DV)-Xα molecular orbital (MO) calculations indicate that each p-electron-withdrawing group on four meso-phenyl substitutes in an Fe(III)-porphyrin complex brings about a unique electron state through the complex because of the electron-withdrawal strength, itself. Consequently, they affect the positive charge of the center Fe(III) ion.
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© 2005 by The Japan Society for Analytical Chemistry
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