Local Structure of Nitrogen Atoms in a Porphine Ring of meso-Phenyl Substituted Porphyrin with an Electron-Withdrawing Group Using X-ray Photoelectron Spectroscopy and X-ray Absorption Spectroscopy

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  • YAMASHIGE Hisao
    Department of Chemistry, Faculty of Science, Fukuoka University
  • MATSUO Shuji
    Advanced Materials Institute, Fukuoka University
  • KURISAKI Tsutomu
    Department of Chemistry, Faculty of Science, Fukuoka University
  • PERERA Rupert C. C.
    Center for X-Ray Optics, Lawrence Berkeley National Laboratory
  • WAKITA Hisanobu
    Department of Chemistry, Faculty of Science, Fukuoka University Advanced Materials Institute, Fukuoka University

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Abstract

This study investigated the protonation of nitrogen atoms in porphyrins with meso-phenyl p-substituted by an electron-withdrawing group using N 1s X-ray photoelectron spectroscopy (XPS), the N K X-ray absorption near-edge structure (XANES), and the discrete variational (DV)-Xα molecular orbital (MO) method. Both tetraphenylporphyrin (TPP) and tetrakis(p-sulfonatophenyl)porphyrin (TSPP) have a single structure: the former has two protonated and two non-protonated N atoms in the porphine ring; the latter has four protonated N atoms in the porphine ring. In contrast, a combination of XPS, XANES, and DV-Xα MO calculations shows that tetrakis(p-carboxyphenyl)porphyrin (TCPP) has a dual structure: one structure has two protonated and two non-protonated N atoms; the other has four protonated N atoms. Furthermore, this result was also considered based on the protonation constants of N atoms in the porphyrins. The correlation between the strength of electron-withdrawing groups and protonation to N atoms in porphyrins can be described using the spectral patterns of the N 1s XPS and N K XANES spectra.

Journal

  • Analytical Sciences

    Analytical Sciences 21 (6), 635-639, 2005

    The Japan Society for Analytical Chemistry

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