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
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- MATSUO Shuji
- Advanced Materials Institute, Fukuoka University
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- KURISAKI Tsutomu
- Department of Chemistry, Faculty of Science, Fukuoka University
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- PERERA Rupert C. C.
- Center for X-Ray Optics, Lawrence Berkeley National Laboratory
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- WAKITA Hisanobu
- Department of Chemistry, Faculty of Science, Fukuoka University Advanced Materials Institute, Fukuoka University
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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.
収録刊行物
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- Analytical Sciences
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Analytical Sciences 21 (6), 635-639, 2005
社団法人 日本分析化学会
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詳細情報 詳細情報について
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- CRID
- 1390001204255754240
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- NII論文ID
- 10016141635
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- NII書誌ID
- AA10500785
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- COI
- 1:CAS:528:DC%2BD2MXlsFers7w%3D
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- ISSN
- 13482246
- 09106340
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- NDL書誌ID
- 7332696
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- PubMed
- 15984197
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- 本文言語コード
- en
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- データソース種別
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- JaLC
- NDL
- Crossref
- PubMed
- CiNii Articles
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- 使用不可