Electronic properties in a five-coordinate azido complex of nonplanar iron(III) porphyrin: Revisiting to quantum mechanical spin admixing

Saburo Neya, Akihiro Takahashi, Hirotaka Ode, Tyuji Hoshino, Akira Ikezaki, Yoshiki Ohgo, Masashi Takahashi, Yuji Furutani, Víctor A. Lórenz-Fonfría, Hideki Kandori, Hirotsugu Hiramatsu, Teizo Kitagawa, Junji Teraoka, Noriaki Funasaki, Mikio Nakamura

研究成果: Article査読

9 被引用数 (Scopus)

抄録

The iron(III) azido complex of 5,10,15,20-tetraisopropylporphyrin was characterized with NMR, EPR, Mössbauer, and magnetic susceptibility. These physical methods indicate mixing of the high (S = 5/2) and intermediate (S = 3/2) spin-states of the iron atom. The results were interpreted in terms of the core contraction after nonplanar deformation of porphyrin ring by the bulky isopropyl substituents. In the IR spectrum of this complex, there are two signals at 2062 and 2048 cm-1 due to the antisymmetric vibration of the coordinated azido ligand. The split IR bands demonstrate that the two spin isomers are present, and that the S = 5/2 and 3/2 transition occurs sufficiently slow on the IR timeseale. This is in remarkable contrast with the homogeneous spin-mixing model proposed for the S = 5/2 and 3/2 system. The present observations further suggests that the three S = 5/2, 3/2, and 1 /2 states in iron(III) porphyrin commonly mix through thermal spin equilibrium.

本文言語English
ページ(範囲)136-141
ページ数6
ジャーナルBulletin of the Chemical Society of Japan
81
1
DOI
出版ステータスPublished - 2008

ASJC Scopus subject areas

  • Chemistry(all)

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