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

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Abstract

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.

Original languageEnglish
Pages (from-to)136-141
Number of pages6
JournalBulletin of the Chemical Society of Japan
Volume81
Issue number1
DOIs
Publication statusPublished - 2008
Externally publishedYes

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Porphyrins
Electronic properties
Iron
Magnetic susceptibility
Isomers
Paramagnetic resonance
Nuclear magnetic resonance
Ligands
Atoms

ASJC Scopus subject areas

  • Chemistry(all)

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Electronic properties in a five-coordinate azido complex of nonplanar iron(III) porphyrin : Revisiting to quantum mechanical spin admixing. / Neya, Saburo; Takahashi, Akihiro; Ode, Hirotaka; Hoshino, Tyuji; Ikezaki, Akira; Ohgo, Yoshiki; Takahashi, Masashi; Furutani, Yuji; Lórenz-Fonfría, Víctor A.; Kandori, Hideki; Hiramatsu, Hirotsugu; Kitagawa, Teizo; Teraoka, Junji; Funasaki, Noriaki; Nakamura, Mikio.

In: Bulletin of the Chemical Society of Japan, Vol. 81, No. 1, 2008, p. 136-141.

Research output: Contribution to journalArticle

Neya, S, Takahashi, A, Ode, H, Hoshino, T, Ikezaki, A, Ohgo, Y, Takahashi, M, Furutani, Y, Lórenz-Fonfría, VA, Kandori, H, Hiramatsu, H, Kitagawa, T, Teraoka, J, Funasaki, N & Nakamura, M 2008, 'Electronic properties in a five-coordinate azido complex of nonplanar iron(III) porphyrin: Revisiting to quantum mechanical spin admixing', Bulletin of the Chemical Society of Japan, vol. 81, no. 1, pp. 136-141. https://doi.org/10.1246/bcsj.81.136
Neya, Saburo ; Takahashi, Akihiro ; Ode, Hirotaka ; Hoshino, Tyuji ; Ikezaki, Akira ; Ohgo, Yoshiki ; Takahashi, Masashi ; Furutani, Yuji ; Lórenz-Fonfría, Víctor A. ; Kandori, Hideki ; Hiramatsu, Hirotsugu ; Kitagawa, Teizo ; Teraoka, Junji ; Funasaki, Noriaki ; Nakamura, Mikio. / Electronic properties in a five-coordinate azido complex of nonplanar iron(III) porphyrin : Revisiting to quantum mechanical spin admixing. In: Bulletin of the Chemical Society of Japan. 2008 ; Vol. 81, No. 1. pp. 136-141.
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AU - Ode, Hirotaka

AU - Hoshino, Tyuji

AU - Ikezaki, Akira

AU - Ohgo, Yoshiki

AU - Takahashi, Masashi

AU - Furutani, Yuji

AU - Lórenz-Fonfría, Víctor A.

AU - Kandori, Hideki

AU - Hiramatsu, Hirotsugu

AU - Kitagawa, Teizo

AU - Teraoka, Junji

AU - Funasaki, Noriaki

AU - Nakamura, Mikio

PY - 2008

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N2 - 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.

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