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

被引：10

作者：

Neya, Saburo ^{[1
]}

Takahashi, Akihiro ^{[1
]}

Ode, Hirotaka ^{[1
]}

Hoshino, Tyuji ^{[1
]}

Ikezaki, Akira ^{[2
]}

Ohgo, Yoshiki ^{[2
]}

Takahashi, Masashi ^{[3
]}

Furutani, Yuji ^{[4
]}

Lorenz-Fonfria, Victor A. ^{[4
]}

Kandori, Hideki ^{[4
]}

Hiramatsu, Hirotsugu ^{[5
]}

Kitagawa, Teizo ^{[5
]}

Teraoka, Junji ^{[6
]}

Funasaki, Noriaki ^{[7
]}

Nakamura, Mikio ^{[2
]}

机构：

[1] Chiba Univ, Grad Sch Pharmaceut Sci, Dept Phys Chem, Inage Ku, Chiba 2638522, Japan

[2] Toho Univ, Sch Med, Dept Chem, Ota Ku, Tokyo 1438540, Japan

[3] Toho Univ, Fac Sci, Dept Chem, Funabashi, Chiba 4668555, Japan

[4] Nagoya Inst Technol, Dept Mat Sci & Engn, Nagoya, Aichi 4668555, Japan

[5] Okazaki Natl Res Inst, Ctr Integrated Biosci, Okazaki, Aichi 4448787, Japan

[6] Osaka City Univ, Grad Sch Sci, Osaka 5588585, Japan

[7] Kyoto Pharmaceut Univ, Dept Phys Chem, Kyoto 6078414, Japan

来源：

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN | 2008年 / 81卷 / 01期

关键词：

D O I：

10.1246/bcsj.81.136

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The iron(M) azido complex of 5,10,15,20-tetraisopropylporphyrin was characterized with NMR, EPR, Mossbauer, 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 timescale. 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.

引用

页码：136 / 141

页数：6

共 40 条

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