Issue 4, 2001
From the journal:

Journal of the Chemical Society, Dalton Transactions

Structure, optical and magnetic behaviour of meso-tetraphenylporphyrinatoiron(III) tetracyanoethenide, [FeIII(TPP)]+[TCNE]˙− †

Shinji Mikami,a   Ken-ichi Sugiura,*a   Tatsuo Maruta,b   Yonezo Maeda,b   Masaaki Ohba,bc   Naoki Usuki,b   Hisashi Ōkawa,b   Tomoyuki Akutagawa,cd   Sadafumi Nisihara,d   Takayoshi Nakamura,d   Kentaro Iwasaki,e   Nobuyuki Miyazaki,e   Shojun Hino,e   Eiji Asato,f   Joel S. Miller*g  and  Yoshiteru Sakata*a  

* Corresponding authors

a The Institute of Scientific and Industrial Research (ISIR), Osaka University, 8-1 Mihogaoka, Ibaraki, Japan
E-mail: sugiura@sanken.osaka-u.ac.jp

b Department of Chemistry, Faculty of Sciences, Kyushu University, Hakozaki-ku 6-10-1, Fukuoka, Japan

c PREST, Japan Science and Technology Corporation (JST), Kawaguchi Center Building 1–8, Honcho 4-chome, Kawaguchi City, Japan

d Research Institute for Electronic Science, Hokkaido University, Japan

e Faculty of Engineering, Chiba University, Inageku, Chiba, Japan

f Department of Chemistry, Biology, and Marine Science, University of the Ryukyus, Nishihara-cho, Okinawa, Japan

g Department of Chemistry, University of Utah, Salt Lake City, USA
E-mail: jsmiller@chemistry.chem.utah.edu

Abstract

The direct redox reaction between tetracyanoethylene (TCNE) and meso-tetraphenylporphyrinatoiron(II), [FeII(TPP)], formed the electron transfer salt (ETS) [FeIII(TPP)][TCNE], which has been structurally, spectroscopically, and magnetically characterized. It has an extended one-dimensional linear chain with coordination polymer motif comprised of [FeIII(TPP)]+ and bridging μ-[TCNE]˙− with Fe–NTCNE distance 1.889(2) Å. This coordination geometry is consistent with a low-spin iron(III) ion, i.e., one electron transfer from FeII to TCNE produces S = 1/2 [FeIII(TPP)]+ having a (dxy)2(dyz,dzx)3 configuration and S = 1/2 [TCNE]˙−. 57Fe Mössbauer data, δ = 0.28 mm s−1 and ΔE = 2.19 mm s−1 at 77 K, also support the low-spin state. The room temperature magnetic moment of the ETS, 1.20 μB, arises from two S = 1/2 systems having antiferromagnetic coupling, −190 cm−1 (H = −2Σ Ji jSiSj).

Graphical abstract: Structure, optical and magnetic behaviour of meso-tetraphenylporphyrinatoiron(III) tetracyanoethenide, [FeIII(TPP)]+[TCNE]˙− [ ]

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Article information

DOI
https://doi.org/10.1039/B007931F
Article type
Paper
Submitted
02 Oct 2000
Accepted
04 Dec 2000
First published
18 Jan 2001

J. Chem. Soc., Dalton Trans., 2001, 448-455

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Structure, optical and magnetic behaviour of meso-tetraphenylporphyrinatoiron(III) tetracyanoethenide, [FeIII(TPP)]+[TCNE]˙−

S. Mikami, K. Sugiura, T. Maruta, Y. Maeda, M. Ohba, N. Usuki, H. Ōkawa, T. Akutagawa, S. Nisihara, T. Nakamura, K. Iwasaki, N. Miyazaki, S. Hino, E. Asato, J. S. Miller and Y. Sakata, J. Chem. Soc., Dalton Trans., 2001, 448 DOI: 10.1039/B007931F

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