Slow Magnetic Relaxation in a Series of Non-Heme Trigonal Pyramidal Iron(II) Pyrrolide Complexes

[en] We present a family of novel non-heme trigonal pyramidal iron(II) complexes supported by tris(pyrrolyl-α-methyl)amine ligands of the form [M(solv)n][(tpaR)Fe] (M = Na, R = tert-butyl (1), phenyl (4); M = K, R = mesityl (2), 2,4,6-triisopropylphenyl (3), 2,6-difluorophenyl (5)) and their characterization by X-ray crystallography, cyclic voltammetry, and Mössbauer spectroscopy. Expanding on the initial discovery of slow magnetic relaxation in the recently reported mesityl derivative 2, we report the static and dynamic magnetic properties of a homologous series of high-spin mononuclear iron(II) complexes that exhibit this intriguing behavior. Magnetization experiments reveal large, negative zero-field splitting parameters of D = −48, −40, −36, −26 and −6.2 cm−1 for 1-5, respectively. In the case of 2,6-difluorophenyl 5, high-field EPR experiments provide an independent determination of the zero-field splitting parameters (D = −4.397(9)) that are in reasonable agreement with the magnetization data. Ac susceptibility measurements indicate field-dependent, thermally-activated spin reversal barriers in complexes 1, 2 and 4 of Ueff = 60, 42 and 25 cm−1, respectively. In the case of 1, this value constitutes the highest spin-reversal barrier observed for a mononuclear transition metal complex, a property that has broad implications for the design of molecules that can potentially store and process magnetic information.

Disciplines :

Chemistry

Author, co-author :

Harmann, Hill E; Berkeley University of California - UC Berkeley > Chemistry

Harris, T David; Berkeley University of California - UC Berkeley > Chemistry

Freedman, Danna E; Berkeley University of California - UC Berkeley > Chemistry

Fong, H.; Berkeley University of California - UC Berkeley > Chemistry

Chang, A.; Berkeley University of California - UC Berkeley > Chemistry

Rinehart, Jeffrey D; Berkeley University of California - UC Berkeley > Chemistry

Grandjean, Fernande ; Université de Liège - ULiège > Département de physique > Département de physique

Ozarowski, Andrew; National Magnet Laboratory Florida

Long, Gary J; Missouri University of Science and Technology > Chemistry

Long, Jeffrey R; Berkeley University of California - UC Berkeley > Chemistry

Chang, Christopher; University of California-Berkeley > Chemist6ry

Language :

English

Title :

Slow Magnetic Relaxation in a Series of Non-Heme Trigonal Pyramidal Iron(II) Pyrrolide Complexes

Publication date :

2010

Journal title :

Journal of the American Chemical Society

ISSN :

0002-7863

eISSN :

1520-5126

Publisher :

American Chemical Society, Washington, United States - District of Columbia

Volume :

132

Pages :

18115

Peer reviewed :

Peer Reviewed verified by ORBi

Available on ORBi :

since 12 January 2011

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299

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327

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