Abstract: Metal complexation reactions of N-t-butyl-N-oxidanyl-2-amino(nitronyl nitroxide) diradical (1) with M(hfac)2 (M: Mn or Cu) were investigated. These reactions were found to be very sensitive to the type of metal ion employed. Complex [Mn(hfac)2·1], consisting of Mn(hfac)2 and diradical 1, was readily prepared by mixing the components. However, the reaction of Cu(hfac)2 with 1 or N-t-butyl-N-oxidanyl-2-amino(iminonitroxide) diradical (2) involved the reduction of the diradical to the N-t-butyl-N-oxidanide-2-amino(iminonitroxide) radical anion (3) and finally produced the polymer-chain complex [Cu2(hfac)2·32·Cu(hfac)2]n. The structures of these complexes were elucidated by X-ray analysis, and their magnetic properties were investigated in detail. The temperature dependence of χpT (χp: magnetic susceptibility) for [Mn(hfac)2·1] exhibited a strong antiferromagnetic interaction (H = −2JS1·S2, J/kB = −217 K) between the Mn(II) spin (S = 5/2) and the diradical 1 spin (S = 1). However, the χpT–T plots for [Cu2(hfac)2·32·Cu(hfac)2]n indicated the presence of several magnetic interactions: a large ferromagnetic interaction (J/kB = 510 K) between iminonitroxide 3 and the imino-coordinating Cu(II) atom, a moderately large ferromagnetic interaction (J/kB = 58 K) between the iminonitroxide and (iminonitroxide oxygen)-coordinating Cu(hfac)2, and a weak antiferromagnetic interaction (J/kB = −1.4 K) between the two Cu(hfac)-3 moieties within a Cu2O2 square.

Cite: Furui T. , Suzuki S. , Kozaki M. , Shiomi D. , Sato K. , Takui T. , Okada K. , Tretyakov E.V. , Tolstikov S.E. , Romanenko G.V. , Ovcharenko V.I.
Preparation and Magnetic Properties of Metal-Complexes from N-t-Butyl-N-oxidanyl-2-amino-(nitronyl nitroxide)
Inorganic Chemistry. 2014. V.53. N2. P.802-809. DOI: 10.1021/ic4020898 WOS Scopus

Dates:

Published print:

Jan 21, 2014

Identifiers:

Web of science:	WOS:000330204000025
Scopus:	2-s2.0-84892731338

Citing:

DB	Citing
Scopus	31
Web of science	29

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