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J Am Chem Soc. 2010 Mar 24;132(11):3980-8. doi: 10.1021/ja910963x.

[ReCl4(CN)2]2-: a high magnetic anisotropy building unit giving rise to the single-chain magnets (DMF)4MReCl4(CN)2 (M = Mn, Fe, Co, Ni).

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  • 1Department of Chemistry, University of California, Berkeley, California 94720, USA.


An S = 3/2, high-anisotropy building unit, trans-[ReCl(4)(CN)(2)](2-), representing the first paramagnetic complex with a mixture of just cyanide and halide ligands, has been synthesized through the reaction of (Bu(4)N)CN with ReCl(4)(THF)(2). This species is characterized in detail and employed in directing the formation of a series of one-dimensional coordination solids of formula (DMF)(4)MReCl(4)(CN)(2) (M = Mn (2), Fe (3), Co (4), Ni (5)). Variable-temperature dc magnetic susceptibility measurements demonstrate the presence of intrachain antiferromagnetic (2) and ferromagnetic (3-5) exchange coupling within these solids. In addition, probing the ac magnetic susceptibility as a function of both temperature and frequency reveals that all of the chain compounds exhibit slow relaxation of the magnetization. The relaxation time is shown to be thermally activated, with energy barriers to relaxation of Delta(tau) = 31, 56, 17, and 20 cm(-1) for 2-5, respectively. Notably, the field-dependent magnetization of the iron congener exhibits a significant hysteresis effect at low temperature, with a coercive field of H(C) = 1.0 T, thus demonstrating magnetlike behavior in this one-dimensional system. Finally, the magnetization dynamics of all solids occur within the finite-size regime, where the magnetic domain growth is limited due to physical defects along the chains within the crystals.

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