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Published on: September 5, 2016
Sulfate-Bridged, Octanuclear Chromic and Ferric Wheels
Maurice G Sorolla1, Xiqu Wang1, Tatyana Makarenko1
1Department of Chemistry and Texas Center for Superconductivity , University of Houston , Houston , Texas 77204 , United States.
Abstract:
Two new amine-templated transition metal-based sulfates, [(CH3)2NH2]17.4 [SO4]0.7 [MIII8(μ2-OH)8(μ2-SO4)16] where M = Cr and Fe, have been synthesized via mild solvothermal synthesis. The compounds are isostructural and were refined in the monoclinic space group P21/n. They feature the rare sulfate-bridged inorganic molecular wheels [CrIII8(OH)8(SO4)16]16- and [FeIII8(OH)8(SO4)16]16-. In both the octanuclear chromic (J = -2.4 cm-1 based on Ĥex = -J · convention) and ferric wheels (J = -38.3 cm-1), the coupling between the adjacent metal ions is antiferromagnetic giving spin-singlet ground states. The variation in the magnitude of the exchange coupling constants is due to the differences in the superexchange mechanisms, namely, a π-pathway for the Cr- and a σ-pathway for the Fe-wheel cluster.
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