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Reversible shuttle action upon dehydration and rehydration processes in cationic coordinatively-bonded (4,4)
Yi-Min Jiang1, Zheng Yin, Kun-Huan He
1Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources (Ministry of Education), School of Chemistry and Chemical Engineering of Guangxi Normal University, Guilin 541004, PR China.
Abstract:
{[Cu(II)(4,4'-bpy)(2)(H(2)O)][Cu(II)(2-pySO(3))(3)](NO(3))}·H(2)O, obtained serendipitously by the reaction of the constituents in water, consists of parallel coordinatively bonded cationic (4,4) corrugated square-grids polymer of {[Cu(II)(4,4'-bpy)(2)(H(2)O)](2+)}(n) threaded by π-π and H-bonded supramolecular chains of [Cu(II)(2-pySO(3))(3)](-) through the open squares. A single-crystal to single-crystal transformation takes place upon removal of the noncoordinated water by controlled heating. The resulting structure exhibits a rearrangement of the coordination of the copper atoms in the grids, where the Cu-H(2)O bond is elongated from 2.250(3) to 2.628(3) Å while the Cu-NO(3) is shortened from 3.122(3) to 2.796(1) Å. This process is reversible as demonstrated by the single crystal structure after rehydration with corresponding bond distances of 2.224(3) and 3.152(3) Å. Such a cooperative effect may be associated with the Jahn-Teller distortion of the copper(II) ion accompanying the shuttle action of the hydrogen-bonded water and nitrate moiety.
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