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Supramolecular complexation of alkali cations through mechanochemical reactions between crystalline solids

Braga, Dario and Maini, Lucia and Giaffreda, Stefano Luca and Grepioni, Fabrizia and Chierotti, Michele Remo and Gobetto, Roberto (2004) Supramolecular complexation of alkali cations through mechanochemical reactions between crystalline solids. Chemistry: a European Journal, Vol. 10 (13), p. 3261-3269. eISSN 1521-3765. Article.

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DOI: 10.1002/chem.200305751


The organometallic zwitterion [CoIII5-C5H4COOH)(η5-C5H4COO)] reacts quantitatively as a solid polycrystalline phase with a number of crystalline alkali salts MX (M = K+, Rb+, Cs+, NH4+; X = Cl-, Br-, I-, PF6-, although not in all cation/anion permutations) to afford supramolecular complexes of the formula [CoIII5-C5H4COOH)(η5-C5H4COO)]2•M+X-. In some cases, the mechanochemical complexation requires kneading of the two solids with a catalytic amount of water. The characterization of the solid-state products has been achieved by a combination of X-ray single-crystal and powder-diffraction experiments. The hydrogen-bonding interactions have been investigated by solid-state NMR spectroscopy. The mechanochemical reactions imply a profound solid-state rearrangement accompanied by breaking and forming of O-H•••O hydrogen-bonding interactions between the organometallic molecules. All compounds could also be obtained by solution crystallization of the inorganic salts in the presence of the organometallic unit. The solid-state complexation of alkali cations by the organometallic zwitterion has been described as a special kind of solvation process taking place in the solid state.

Item Type:Article
ID Code:2525
Uncontrolled Keywords:Crystal engineering, hydrogen bonds, mechanochemistry, NMR spectroscopy, organometallic compounds, solid-solid reactions
Subjects:Area 03 - Scienze chimiche > CHIM/03 Chimica generale e inorganica
Divisions:001 Università di Sassari > 01 Dipartimenti > Chimica
Deposited On:18 Aug 2009 10:08

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