Supramolecular complexation of alkali cations through mechanochemical reactions between crystalline solids

Chemistry : a European Journal
Dario BragaRoberto Gobetto

Abstract

The organometallic zwitterion [Co(III)(eta(5)-C(5)H(4)COOH)(eta(5)-C(5)H(4)COO)] reacts quantitatively as a solid polycrystalline phase with a number of crystalline alkali salts MX (M = K(+), Rb(+), Cs(+), NH(4) (+); X = Cl(-), Br(-), I(-), PF(6)(-), although not in all cation/anion permutations) to afford supramolecular complexes of the formula [Co(III)(eta(5)-C(5)H(4)COOH)(eta(5)-C(5)H(4)COO)](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...Continue Reading

Citations

Feb 3, 2007·Chemical Communications : Chem Comm·Dario BragaFabrizia Grepioni
Jan 15, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Nicholas R Rightmire, Timothy P Hanusa
Jul 20, 2005·Chemical Communications : Chem Comm·Dario Braga, Fabrizia Grepioni
Mar 1, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Dario BragaMarco Polito
Sep 6, 2011·Chemical Society Reviews·Stuart L JamesDaniel C Waddell
Feb 2, 2012·Chemical Communications : Chem Comm·Mangayarkarasi NagarathinamJagadese J Vittal
Apr 4, 2013·Chemical Society Reviews·Dario BragaFabrizia Grepioni
Jan 25, 2013·Chemical Society Reviews·Laszlo Takacs
Dec 14, 2017·Beilstein Journal of Organic Chemistry·Vânia AndréM Teresa Duarte
Feb 24, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Dario BragaKatia Rubini
Jun 1, 2011·Chemistry, an Asian Journal·Dario BragaFabrizia Grepioni
Dec 21, 2013·ChemSusChem·Manoj B GawandeRajender S Varma
Jun 9, 2021·Nature Communications·Hong ZhangMichael Grätzel

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