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Issue 3, 2012
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Potassium ion-mediated non-covalent bonded coordination polymers

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Abstract

Crystal structures and vibrational spectra of three related network-forming coordination complexes have been studied. Two novel thermodynamically stable pseudo-polymorphic solvated rhodium chloro compounds, [cis-RhCl4(DMSO-κS)2K]n, 1, and [cis-RhCl4(DMSO-κS)2K·3H2O]n, 2, and one metastable compound [trans-RhCl4(DMSO-κS)2K·0.25H2O]n, 3, crystallize at ambient temperature in the orthorhombic space groupP212121 for 1, and the monoclinic space groupsP21/n and P21/c for 2 and 3, respectively. All three structures contain [RhCl4(DMSO-κS)2] complexes in which the rhodium(III) ions bind to two dimethyl sulfoxide (DMSO) sulfur atoms and four chloride ions in distorted octahedral coordination geometries. The complexes are connected in networks viapotassium ions interacting with the Cl and the DMSO oxygen atoms. As the sum of Shannon ionic radii of K+ and Cl exceeds the K–Cl distances in compounds under study, these compounds can be described as Rh–Cl–K coordination polymers with non-covalent bonding, which is not common in these systems, forming 1- and 2-D networks for 1/2 and 3, respectively. The 2-D network with nano-layered sheets for compound 3 was also confirmed by TEM images. Further evaluation of the bonding in the cis- and trans-[RhCl4(DMSO-κS)2] entities was obtained by recording Raman and FT-IR absorption spectra and assigning the vibrational frequencies with the support of force-field calculations. The force field study of complexes reveals the strong domination of trans-effect (DMSO-κS > Cl) over the effect of non-covalent bonding in coordination polymeric structures. The comparison of calculated RhCl, RhS and SO stretching force constants showed evidence of K+ligand interactions whereas direct experimental evidences of K+–Cl interaction were not obtained because of strong overlap of the corresponding spectral region with that where lattice modes and Rh–ligand bendings appear.

Graphical abstract: Potassium ion-mediated non-covalent bonded coordination polymers

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Publication details

The article was received on 07 Sep 2011, accepted on 30 Sep 2011 and first published on 22 Nov 2011


Article type: Paper
DOI: 10.1039/C1DT11698C
Citation: Dalton Trans., 2012,41, 850-859

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    Potassium ion-mediated non-covalent bonded coordination polymers

    A. Abbasi, S. Geranmayeh, M. Y. Skripkin and L. Eriksson, Dalton Trans., 2012, 41, 850
    DOI: 10.1039/C1DT11698C

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