NDLI: Potassium ion-mediated non-covalent bonded coordination polymers

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Abbasi, Alireza Eriksson, Lars Skripkin, Mikhail Y. Geranmayeh, Shokoofeh
Description	Author Affiliation: Abbasi A ( School of Chemistry, College of Science, University of Tehran, Tehran, Iran. aabbasi@khayam.ut.ac.ir)
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, $[cis-RhCl_{4}(DMSO-κS)_{2}K]_{n},$ 1, and $[cis-RhCl_{4}(DMSO-κS)_{2}K·3H_{2}O]_{n},$ 2, and one metastable compound $[trans-RhCl_{4}(DMSO-κS)_{2}K·0.25H_{2}O]_{n},$ 3, crystallize at ambient temperature in the orthorhombic space $groupP2_{1}2_{1}2_{1}$ for 1, and the monoclinic space $groupsP2_{1}/n$ and $P2_{1}/c$ for 2 and 3, respectively. All three structures contain $[RhCl_{4}(DMSO-κS)_{2}]^{−}$ 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 $trans-[RhCl_{4}(DMSO-κS)_{2}]^{−}$ 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.
ISSN	14779226
Issue Number	3
Journal	Dalton Trans.
Volume Number	41
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2012-01-21
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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