| Potassium ion-mediated non-covalent bonded coordination polymers. | |
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MedLine Citation:
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PMID: 22105187 Owner: NLM Status: Publisher |
Abstract/OtherAbstract:
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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 group P2(1)2(1)2(1) for 1, and the monoclinic space groups P2(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 via potassium 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. |
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Authors:
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Alireza Abbasi; Shokoofeh Geranmayeh; Mikhail Y Skripkin; Lars Eriksson |
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Publication Detail:
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Type: JOURNAL ARTICLE Date: 2011-11-22 |
Journal Detail:
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Title: Dalton transactions (Cambridge, England : 2003) Volume: - ISSN: 1477-9234 ISO Abbreviation: - Publication Date: 2011 Nov |
Date Detail:
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Created Date: 2011-11-22 Completed Date: - Revised Date: - |
Medline Journal Info:
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Nlm Unique ID: 101176026 Medline TA: Dalton Trans Country: - |
Other Details:
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Languages: ENG Pagination: - Citation Subset: - |
Affiliation:
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School of Chemistry, College of Science, University of Tehran, Tehran, Iran. aabbasi@khayam.ut.ac.ir. |
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