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Flexibility of inorganic tennis ball structures inducing anion selectivity

Title
Flexibility of inorganic tennis ball structures inducing anion selectivity
Authors
Kim K.-H.Park J.S.Kang T.Y.Oh K.Seo M.-S.Sohn Y.S.Jun M.-J.Nam W.Kim K.M.
Ewha Authors
남원우손연수김관묵서미숙
SCOPUS Author ID
남원우scopus; 손연수scopus; 김관묵scopus
Issue Date
2006
Journal Title
Chemistry - A European Journal
ISSN
0947-6539JCR Link
Citation
vol. 12, no. 27, pp. 7078 - 7083
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
Inorganic tennis balls (ITBs), [[{Pt(betmp)(dach)} 2Cu] 2(X)][X] 3 (in which X = ClO 4 - (3), NO 3 - (4), CT - (5) and Br - (6); dach = trans-1,2-diaminocyclohexane and betmp = bisethylthio-methylidenepropanedioate) and [[{Pt-(dteym)(dach)} 2Cu] 2(PF 6)][PF 6] 3 (7; dteym = 1,3-dithiepane-2-ylidenemalonate), were prepared as crystals. Investigation of their X-ray crystal structures revealed that shapes of the cavities in ITBs show significant distortions that depend on the properties of the encapsulated anions. The Cu⋯Cu* distance was observed to be longest in 7 and shortest in 5, the difference between them being 2.05 Å. The flexibility of cavity structures of ITBs makes it possible to encapsulate various anions inside the cavity, while their distortions may be a reason for the difference in the encapsulating ability for anions, that is, anion selectivity. Especially, the distortions observed in 7 are so severe that the encapsulating ability of the cavity for PF 6 - is very low compared to other anions. The shapes of ITBs with ClO 4 - and BF 4 - ions inside their cavities are very similar; however, ClO 4 - is encapsulated by the cavity better than BF 4 -, which is explicable by the difference of metal-anion interactions. This structural study on ITBs gives a clue to the origin of the anion selectivity of the cavity in ITBs previously investigated by 19F NMR spectroscopy of the ITBs in methanol. © 2006 Wiley-VCH Verlag GmbH & Co. KGaA.
DOI
10.1002/chem.200501626
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자연과학대학 > 화학·나노과학전공 > Journal papers
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