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Helices, chirality and interpenetration: the versatility and remarkable interconversion of silver-copper cyanide frameworks

Chippindale, A. M. and Hibble, S. J. (2009) Helices, chirality and interpenetration: the versatility and remarkable interconversion of silver-copper cyanide frameworks. Journal of the American Chemical Society, 131 (35). pp. 12736-12744. ISSN 0002-7863

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To link to this article DOI: 10.1021/ja903841e

Abstract/Summary

The structural transformations between cesium silver-copper cyanides under modest conditions, both in solution and in the solid state, are described. Three new cesium silver(I) copper(I) cyanides with three-dimensional (3-D) framework structures were prepared as single crystals from a one-pot reaction initially heated under hydrothermal conditions. The first product to appear, Cs3Ag2Cu3(CN)(8) (I), when left in contact with the supernatant produced CsAgCu(CN)(3) (II) and CsAgCu(CN)(3)center dot 1/3H(2)O (III) over a few months via a series of thermodynamically controlled cascade reactions. Crystals of the hydrate (III) can be dehydrated to polycrystalline CsAgCu(CN)(3) (II) on heating at 100 degrees C in a remarkable solid-state transformation involving substantial breaking and reconnection of metal-cyanide linkages. Astonishingly, the conversion between the two known polymorphs of CsAg2Cu(CN)(4), which also involves a major change in connectivity and topology, occurs at 180 degrees C as a single-crystal to single-crystal transformation. Structural features of note in these materials include the presence of helical copper-cyanide chains in (I) and (II), which in the latter compound produce a chiral material. In (II) and (III), the silver-copper cyanide networks are both self- and interpenetrating, features also seen in the known polymorphs of CsAg2Cu(CN)(4).

Item Type:Article
Refereed:Yes
Divisions:Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:11133
Uncontrolled Keywords:NEGATIVE THERMAL-EXPANSION, TOTAL NEUTRON-DIFFRACTION, PRUSSIAN BLUE, ANALOGS, CRYSTAL-STRUCTURE, COORDINATION POLYMER, SINGLE-CRYSTAL, CHEMISTRY, NETWORKS, MAGNET, CHAINS
Publisher:American Chemical Society

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