Guest-dependent negative thermal expansion in nanoporous Prussian blue analogues MIIPtIV(CN)6 x {H20} (0 < x < 2; M = Zn, Cd)

Goodwin, A. L. and Chapman, K. W. and Kepert, C. J. (2005) Guest-dependent negative thermal expansion in nanoporous Prussian blue analogues MIIPtIV(CN)6 x {H20} (0 < x < 2; M = Zn, Cd). Journal of the American Chemical Society, 127 (51). pp. 17980-17981. DOI 10.1021/ja056460f

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Abstract

The guest-dependent thermal expansion behavior of the nanoporous Prussian Blue analogues MIIPtIV(CN)6.x{H2O} (0 </= x </= 2; M = Zn, Cd) has been investigated using variable temperature single-crystal X-ray diffraction. The dehydrated phases MIIPtIV(CN)6 were found to exhibit negative thermal expansion, attributed to thermal population of low energy transverse vibrations of the bridging cyanide ligands. The presence of guest molecules within the framework pore system was found capable of dampening the effect of these transverse vibrational modes. The guest-loaded ZnII phase, in which the available pore volume is commensurate with the volume occupied by individual water molecules, possesses a considerably higher coefficient of thermal expansion, with the material switching from positive to negative thermal expansion behavior upon guest removal.

Item Type: Article
Uncontrolled Keywords: 2006 AREP IA49 2005 P IA50
Subjects: 03 - Mineral Sciences
Divisions: 03 - Mineral Sciences
Journal or Publication Title: Journal of the American Chemical Society
Volume: 127
Page Range: pp. 17980-17981
Identification Number: 10.1021/ja056460f
Depositing User: Sarah Humbert
Date Deposited: 05 May 2011 09:35
Last Modified: 23 Jul 2013 09:58
URI: http://eprints.esc.cam.ac.uk/id/eprint/1655

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