Guest-Dependent Negative Thermal Expansion in Nanoporous Prussian Blue Analogues MIIPtIV(CN)6·x{H2O} (0 ≤ x ≤ 2; M = Zn, Cd)
- 1 December 2005
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 127 (51) , 17980-17981
- https://doi.org/10.1021/ja056460f
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.Keywords
This publication has 9 references indexed in Scilit:
- Negative thermal expansion and low-frequency modes in cyanide-bridged framework materialsPhysical Review B, 2005
- A comparison between thermal expansion properties of hydrated and dehydrated orthorhombic HZSM-5 zeoliteMicroporous and Mesoporous Materials, 2004
- Handbook of Zeolite Science and TechnologyPublished by Taylor & Francis ,2003
- The widespread occurrence of negative thermal expansion in zeolitesJournal of Materials Chemistry, 2000
- Synthesis and Properties of the Negative Thermal Expansion Material Cubic ZrMo2O8Chemistry of Materials, 1998
- ISOTROPIC NEGATIVE THERMAL EXPANSIONAnnual Review of Materials Science, 1998
- The Disordered Crystal Structures of Zn(CN)2and Ga(CN)3Journal of Solid State Chemistry, 1997
- Homogeneous NMR Spectra in Inhomogeneous FieldsScience, 1996
- Negative Thermal Expansion and Phase Transitions in the ZrV2-xPxO7 SeriesChemistry of Materials, 1995