Impact of Metallophilicity on “Colossal” Positive and Negative Thermal Expansion in a Series of Isostructural Dicyanometallate Coordination Polymers
- 16 March 2009
- journal article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 131 (13), 4866-4871
- https://doi.org/10.1021/ja809631r
Abstract
Five isostructural dicyanometallate coordination polymers containing metallophilic interactions (In[M(CN)(2)](3) (M = Ag, Au), KCd[M(CN)(2)](3), and KNi[Au(CN)(2)](3)) were synthesized and investigated by variable-temperature powder X-ray diffraction to probe their thermal expansion properties. The compounds have a trigonal unit cell and show positive thermal expansion (PTE) in the ab plane, where Kagome sheets of M atoms reside, and negative thermal expansion (NTE) along the trigonal c axis, perpendicular to these sheets. The magnitude of thermal expansion is unusually large in all cases (40 x 10(-6) K(-1) < |alpha| < 110 x 10(-6) K(-1)). The system with the weakest metallophilic interactions, In[Ag(CN)(2)](3), shows the most "colossal" thermal expansion of the series (alpha(a) = 105(2) x 10(-6) K(-1), alpha(c) = -84(2) x 10(-6) K(-1) at 295 K), while systems containing stronger Au-Au interactions show relatively reduced thermal expansion. Thus, it appears that strong metallophilic interactions hinder colossal thermal expansion behavior. Additionally, the presence of K(+) counterions also reduces the magnitude of thermal expansion.Keywords
This publication has 58 references indexed in Scilit:
- Thermal expansion in cuprite-type structures from 10 K to decomposition temperature: Cu2O and Ag2OJournal of Applied Crystallography, 2003
- Strong Negative Thermal Expansion along the O−Cu−O Linkage in CuScO2Chemistry of Materials, 2002
- The widespread occurrence of negative thermal expansion in zeolitesJournal of Materials Chemistry, 2000
- Negative Thermal Expansion in the Siliceous Zeolites Chabazite and ITQ-4: A Neutron Powder Diffraction StudyChemistry of Materials, 1999
- Negative thermal expansion materials †J. Chem. Soc., Dalton Trans., 1999
- Synthesis and Properties of the Negative Thermal Expansion Material Cubic ZrMo2O8Chemistry of Materials, 1998
- Exceptional Negative Thermal Expansion in AlPO4-17Chemistry of Materials, 1998
- Strong negative thermal expansion in siliceous faujasiteChemical Communications, 1998
- Negative Thermal Expansion from 0.3 to 1050 Kelvin in ZrW 2 O 8Science, 1996
- Negative Thermal Expansion and Phase Transitions in the ZrV2-xPxO7 SeriesChemistry of Materials, 1995