Article (Scientific journals)
Uniaxial negative thermal expansion and metallophilicity in Cu3[Co(CN)6]
Sapnik, A. F.; Liu, X.; Böstrom, H. L. B. et al.
2018In Journal of Solid State Chemistry, 258, p. 298–306
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Abstract :
[en] We report the synthesis and structural characterisation of the molecular framework copper(I) hexacyanocobaltate(III), Cu3[Co(CN)6], which we find to be isostructural to H3[Co(CN)6] and the colossal negative thermal expansion material Ag3[Co(CN)6]. Using synchrotron X-ray powder diffraction measurements, we find strong positive and negative thermal expansion behaviour respectively perpendicular and parallel to the trigonal crystal axis: α = 25.4(5) MK a −1 and α = − 43.5(8) MK c −1. These opposing effects collectively result in a volume expansivity α = 7.4(11) MK V −1 that is remarkably small for an anisotropic molecular framework. This thermal response is discussed in the context of the behaviour of the analogous H- and Ag-containing systems. We make use of density-functional theory with many-body dispersion interactions (DFT + MBD) to demonstrate that Cu+…Cu+ metallophilic (‘cuprophilic’) interactions are significantly weaker in Cu3[Co(CN)6] than Ag+…Ag+ interactions in Ag3[Co(CN)6], but that this lowering of energy scale counterintuitively translates to a more moderate—rather than enhanced—degree of structural flexibility. The same conclusion is drawn from consideration of a simple GULP model, which we also present here. Our results demonstrate that strong interactions can actually be exploited in the design of ultra-responsive materials if those interactions are set up to act in tension.
Disciplines :
Physics
Chemistry
Author, co-author :
Sapnik, A. F.
Liu, X.
Böstrom, H. L. B.
Coates, C. S.
Overy, A. R.
Reynolds, E. M.
Tkatchenko, Alexandre ;  University of Luxembourg > Faculty of Science, Technology and Communication (FSTC) > Physics and Materials Science Research Unit
Goodwin, A. L.
External co-authors :
yes
Language :
English
Title :
Uniaxial negative thermal expansion and metallophilicity in Cu3[Co(CN)6]
Publication date :
January 2018
Journal title :
Journal of Solid State Chemistry
ISSN :
1095-726X
Publisher :
Academic Press, San Diego, United States - California
Volume :
258
Pages :
298–306
Peer reviewed :
Peer Reviewed verified by ORBi
Focus Area :
Physics and Materials Science
Computational Sciences
Available on ORBilu :
since 03 February 2018

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