| Reference : Uniaxial negative thermal expansion and metallophilicity in Cu3[Co(CN)6] |
| Scientific journals : Article | |||
| Physical, chemical, mathematical & earth Sciences : Chemistry Physical, chemical, mathematical & earth Sciences : Physics | |||
| Physics and Materials Science; Computational Sciences | |||
| http://hdl.handle.net/10993/34381 | |||
| Uniaxial negative thermal expansion and metallophilicity in Cu3[Co(CN)6] | |
| English | |
| 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. [] | |
| Jan-2018 | |
| Journal of Solid State Chemistry | |
| Academic Press | |
| 258 | |
| 298–306 | |
| Yes (verified by ORBilu) | |
| International | |
| 0022-4596 | |
| 1095-726X | |
| San Diego | |
| CA | |
| [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. | |
| http://hdl.handle.net/10993/34381 |
| File(s) associated to this reference | ||||||||||||||
|
Fulltext file(s):
| ||||||||||||||
All documents in ORBilu are protected by a user license.
