Uniaxial negative thermal expansion and metallophilicity in Cu3[Co(CN)6]
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 colossalnegative thermal expansion material Ag3[Co(CN)6]. Using synchrotron X-ray powder diffraction measurements,...
| Príomhchruthaitheoirí: | , , , , , , , |
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| Formáid: | Journal article |
| Foilsithe / Cruthaithe: |
Elsevier
2017
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| Achoimre: | 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 colossalnegative 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 thetrigonal crystal axis:α= 25.4(5) MKa−1andα= − 43.5(8) MKc−1. These opposing effects collectively result in avolume expansivityα= 7.4(11) MKV−1that is remarkably small for an anisotropic molecular framework. Thisthermal 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) todemonstrate 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 translatesto a more moderate—rather than enhanced—degree of structural flexibility. The same conclusion is drawn fromconsideration of a simple GULP model, which we also present here. Our results demonstrate that stronginteractions can actually be exploited in the design of ultra-responsive materials if those interactions are set upto act in tension. |
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