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تسجيل مستخدم جديدNegative thermal expansion and metallophilicity in Cu$_3$[Co(CN)$_6$]
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We report the synthesis and structural characterisation of the molecular framework copper(I) hexacyanocobaltate(III), Cu$_3$[Co(CN)$_6$], which we find to be isostructural to H$_3$[Co(CN)$_6$] and the colossal negative thermal expansion material Ag$_3$[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: $alpha_a$ = 25.4(5),MK$^{-1}$ and $alpha_c$ = $-$43.5(8),MK$^{-1}$. These opposing effects collectively result in a volume expansivity $alpha_V$ = 7.4(11),MK$^{-1}$ 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$ldots$Cu metallophilic (`cuprophilic) interactions are significantly weaker in Cu$_3$[Co(CN)$_6$] than Ag$ldots$Ag interactions in Ag$_3$[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 lattice dynamical 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.
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