Novel Porous Polymorphs of Zinc Cyanide with Rich Thermal and Mechanical Behavior

Fabien Trousselet (1) , Anne Boutin (2) , François-Xavier Coudert (1)

1 IRCP - Institut de Recherche de Chimie Paris
2 PASTEUR - Processus d'Activation Sélective par Transfert d'Energie Uni-électronique ou Radiatif (UMR 8640)

We investigate the feasibility of four-connected nets as hypothetical zinc cyanide polymorphs, as well as their thermal and mechanical properties, through quantum chemical calculations and molecular dynamics simulations. We confirm the metastability of the two porous phases recently discovered experimentally [Lapidus, S. H.; et al. J. Am. Chem. Soc.2013, 135, 7621–7628], suggest the existence of seven novel porous phases of Zn(CN)2, and show that isotropic negative thermal expansion is a common occurrence among all members of this family of materials, with thermal expansion coefficients close to that of the dense dia-c phase. In constrast, we find a wide variety in the mechanical behavior of these porous structures with framework-dependent anisotropic compressibilities. All porous structures, however, show pressure-induced softening leading to a structural transition at modest pressure.

Domaines: Chimie; Chimie théorique et/ou physique; Matériaux

Fabien Trousselet, Anne Boutin, François-Xavier Coudert. Novel Porous Polymorphs of Zinc Cyanide with Rich Thermal and Mechanical Behavior. Chemistry of Materials, 2015, 27 (12), pp.4422-4430. ⟨10.1021/acs.chemmater.5b01366⟩. ⟨hal-02310244⟩