Exploiting high pressures to generate porosity, polymorphism, and lattice expansion in the nonporous molecular framework Zn(CN)₂

Systematic exploration of the molecular framework material Zn(CN) ₂ at high pressure has revealed several distinct series of transitions leading to five new phases: four crystalline and one amorphous. The structures of the new crystalline phases have been resolved through ab initio structural determination, combining charge flipping and direct space methods, based on synchrotron powder diffraction data. The specific transition activated under pressure depends principally on the pressure-transmitting fluid used. Without fluid or in large molecule fluids (e.g., isopropanol, ethanol, or fluorinert), the high-pressure behavior intrinsic to Zn(CN)₂ is observed; the doubly interpenetrated diamondoid framework structure transforms to a distorted, orthorhombic polymorph, Zn(CN)₂-II (Pbca) at ∼1.50-1.58 GPa with asymmetric displacement of the bridging CN ligand and reorientation of the Zn(C/N)₄ tetrahedra. In small molecule fluids (e.g., water, methanol, methanol-ethanol-water), the nonporous interpenetrated Zn(CN)₂ framework can undergo reconstructive transitions to porous, non-interpenetrated polymorphs with different topologies: diamondoid (dia-Zn(CN)₂, Fd3m, P_trans ∼ 1.2 GPa), londaleite (lon-Zn(CN)₂, P6₃/mmc, P_trans ∼ 0.9 GPa), and pyrite-like (pyr-Zn(CN)₂, Pa3, P_trans ∼ 1.8 GPa). Remarkably, these pressure-induced transitions are associated with near 2-fold volume expansions. While an increase in volume with pressure is counterintuitive, the resulting new phases contain large fluid-filled pores, such that the combined solid + fluid volume is reduced and the inefficiencies in space filling by the interpenetrated parent phase are eliminated. That both dia-Zn(CN)₂ and lon-Zn(CN)₂ phases were retained upon release to ambient pressure demonstrates the potential for application of hydrostatic pressures to interpenetrated framework systems as a novel means to generate new porous materials.