Readily accessible shape-memory effect in a porous interpenetrated coordination network

Shape-memory effects are quite well-studied in general, but there is only one reported example in the context of porous materials. We report the second example of a porous coordination network that exhibits a sorbate-induced shape-memory effect and the first in which multiple sorbates, N₂, CO₂ and CO promote this effect. The material, a new threefold interpenetrated pcu network, [Zn₂(4,4′-biphenyldicarboxylate)₂(1,4-bis(4-pyridyl)benzene)]_n (X-pcu-3-Zn-3i), exhibits three distinct phases: the as-synthesized a phase; a denser-activated b phase; and a shape-memory g phase, which is intermediate in density between the a and b phases. The g phase is kinetically stable over multiple adsorption/ desorption cycles and only reverts to the b phase when heated at >400 K under vacuum. The a phase can be regenerated by soaking the g phase in N,N′-dimethylformamide. Single-crystal x-ray crystallography studies of all three phases provide insight into the shape-memory phenomenon by revealing the nature of interactions between interpenetrated networks. The b and g phases were further investigated by in situ coincidence powder x-ray diffraction, and their sorption isotherms were replicated by density functional theory calculations. Analysis of the structural information concerning the three phases of X-pcu-3-Zn-3i enabled us to understand structure-function relationships and propose crystal engineering principles for the design of more examples of shape-memory porous materials.