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Sci Adv. 2018 Apr 27;4(4):eaaq1636. doi: 10.1126/sciadv.aaq1636. eCollection 2018 Apr.

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

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Department of Chemical Sciences, Bernal Institute, University of Limerick, Limerick, Republic of Ireland.
Institute for Integrated Cell-Material Sciences (WPI-iCeMS), Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan.
Department of Chemistry, University of South Florida, 4202 East Fowler Avenue, Tampa, FL 33620, USA.


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 α phase; a denser-activated β phase; and a shape-memory γ phase, which is intermediate in density between the α and β phases. The γ phase is kinetically stable over multiple adsorption/desorption cycles and only reverts to the β phase when heated at >400 K under vacuum. The α phase can be regenerated by soaking the γ 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 β and γ 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.

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