Probing solid-state breathing and structural transformations in a series of silver(I) porous coordination polymers

Abstract

Key observations of the role anions and solvents play in the solid-state flexibility of a series of isostructural silver, I, porous coordination polymers, PCPs, are reported. Building upon earlier results for the perchlorate salt, the structural transformations of two new analogues of a, D PCP, Ag, dpzm, X, dpzm, -dipyrazinylmethane, X, PF, ClO, BF, which contain either PF, a, orBF, c, counteri- ons, are investigated. These materials undergo a remarkable guest-induced single-crystal to single-crystal, SC-SC, solid- state contraction and expansion, which is accurately elucidated by X-ray crystallography. The extent of breathing for PCPs, a, c is shown to relate to the type of anion contained within their, D structures and the nature of the solvent guest. Using X-ray diffraction, further light is shed on structural transformations that take place upon desolvation for this group of materials. These investigations reveal that, while the as-synthesised forms, containing DMSO, undergo a transformation, porous, D to close-packed, D, porous, D to, D, upon desolvation, the solvent-exchanged forms are more stable.