Probing Solid‐State Breathing and Structural Transformations in a Series of Silver(I) Porous Coordination Polymers

Abstract

AbstractKey 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 3D PCP [Ag(dpzm)]X (1) (dpzm = 2,2′‐dipyrazinylmethane; X = PF6, ClO4, BF4), which contain either PF6 (1a) or BF4 (1c) counterions, 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 1a–1c is shown to relate to the type of anion contained within their 3D 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 3D to close‐packed 3D; porous 3D to 2D) upon desolvation, the solvent‐exchanged forms are more stable.