Chemical transformations of a crystalline coordination polymer: a multi-stage solid–vapour reaction manifold

In its crystal structure the one-dimensional coordination polymer [Ag4(O2C(CF2)2CF3)4(TMP)3]n (1) (TMP = 2,3,5,6-tetramethylpyrazine) adopts a zig-zag arrangement in which pairs of silver(I) centres bridged by two fluorocarboxylate ligands are linked alternately via one or two neutral TMP ligands. This material can reversibly absorb/desorb small alcohols (ROH) in single-crystal-to-single-crystal transformations, despite the lack of porosity in the crystals, to yield a related material of formula [Ag4(O2C(CF2)2CF3)4(TMP)3(ROH)2]n (1-ROH). The absorption process includes coordination of the alcohol to silver(I) centres and, in the process, insertion of the alcohol into one-quarter of the Ag–O…