Metal-ligand Lability and Ligand Mobility Enables Framework Transformation via Ligand Release in a Family of Crystalline 2D Coordination Polymers.

A family of seven silver(I)-perfluorocarboxylate-quinoxaline coordination polymers, [Ag (O CR ) (quin) ] 1-5 (R =(CF ) CF ) , n=1 to 5); [Ag (O C(CF ) CO ) (quin) ] 6; [Ag (O CC F ) (quin) ] 7 (quin=quinoxaline), denoted by composition as 4 : 4 : 4 phases, was synthesised from reaction of the corresponding silver(I) perfluorocarboxylate with excess quinoxaline. Compounds 1-7 adopt a common 2D layered structure in which 1D silver-perfluorcarboxylate chains are crosslinked by ditopic quinoxaline ligands. Solid-state reaction upon heating, involving loss of one equivalent of quinoxaline, yielding new crystalline 4 : 4 : 3 phases [Ag (O C(CF ) CF ) (quin) ] (8-10, n=1 to 3), was followed in situ by PXRD and TGA studies.