Unusual endo/exocyclic silver(i) coordination polymers of an NS4-macrocycle exhibiting solvent-induced single-crystal to single-crystal transformation

Abstract

The one-pot reaction of a ditopic NS₄-macrocycle L with silver(I) perchlorate in CH₂Cl₂–CH₃OH afforded the unusual one dimensional coordination polymer {[Ag₃(L)₂](ClO₄)₃·2CH₂Cl₂·CH₃OH}_n (1), in which no anion or solvent molecules are coordinated. In 1, two silver(I) ions are sandwiched by two macrocycles and the resulting disilver(I) sandwich unit is further linked by one silver(I) ion in an exocyclic manner, giving rise to an infinite array. Exposure of 1 to DMF–ether induces a single-crystal to single-crystal transformation resulting in an anion-coordinated one-dimensional array {[Ag₃(L)₂ClO₄](ClO₄)₂·DMF}_n (2) formed through rearrangement of the metal coordination sphere coupled with a framework distortion.