On rhenium(i)–silver(i) cyanide porous macrocyclic clusters

Abstract

The first cyanide rhenium(I)–silver(I) clusters were synthesized in the course of simple one-pot high-yielding reactions. This new class of obtained self-assembled, cyclic octanuclear complexes is composed of pseudo-square-shaped {Re₄Ag₄(μ-CN)₈} units, which, along with PPh₃ ligands, adopt an approximately block-like overall geometry. We discovered that the studied cavity-shaped clusters feature a channeling crystal network capable of hosting smaller molecules and exhibit the ability to undergo reversible guest solvent sorption. Depending on the reaction conditions, the tetranuclear complex [Re₂Ag₂(μ-CN)₄(CO)₄(PPh₃)₆] and the species of the formal motif {ReAg_1.5(CN)_2.5(CO)₂(PPh₃)₂} can be formed.