Subtle anion effects on anion exchange and thermolysis: Square supra-channels via array of sinusoidal coordination polymers

Self-assembly of AgX (X^-=ClO4-,BF4-) with a new diethylbis(4-pyridyl)silane (L) ligand basically gives rise to a one-dimensional (1D) sinusoidal structure. Weak C-H⋯ interactions between ethyl and pyridyl groups result in the formation of infinite square supra-channel structures via a molecular array of four sinusoidal chains. The supra-channel size is 10.1-10.7 Å with a void cross-section of 2.1-3.1 Å for [Ag(L)](ClO₄) and 9.9-10.5 Å with a void cross-section of 2.0-3.0 Å for [Ag(L)](BF₄). The supra-channels are occupied by each counteranion. Anion exchange of [Ag(L)](BF₄) with NaClO ₄ occurs smoothly, whereas the reverse anion exchange of [Ag(L)](ClO₄) with NaBF₄ does not. Calcination of [Ag(L)](ClO₄) crystals at 400 C produces a circle morphology with evolving burned organics, and, at 600 C, forms network circles consisting of a silver(0)/silver chloride (chlorargyrite)/silicon(IV) oxide composite with a micro-sized convexo-concave surface. In contrast, calcination of [Ag(L)](BF ₄) crystals at 600 C produces silver(0) materials without silicon(IV) oxide.