Insight into systematic formation of hexafluorosilicate during crystallization self-assembly in a glass vessel.

Formation of the unexpected hexafluorosilicate (SiF ) anion during crystallization self-assembly in glassware is scrutinized. Self-assembly of M(BF) (M = Cu and Zn) with tridentate N-donors (L) in a mixture solvent including methanol in a glass vessel gives rise to an SiF -encapsulated CuL double-decker cage and a ZnL cage, respectively. Induced reaction of CuX (X = PF and SbF ) instead of Cu(BF), with the tridentate ligands, produces the same species. The formation time of SiF is in the order of anions BF < PF < SbF under the given reaction conditions. The SiF anion, acting as a cage template or cage-to-cage bridge, seems to be formed from the reaction of polyatomic anions containing fluoride with the SiO of the surface of the glass vessel.