Silver(I) Multiple Salts Assembled with Phosphonate, Perfluorocarboxylate, and the Multinuclear Silver-Ethynediide Supramolecular Synthon

A series of seven new silver­(I) multiple salts containing C22– (ethynediide, acetylenediide), phosphonate, and perfluorocarboxylate ligands, Ag2C2·2AgCF3CO2·2Ag2­PhPO3·Ag3[(PhPO3)2H] (1), 4Ag2C2·4AgCF3CO2·6Ag2­PhPO3·2AgPhPO3H·3H2O (2), Ag2C2·2AgCF3CO2·Ag2­PhPO3·3AgPhPO3H (3), Ag2C2·AgCF3CO2·Ag2­tBuPO3·2AgtBuPO3H (4), Ag2C2·AgCF3CO2·2Ag2­tBuPO3 (5), 2Ag2C2·2AgC2F5CO2·4Ag2­PhPO3·H2O (6), and 1.5Ag2C2·6AgC2F5CO2·Ag2­PhCH2PO3·AgPhCH2PO3H·6H2O (7), have been synthesized under hydrothermal conditions by varying the types of phosphonic and perfluorocarboxylic acid employed, as well as the mole ratios of the reactants. In compound 1, C2@Ag9 building units (each with a C22– species located inside a Ag9 monocapped distorted square antiprism) are consolidated by trifluoroacetate ligands and interconnected by phenylphosphonate groups to form a two-dimensional coordination network. Compound 2 is composed of two kinds of C2@Ag6 silver cages that are fused together to form an argentophilic chain; such chains are in turn further linked by the phenylphosphonate ligands into a two-dimensional network. Compound 3 also has a layer structure, whose core is a centrosymmetric (C2)2@Ag18 aggregate. In compound 4, centrosymmetric (C2)2@Ag14 aggregates are cross-linked into a coordination layer, and such layers are further assembled into a three-dimensional supramolecular architecture via hydrogen bonding. Compound 5 has an argentophilic layer structure generated from the fusion and linkage of C2@Ag8 cages. Compound 6 exhibits an argentophilic layer structure in which the basic building unit is an unusual silver­(I) aggregate composed of four different kinds of C2@Ag6 cages. The crystal structure of compound 7 is a three-dimensional coordination network, in which the coordination chains containing two kinds of C2@Ag8 single cages are bridged by aqua ligands.