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.