Silver(I) Double and Multiple Salts Containing the 1,3-Butadiynediide Dianion:Coordination Diversity and Assembly with the Supramolecular Synthon Ag4 is contained in C ident to C-C ident to C contains Ag4

摘要

A series of 13 silver(I) double and multiple salts containing 1,3-butadiynediide,C_4~(2-),were synthesized by dissolving the silver carbide Ag2C4 in a concentrated aqueous solution of one or more of the silver salts AgNO3,AgCF3CO2,AgC2F5CO2,AgF,AgBF4,and AgPF6.The 1,3-butadiynediide anion invariably adopts a mu 4,mu 4 coordination mode in these compounds,which indicates that the Ag4 is contained in C ident to C-C ident to C contains Ag4 moiety can be used as a new type of metalloligand supramolecular synthon for the construction of coordination networks.Fine-tuning with various ancillary anionic ligands caused the Ag4 aggregate at each ethynide terminus to adopt a butterfly-shaped,planar,or barblike configuration,within which the silver-ethynide interactions can be classified into three types:sigma,pi,and mixed (sigma,pi).The effect of coexisting ni-trile ligands and quaternary ammonium salts on supramolecular assembly with the above synthon was also explored.The hydrolysis of PF6~- and BF_4~- led to the formation of the quadruple salt Ag2C4 centre dot 4AgNO3 centre dot AgPF2O2 centre dot Ag3PO4 and a novel (F)2(H2O)18 hydrogen-bonded tape in the triple salt Ag2C4 centre dot 2AgF centre dot 10AgC2F5CO2 centre dot CH3CN centre dot 12H2O,respectively.The largest silver-ethynide cluster aggregate described to date,(C4)3@Ag18,occurs in 3Ag2C4 centre dot 12AgC2F5CO2 centre dot 5[(BnMe3N)C2F5CO2] centre dot 4H2O (Bn=benzyl).