Silver(I) Double and Multiple Salts Containing the 1,3‐Butadiynediide Dianion: Coordination Diversity and Assembly with the Supramolecular Synthon Ag 4 ⊂CCCC⊃Ag 4

A series of 13 silver(I) double and multiple salts containing 1,3‐butadiynediide, C 4 2− , were synthesized by dissolving the silver carbide Ag 2 C 4 in a concentrated aqueous solution of one or more of the silver salts AgNO 3 , AgCF 3 CO 2 , AgC 2 F 5 CO 2 , AgF, AgBF 4 , and AgPF 6 . The 1,3‐butadiynediide anion invariably adopts a μ 4 ,μ 4  coordination mode in these compounds, which indicates that the Ag 4 ⊂CCCC⊃Ag 4 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 Ag 4 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: σ, π, and mixed (σ,π). The effect of coexisting nitrile ligands and quaternary ammonium salts on supramolecular assembly with the above synthon was also explored. The hydrolysis of PF 6 − and BF 4 − led to the formation of the quadruple salt Ag 2 C 4 ⋅4 AgNO 3 ⋅AgPF 2 O 2 ⋅Ag 3 PO 4 and a novel (F) 2 (H 2 O) 18 hydrogen‐bonded tape in the triple salt Ag 2 C 4 ⋅2 AgF⋅ 10 AgC 2 F 5 CO 2 ⋅CH 3 CN⋅12 H 2 O, respectively. The largest silver–ethynide cluster aggregate described to date, (C 4 ) 3 @Ag 18 , occurs in 3 Ag 2 C 4 ⋅ 12 AgC 2 F 5 CO 2 ⋅5[(BnMe 3 N)C 2 F 5 CO 2 ]⋅ 4 H 2 O (Bn=benzyl).