Betaine-induced assembly of neutral infinite columns and chains of linked silver(I) polyhedra with embedded acetylenediide

Ten polymeric silver(I) double salts containing embedded acetylenediide: (Ag2C2)2(AgCF3CO2)9(L1)3] (1), (Ag2C2)2(AgCF3CO2)10(L2)3]H2O (2), (Ag2C2)(AgCF3CO2)4(L3)(H2O)]0.75 H2O (3), (Ag2C2)(1.5)(AgCF3CO2)7(L4)2] (4), (Ag2C2)(AgCF3CO2)7(L5)2(H2O)] (5), (Ag2C2) (AgC2F5CO2)7(L1)3(H2O)] (6), (Ag2C2)(AgCF3CO2)7(L1)3(H2O)]2 H2O (7), (Ag2C2)(AgC2F5CO2)6(L3)2] (8), (Ag2C2)2(AgC2F5CO2)12(L4)2(H2O)4]H2O (9), and (Ag2C2)(AgCF3CO2)6(L3)2(H2O)]H2O (10) have been isolated by varying the types of betaines, the perfluorocarboxylate ligands employed, and the reaction conditions. Single-crystal X-ray analysis has shown that 1-4 all have a columnar structure composed of fused silver(I) double cages, with C2(2-) species embedded in its stem and an exterior coat comprising anionic and zwitterionic carboxylates. For 5 and 6, single silver(I) cages are linked into a beaded chain through both types of carboxylate ligands. In 7, two different coordination modes of L1 connect the silver(I) polyhedra into a chain. For 8, the mu(2)-O,O' coordination mode of L3 connects the silver(I) double cages into a chain. Compound 9 exhibits a two-dimensional architecture generated from the cross-linkage of double cages by C2F5CO2-, L4, and Ag2(C2F5CO2)2] units. Similar to 9, 10 is also a two-dimensional structure, which is formed by connecting the chains of linked double cages through Ag2(CF3CO2)2] bridging.