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: [(Ag 2 C 2 ) 2 (AgCF 3 CO 2 ) 9 (L 1 ) 3 ] ( 1 ), [(Ag 2 C 2 ) 2 (AgCF 3 CO 2 ) 10 (L 2 ) 3 ]⋅H 2 O ( 2 ), [(Ag 2 C 2 )(AgCF 3 CO 2 ) 4 (L 3 )(H 2 O)]⋅0.75 H 2 O ( 3 ), [(Ag 2 C 2 ) 1.5 (AgCF 3 CO 2 ) 7 (L 4 ) 2 ] ( 4 ), [(Ag 2 C 2 )(AgCF 3 CO 2 ) 7 (L 5 ) 2 (H 2 O)] ( 5 ), [(Ag 2 C 2 ) (AgC 2 F 5 CO 2 ) 7 (L 1 ) 3 (H 2 O)] ( 6 ), [(Ag 2 C 2 )(AgCF 3 CO 2 ) 7 (L 1 ) 3 (H 2 O)]⋅2 H 2 O ( 7 ), [(Ag 2 C 2 )(AgC 2 F 5 CO 2 ) 6 (L 3 ) 2 ] ( 8 ), [(Ag 2 C 2 ) 2 (AgC 2 F 5 CO 2 ) 12 (L 4 ) 2 (H 2 O) 4 ]⋅H 2 O ( 9 ), and [(Ag 2 C 2 )(AgCF 3 CO 2 ) 6 (L 3 ) 2 (H 2 O)]⋅H 2 O ( 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 C 2 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 L 1 connect the silver( I ) polyhedra into a chain. For 8 , the μ 2 ‐O,O′ coordination mode of L 3 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 C 2 F 5 CO 2 − , L 4 , and [Ag 2 (C 2 F 5 CO 2 ) 2 ] units. Similar to 9 , 10 is also a two‐dimensional structure, which is formed by connecting the chains of linked double cages through [Ag 2 (CF 3 CO 2 ) 2 ] bridging.