Architectural Diversity for Anion-Mediated Self-Assembly of Four Pairs of Silver(I) Polymeric Isomers Having Linear and V‑Shaped Imidazole/Thiophene/Imidazole Bridging Spacers

A pair of linear and V-shaped acceptor–donor–acceptor (A–D–A) thiophene-based diazole structural isomers [i.e., 2,5-di­(1H-imidazol-1-yl)­thiophene (L1) and 3,4-di­(1H-imidazol-1-yl)­thiophene (L2)] have been used as bidentate bridging ligands to build Ag­(I) fluorescent and semiconducting coordination polymers in the presence of different counterions. X-ray single-crystal diffraction analyses for eight complexes 1–8 reveal that they are four pairs of polymeric isomers formulated as {[Ag­(L1)­(CF3COO)]}n (1), {[Ag­(L2)­(CF3COO)]}n (2), [Ag­(L1)­(NO3)]n (3), {[Ag­(L2)­(NO3)]·(H2O)}n (4), [Ag­(L1)­(ClO4)]n (5), {[Ag­(L2)]­(ClO4)}n (6), {[Ag­(L1)­(CH3CN)]­(PF6)}n (7), and {[Ag­(L2)]­(PF6)·(CH3CN)}n (8). They exhibit abundant structural diversity, namely, a one-dimensional (1D) dimeric chain 1, a double-strand helix 2, a cosinelike chain 3, wavelike chains 4 and 8, linear chains 5 and 7, and a zigzag chain 6 because of the alterations of conformation for μ2 bridging ligands L1 and L2 (cis/cis, cis/trans, and trans/trans) and the participancy of different counterions (CF3COO–, NO3–, ClO4–, and PF6–). It is noted that weak Ag­(I)–thiophene coordinative bonds are observed in the case of 7 with the Ag–S distance of 3.057(4) Å, which lead to a 13.8× enhancement of solid-state conductivity in comparison with the semiconducting single crystal of 8 at room temperature.