Three Silver(I) Coordination Polymers Constructed from Flexible Bis(benzimidazole) and Carboxylates Ligands

Under hydrothermal conditions, three new Ag I coordination polymers, [Ag(L1)(Hmip)] n ( 1 ), [Ag(L2) 0.5 (ndc) 0.5 ] n ( 2 ), and {[Ag(L3) 0.5 (Htbi)] · 0.25H 2 O} n ( 3 ) [H 2 mip = 5‐methylisophthalic acid, L1 = 1,4‐bis(2‐methylbenzimidazol‐1‐ylmethyl)benzene, H 2 ndc = 2,6‐naphthalenedicarboxylic acid, L2 = 1,3‐bis(2‐methylbenzimidazol‐1‐ylmethyl)benzene, H 2 tbi = 5‐ tert ‐butyl isophthalic acid, L3 = 1,4‐bis(5,6‐dimethylbenzimidazole)butane] were synthesized by employing flexible bis(benzimidazole) and dicarboxylic acid ligands. Polymer 1 displays a 2D 4‐connected 4L2 underlying net topology with the point symbol of (6 5 .8) in standard representation. Compound 2 possesses a 2D uninodal 4‐connected Shubnikov tetragonal plane net (sql) based on a dinuclear Ag I clusters with the point symbol (4 4 .6 2 ), which is further extended into a 3D supramolecular framework by π–π interactions. Compound 3 possesses dinuclear molecular complex groups, which form chains by weak Ag–O (2.6 Å) coordination bonds, and further assembled into a 2D supramolecular layer by hydrogen bonds and π–π stacking interactions. These complexes exhibit intense fluorescent emissions in solid state. UV/Vis diffuse reflection spectra and the excellent catalytic activity for the degradation of the congo red azo dye in a Fenton‐like process are discussed.