Anion and Guest Directed Tetracyclic Macrocycles of Ag₅L₄ and Ag₆L₄ with an Arc-Shaped Ligand Containing Pyridine and Benzimidazole Units: Reversal of Anion Selectivity by Guest

An arc shaped tridentate ligand pyridine-3,5-bis­(1-methyl-benzimidazole-2-yl), L, and Ag­(I) were shown to form two isomers of Ag₅L₄ and Ag₆L₄ templated by ClO₄^– and CF₃SO₃^– anions, respectively, in DCM-MeOH. Further, the Ag₆L₄ cluster containing triflate was also found to form in the presence of nitrobenzene, toluene, and p-xylene. Interestingly, the presence of benzonitrile as guest exhibits reversal of anion selectivity that is perchlorate templated Ag₆L₄ while triflate templated Ag₅L₄. The guest exchange form the crystalline solid of Ag₆L₄ resulted in the solid-to-solid transformation to Ag₅L₄.