Pyridine and benzonitrile adducts of bis(4-nonafluorobiphenyl)zinc

Treatment of (Ar_F')₂Zn(OEt₂)₂ (Ar_F' = 4-C₆F₅C₆F₄) with 2 equiv. of benzonitrile, 4-(phenyl)benzonitrile, 4-(pyrrolyl)benzonitrile, pyridine, 4-(phenyl)pyridine or 4-(pyrrolyl)pyridine in dichloromethane afforded the corresponding adducts (Ar_F')₂ZnL₂ in near quantitative yield. The 2,2'-bipyridine adduct was prepared similarly. Multinuclear NMR spectroscopy indicated that zinc's four-coordinate character was maintained in solution. The pyridine complex crystallized from dichloromethane with a solid-state structure free of face-to-face aryl–aryl interactions. In contrast, the 4-(pyrrolyl)pyridine adduct crystallized from both dichloromethane and 1,2-difluorobenzene, with solvent of crystallization, but otherwise essentially identical supramolecular architectures assembled through aryl–aryl synthons, including a face-to-face pentafluorophenyl–pyrrole interaction.