Spiral, herringbone, and triple-decker silver(I) complexes of benzopyrene derivatives assembled through eta(2)-coordination

Three novel silver(I) complexes with benzopyrene derivatives were synthesized and characterized in this paper. Treatment of AgClO(4)*H(2)O with 7-methylbenzoa]pyrene (L(1)) afforded Ag(2)(L(1))(toluene)(0.5)(ClO(4))(2)](n)() (1) which exhibits a 2-D sheet structure with double-stranded helical motifs. Reaction of AgCF(3)SO(3) with dibenzob,def ]chrysene (L(2)) gave rise to an unprecedented cocrystallization structure, (Ag(2)(L(2))(CF(3)SO(3))(2)]Ag(2)(toluene)(2)(CF(3)SO(3))(2)])(n)() (2), formed by a 2-D neutral lamellar polymer and a 1-D neutral rodlike one. The ligand benzoe]pyrene (L(3)) coordinated to silver(I) ions generating a closed triple-decker tetranuclear complex Ag(4)(L(3))(4)(p-xylene)(ClO(4))(4)] (3) which can be regarded as a stacking polymer owing to existing intermolecular pi-pi stack interactions. The structural diversity of the silver(I) coordination polymers with polycyclic aromatic hydrocarbons is not only related to the stacking patterns of free polycyclic aromatic hydrocarbons in the crystalline state, but also the geometric shapes of the molecules for these free ligands. In addition, the coordination of solvents to metal ions plays a crucial role in the formation of the unprecedented coordination polymeric architectures. The ESR spectroscopic results, conductivity, and synthesis properties are also discussed.