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 synthesiz ed and characterized in this paper. Treatment of AgClO4.H2O with 7-methylbe nzo[a] pyrene (L-1) afforded [Ag-2(L-1) (toluene)(0.5)(ClO4)(2)](n) (1) whi ch exhibits a 2-D sheet structure with double-stranded helical motifs. Reac tion of AgCF3SO3 with dibenzo[b,def]chrysene (L-2) gave rise to an unpreced ented cocrystallization structure, {[Ag-2(L-2)(CF3SO3)(2)][Ag-2(toluene)(2) (CF3SO3)(2)]}(n) (2)1 formed by a 2-D neutral lamellar polymer and a 1 D ne utral rodlike one. The ligand benzo[e]pyrene (L-3) coordinated to silver(I) ions generating a closed triple-decker tetranuclear complex [Ag-4(L-3)(4)( p-xylene)(ClO4)(4)] (3) which can be regarded as a stacking polymer owing t o existing intermolecular pi-pi stack interactions. The structural diversit y of the silver(I) coordination polymers with polycyclic aromatic hydrocarb ons is not only related to the stacking patterns of free polycyclic aromati c hydrocarbons in the crystalline state, but also the geometric shapes of t he molecules for these free ligands. In addition, the coordination of solve nts to metal ions plays a crucial role in the formation of the unprecedente d coordination polymeric architectures. The ESR spectroscopic results, cond uctivity, and synthesis properties are also discussed.