Spiral, Herringbone, and Triple-Decker Silver(I) Complexes of Benzopyrene Derivatives Assembled through η²-Coordination

Abstract

Three novel silver(I) complexes with benzopyrene derivatives were synthesized and characterized in this paper. Treatment of AgClO(4)*H(2)O with 7-methylbenzo[a]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 dibenzo[b,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 benzo[e]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.

Mesomorphism of Four-Coordinated Four-Chained Metal Complexes Based on Pyrazolylpyridine Derivatives

“…1260 and 1035 cm À1 in agreement with the presence of a OTf À group coordinated to the silver atom [13,15]. Taking into account these results, as well as the structural analysis of the similar complex [Ag(pz bp2 py) 2 ][OTf] which exhibited a fivecoordinated metal environment produced by coordination of two pz bp2 py ligands and the OTf À anion (Fig.…”

Solvent-vapour-assisted pathways and the role of pre-organization in solid-state transformations of coordination polymers

“…The one-dimensional tapes are crosslinked via toluene molecules, which bridge silver(I) centres in a -1 , 1 manner. Although there are many examples ofcoordination to Ag(I) centres, to the best of our knowledge, this toluene bridging mode has not previously been observed, although bridging in a -2 , 2 fashion has been reported (Zhong et al, 2001). The cross-linking creates two-dimensional layers of silver coordination polymer, with an additional two toluene molecules per formula unit residing between the layers (Fig.…”

Synthesis and Molecular Structures of the Cationic Silver Complexes of the Polycondensed Aromatics Fluorene, Pseudorubrene, and Truxene

“…In analogy to 1 , a two‐dimensional herringbone arrangement was reported for {[(L DBC )Ag 2 (Tfl) 2 ][(tol) 2 Ag 2 (Tfl) 2 ]} n and {[(L NPyr )Ag 2 (Tfl) 2 ]} n , in which two AgTfl units coordinate towards dibenzo[ b , def ]‐chrysene (L DBC ) and toluene (tol) and towards naphtho[2,3‐ a ]pyrene (L NPyr ). As reported for the crystal packing of the free fluorene ligand, the Ag I coordination mode towards fluorene in 1 maintains the herringbone pattern with an inclination angle of about 82° (Figure b) and a shortest π–π distance of 337 pm [C3(I)–C9(II)] between two stacked fluorene molecules I and II (Figure a,b).…”

“…Atomic numbering scheme for pseudorubrene in bis[(η 2 ‐pseudorubrene)(η 2 ‐toluene)AgClO 4 ] · toluene solv ( 2 ). For comparative NMR spectroscopic data of the free L Psrub , see ref …”