Organometallic Silver(I) Supramolecular Complexes Generated from Multidentate Furan-Containing Symmetric and Unsymmetric Fulvene Ligands and Silver(I) Salts

One new conjugated symmetric fulvene ligand L1 and two new unsymmetric fulvene ligands L2 and L3 were
synthesized. Five new supramolecular complexes, namely Ag2(L1)3(SO3CF3)3 (1) (1, monoclinic, P21/c; a = 12.702(3)
Å, b = 26.118(7) Å, c = 13.998(4) Å, β = 96.063(4)°, Z = 4), [Ag(L1)]ClO4 (2) (monoclinic, C2/c; a = 17.363(2)
Å, b = 13.2794(18) Å, c = 13.4884(18) Å, β = 100.292(2)°, Z = 8), [Ag(L1)(C6H6)SbF6]·0.5C6H6·H2O (3) (monoclinic,
P21/c; a = 6.8839(11) Å, b = 20.242(3) Å, c = 18.934(3) Å, β = 91.994(3)°, Z = 4), Ag(L2)(SO3CF3) (4)
(triclinic, P1̄; a = 8.629(3) Å, b = 10.915(3) Å, c = 11.178(3) Å, α = 100.978(4)°, β = 91.994(3)°, γ = 105.652(4)°,
Z = 2), and Ag(L3)(H2O)(SO3CF3) (5) (triclinic, P1̄; a = 8.914(5) Å, b = 10.809(6) Å, c = 11.283(6) Å, α =
69.255(8)°, β = 87.163(9)°, γ = 84.993(8)°, Z = 2) were obtained through self-assembly based on these three
new fulvene ligands in a benzene/toluene mixed-solvent system. Compounds 1−5 have been fully characterized
by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The results indicate that the
coordination chemistry of new fulvene ligands is versatile. They can adopt either cis- or trans-conformation to bind
soft acid Ag(I) ion through not only the terminal −CN and furan functional groups but also the fulvene carbon
atoms into organometallic coordination polymers or discrete complexes. In addition, the luminescent properties of
L1−L3 and their Ag(I) complexes were investigated preliminarily in EtOH and solid state.