Syntheses and Structures of Ag(I)-Containing Coordination Polymers and Co(II)-Containing Supramolecular Complex Based on Novel Fulvene Ligands

Three new rigid conjugated fulvene ligands L1−L3 were synthesized. L1 and L3 have been prepared by an aroylation
reaction of cyclohexyl-substituted cyclopentadienyl anions. L2 was prepared by the reaction of L1 with PhNHNH2
in hot enthanol. Six new coordination polymers, namely [Ag(C25H20N2O2)(ClO4)]·3.5C6H6 (1), [Ag2(μ-C31H24N4)(η2-C6H6)(H2O)](ClO4)2·(C6H6)·(H2O)0.5 (3), [Ag(C31H24N4)]SbF6·solvate (4), [Ag(C31H24N4)](SbF6)2·2C6H6·CH2Cl2 (5), [Ag(C25H20N2O2)2]SbF6 (6), and [Ag(C25H20N2O2)2]SbF6 (7), and one seven-membered cobaltacycle-containing complex,
namely Co(C25H20N2O2)2(C2H5OH)2 (2), were obtained through self-assembly based on these three new fulvene
lignads. L2−L3 and compounds 1−7 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 bind metal ions not only through the terminal N-donors and fulvene carbon atoms into
organometallic coordination polymers but also through the two chelating carbonyl groups into unusual seven-membered metallo-ring supramolecular complexes. In the solid state, ligands L1−L3 are luminescent. A blue-shift
in the emission was observed between the free ligand L1 and the one incorporated into Co(II)-containing complex
2, and a red-shift in the emission was observed between the free ligand L3 and the one incorporated into Ag(I)-containing polymeric compounds 6 and 7.