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(C25H2ON2O2)(ClO4)].3.5C(6)H(6) (1), [Ag-2(mu-C31H24N4) (eta(2)-C6H6)(H2O)](ClO4)(2).(C6H6).(H2O)(0.5) (3), [Ag(C31H24N4)]SbF6.solvate (4), [Ag(C31H24N4)](SbF6)(2).2C(6)H(6).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(l)containing polymeric compounds 6 and 7.