Two novel fulvene-type organic ligands L1 and L2 have been synthesized by aroylation reaction of substituted cyclopentadienyl anions. L1 crystallized in the monoclinic space group P2(1), a = 6.7498(4), b = 20.5769(11), c = 8.9532(5) Angstrom, beta = 109.5060(10)degrees, and Z = 2. L2 crystallized in the triclinic space qroup P (1) over bar, a = 11.4126(10), b = 11.4763(10), c = 11.7719(10) Angstrom, alpha = 67.050(2), beta = 74.509(2), gamma = 61.148(2)degrees, and Z = 2. The coordination chemistry of L1 and L2 has been investigated. One novel Ag-I-containing organometallic coordination polymer 3, based on both Ag-I-C and Ag-I-N interactions, has been synthesized by combination of L1 and AgClO4 in a benzene/dichloromethane mixed-solvent system. Two new M-II-containing [M = Cu-II (4) and Co-II (5)] supramolecular complexes with seven-membered metalla-ring unit have been prepared by combination of L2 and the corresponding M(OAc)(2).2H(2)O (M = CUII and Co-II) salts in ethanol. The isostructural compounds 4 and 5 crystallized in the triclinic space group P (1) over bar [4: a = 8.8808(5), b = 10.9928(7), c = 14.2196(9) Angstrom, alpha = 99.9750(10), beta = 95.8190(10), gamma = 93.5610(10)degrees, and Z = 1; 5: a = 8.7964(10), b = 10.8103(12), c = 14.3765(15) Angstrom, alpha = 99.681(2), beta = 95.930(2), gamma = 93.429(2)degrees, and Z = 1]. In the solid state, molecular complexes 4 and 5 are bound by strong intermolecular N...O-H hydrogen bonds in a hand-in-hand fashion to give a novel one-dimensional chain motif.