A novel fulvene-type bidentate ligand 1 has been synthesized by an aroylation reaction of cyclohexyl-substituted cyclopentadienyl anions. Compound 1 crystallizes in the triclinic space group P (1) over bar, with a = 7.0419(5) Angstrom, b = 11.9360(8) Angstrom, c = 15.6470(11) Angstrom, alpha = 85.1440(10)degrees, beta = 78.1140(10)degrees, gamma = 74.5360(10)degrees, V= 1239.76(15) Angstrom(3), and Z = 2. The coordination chemistry of 1 was investigated, and a novel Ag-containing coordination polymer (2), linked by both Ag-heteroatom and Ag-carbon interactions, has been synthesized. The coordination polymer has been fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Compound 2 crystallizes in the triclinic space group P (1) over bar, with a = 7.1654(5) Angstrom, b = 15.7277(11) Angstrom, c = 18.8157(13) Angstrom, alpha = 73.5150(10)degrees, beta = 89.0410(10)degrees, gamma = 89.0970(10)degrees, V = 1355.19(14) Angstrom(3), and Z = 2. The solid-state structure of 2 features a one-dimensional double-chain motif. These double chains are in turn cross-linked to each other via strong interchain O-H...O hydrogen bonds, forming a novel two-dimensional network with remarkably large cavities (effective cross section of ca. 21 x 15 Angstrom) that are occupied by benzene guest molecules. Both compounds 1 and 2 are luminescent in the solid state, and a large blue-shift in the emission between the free ligand 1 and the ligand incorporated into complex 2 is observed.