The mild hydrothermal reaction of Cd, Zn, or Cu(II) acetate salts with the deprotonated flexible linker homophthalic acid (H 2hmph) and the rigid molecule 4,4′-bipyridine (bpy) produced the following complexes, featured structurally by the assembly of various metal carboxylate subunits cohered further by the bpy ancillary ligand: {[Cd 2(hmph) 2(bpy)(H 2O) 2]·H 2O} n ( 1) manifests cadmium carboxylate zigzag chain motifs, containing the alternation of a hmph-bridged Cd 2(hmph) 2 dimer and an edge-shared Cd 2N 4O 10 dimer, connected further by the bpy ligands to form a layered structure with a large 50-membered ring; [Zn(hmph)(bpy)] n ( 2) processes hmph-bridged Cd 2(hmph) 2 dimer motifs inter-linked further by the bpy ligands to generate mutually embedded layered structures with square (4,4) grids; and {[Cu(hmph)(bpy)]·H 2O} n ( 3) consists of copper carboxylate helix motifs, featuring hmph-bridged CuN 2O 4 octahedra cross-linked further by the bpy ligands into a twofold-interpenetrating 3D chiral framework with a homochiral topology of a quartz dual net. This well-defined synthetic system was proposed to highlight the fact that organic linkers display markedly different coordination preferences at specific metal ions. In addition, the fluorescence properties of complexes 1 and 2 were rationalized in terms of the local ligand environments in the crystal structures, and magnetic properties of complex 3 are also given.