The initial employment of the fluorescent bridging ligand N-naphthalidene-2-amino-5-chlorobenzoic acid (nacbH(2)) in metal cluster chemistry has led to new Ni-12 (1) and Ni-5 (2) clusters with wheel-like and molecular chain topologies, respectively. The doubly-deprotonated nacb(2-) ligands were found to adopt four different coordination modes within 1 and 2. The nature of the ligand has also allowed unexpected organic transformations to occur and ferromagnetic and emission behaviors to emerge. The combined work demonstrates the ability of some "ligands-with-benefits" to yield beautiful structures with exciting topologies and interesting physicochemical properties.