In this article, we describe a series of new complex salts in which electron-rich transition-metal centers are coordinated to three electron-accepting N-methyl/aryl-2,2':4,4":4',4"'-quaterpyridinium ligands. These complexes contain either Ru-II or Fell ions and have been characterized by using various techniques, including electronic absorption spectroscopy and cyclic voltammetry. Molecular quadratic nonlinear optical (NLO) responses beta have been determined by using hyper-Rayleigh scattering at 800 nm and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d -> pi* metal-to-ligand charge-transfer bands. The latter experiments reveal that these putatively octupolar D-3 chromophores exhibit two substantial components of the beta tensor which are associated with transitions to dipolar excited states. Computations involving time-dependent density-functional theory and the finite field method serve to further illuminate the electronic structures and associated linear and NLO properties of the new chromophoric salts.