4'-(Ferrocenyl)-2,2':6',2 "-terpyridine (Fctpy) and 4'-(4-pyridyl)-2,2':6',2 "-terpyridine (pytpy) were prepared from the corresponding ferrocene- and pyridinecarboxaldehyle and 2-acetylpyridine using the Krohnke synthetic methodology. Metal complexes, [M(Fctpy)(2)](PF6)(2) (M = Ru, Fe, Zn), [Ru(tpy)(Fctpy)](PF6)(2) (tpy = 2,2':6',6 "-terpyridine), and [Ru(pytpy)(2)](PF6)(2) were prepared and characterized. Cyclic voltammetric analysis indicated Ru-III/II and ferrocenium/ferrocene redox couples near expected potentials (Ru-III/II similar to 1.3 V and ferrocenium/ferrocene similar to 0.6 V vs Ag/AgCl). In addition to dominant pi(tpy) --> pi(tpy)* UV absorptions near 240 and 280 nm and d(pi)(Ru) --> pi(tpy)* MLCT absorptions around 480 nm, the complexes [Ru(Fctpy)(2)](PF6)(2) and [Ru(tpy)(Fctpy)](PF6)(2) exhibit an unusual absorption band around 530 nm. Resonance Raman measurements indicate that this band is due to a (1)[(d(pi)(Fc))(6)] --> (1)[(d(pi)(Fc))(5)(pi*(Ru)(tpy))(1)] transition. For [Ru(Fctpy)(2)](PF6)(2) and [Ru(tpy)(Fctpy)](PF6)(2), excited-state emission and lifetime measurements indicated an upper-limit emission quantum yield of 0.003 and an upper-limit emission lifetime of 0.025 mu s. The influence of the ferrocenyl site on excited-state decay is discussed, and an excited-state energy level diagram is proposed.