A series of trans-(FcC(2n))Ru-2(Y-DMBA)(4)(C(2m)Fc) with n, m = 1 and 2 and Y-DMBA as N,N'-dimethylbenzamidinate or N,N'-dimethyl-(3-methoxy)benzamidinate have been synthesized and characterized. The intramolecular Fc center dot center dot center dot Fc distances, established through single-crystal X-ray diffraction studies, range from 11.6 to 16.6 angstrom. Results from both voltammetric and spectroelectrochemical studies indicate that the (-C-2n)Ru-2(Y-DMBA)(4)(C-2m-) fragments are among the most efficient mediators of intramolecular hole transfer. Density-functional calculations offer both the insight on the ground-state electronic properties and unambiguous assignment for the observed electronic absorptions.