Polyyn-diyls capped by Ru(2)(ap)(4) termini (ap = 2-anilinopyridinate), that is, [Ru2(ap)4](mu-C,C'-C2m)[Ru2(ap)4] (compounds 1-5 with m = 1-4 and 6), were synthesized through either a metathesis reaction between Ru2(ap)4Cl and LiC(2m)Li or a Glaser homocoupling reaction of Ru2(ap)4(CmH) under Eglinton/Hay conditions. X-ray diffraction studies of compounds 2 and 4 revealed both the linear rigid rod topology of these compounds and the fine structural details about the Ru2 cores and polyyn-diyl chains. Cyclic and differential pulse voltammetric (CV and DPV) measurements and spectroelectrochemical studies show that reduced and oxidized forms of 1, 2, 4, and 5 are donor-acceptor systems in which the Ru2 termini are coupled to varying degrees depending upon the length of the polyyn-diyl bridge.

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...Fc distances, established through single-crystal X-ray diffraction studies, range from 11.6 to 16.6 A. 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.