Polyyn-diyls capped by Ru-2(ap)(4) termini (ap = 2-anilinopyridinate), that is, [Ru-2(ap)(4)](mu-C,C'-C-2m)[Ru-2(ap)(4)] (compounds 1-5 with m = 1-4 and 6), were synthesized through either a metathesis reaction between Ru-2(ap)(4)Cl and LiC2mLi or a Glaser homocoupling reaction of Ru-2(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 Ru-2 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 Ru-2 termini are coupled to varying degrees depending upon the length of the polyyn-diyl bridge.