A Ru(II) complex, Ru(alpha2beta), with a trisbipyridyl core and two different receptor sites, alpha- and beta-cyclodextrins, acts as a junction to recognize photoactive guests based on anthracene, Anth, and Os(II), Os-ada, in aqueous solution. Upon light excitation of the self-assembled system Anth.Ru(alpha2beta).Os-ada, an energy cascade process takes place from the Anth guest to the Ru(alpha2beta) core, and subsequently, the energy is funneled to the Os-ada guest. The rates of the two photoinduced processes are determined by time-resolved emission and transient absorption spectroscopic techniques. The system introduces a directed self-assembly approach to unidirectional wires that can lead to nanosized arrays by judicious selection of the individual components.