A mixed-metal supramolecular complex [{(bpy)(2)Ru(dpp)}(2)RhCl2](5+) has been studied and shown to undergo photoinitiated electron collection at the metal center. Reported herein is an analysis of the photochemical properties of this complex, illustrating the ability of this complex to photoreduce by two electrons by converting Rh-III to Rh-I and with the trimetallic assembly remaining intact. Emission-quenching experiments demonstrate efficient quenching of the Ru -> dpp charge-transfer state by the Rh center and the electron-donor dimethylaniline.