Bipyrimidine-bridged trimetallic complexes of the form {[(bpy)(2)Ru(bpm)](2)MCl(2)}(5+), where M = Rh-III or Ir-III, bpy = 2,2’-bipyridine, and bpm = 2,2’-bipyrimidine, have been synthesized and characterized. These complexes are of interest in that they couple catalytically active rhodium(III) and iridium(III) metals with light-absorbing ruthenium(II) metals within a polymetallic framework. Their molecular composition is a light absorber-electron collector-light absorber core of a photochemical molecular device (PMD) for photoinitiated electron collection. The variation of the central metal has some profound effects on the observed properties of these complexes. The electrochemical data for the title trimetallics consist of a Ru-II/III oxidation and sequential reductions assigned to the bipyrimidine ligands, Ir or Rh metal centers, and bipyridines. In both trimetallic complexes, the first oxidation is Ru based and the bridging ligand reductions occur prior to the central metal reduction. This illustrates that the highest occupied molecular orbital (HOMO) is localized on the ruthenium metal center and the lowest unoccupied molecular orbital resides on the bpm ligand. This bpm-based LUMO in {[(bpy)(2)Ru(bpm)]2RhCl2}(5+) is in contrast with that observed for the monometallic [Rh(bpm)(2)Cl-2](+) where the Rh-III/Rh-I reduction occurs prior to the bpm reduction. This orbital inversion is a result of bridge formation upon construction of the trimetallic complex. Both the Ir- and Rh-based trimetallic complexes exhibit a room temperature emission centered at 800 nm with tau = 10 ns. A detailed comparison of the spectroscopic, electrochemical, and spectroelectrochemical properties of these polymetallic complexes is described herein.