Surface-Confined Heterometallic Molecular Dyads: Merging the Optical and Electronic Properties of Fe, Ru, and Os Terpyridyl Complexes

Molecular assemblies of surface-confined heterometallic molecular dyads (SURHMDs) composed of optically rich and redox-active Fe(pytpy)(2)center dot 2PF(6) (Fe-PT), Ru(pytpy)(2)center dot 2PF(6) (Ru-PT) and Os(pytpy)(2)center dot 2PF(6) (Os-PT) pytpy = 4'-(4-pyridyl)-2,2':6',2 ''-terpyridyl] complexes are fabricated via bottom-up approach on SiOx based solid supports. Pairing of the two different metal-organic complexes at a single platform results in significant enlargement of the optical window (lambda = 400-800 nm), which can be of interest for potential applications. The use of the Cu-based linker ensures intramolecular electronic communication between these complexes. In addition, SURHMDs are electrochemically stable under large numbers of read-write cycles (10(3)) and exhibit multiple redox states at relatively low potentials (<1.2 V). Moreover, an electrochemical input at controlled potentials creates a mixed-valence multicomponent system.