Energy Transfer by a Hopping Mechanism in Dinuclear IrIII/RuII Complexes: A Molecular Wire?

Abstract

The synthesis and electrochemical and photophysical properties of a series of heterodinuclear ruthenium–iridium complexes linked by a modular para-phenylene bridge [Ir–ph_n–Ru]³⁺ (Ir=Ir(ppyFF)₂bpy, Ru=Ru(bpy)₃, ppyFF=2-(2,4-difluorophenyl)pyridine), bpy=2,2′-bipyridine, ph=phenylene, n=2, 3, 4, 5) are reported. The use of a high-energy iridium complex, which can act as an energy donor when coupled to the lower energy ruthenium-based component, allows the investigation of photoinduced energy transfer from the excited iridium-centre to the ruthenium fragment (energy acceptor). The rate constants of the energy-transfer processes are determined by time-resolved emission and sub-picosecond transient absorption spectroscopy. Interestingly, there is almost no decrease in transfer efficiency or rates as the length between the two chromophores (number of spacers) is increased. This “molecular wire” behavior indicates the dominance of the incoherent hopping mechanism, allowing a very fast energy transfer over long distances (with n=5 the metal-to-metal distance is estimated to be 32.5 Å). This is the first case in which such behavior is observed for metal complexes, and could lead to new development in molecular electronics.