title: On the mechanism of d-f energy transfer in RuII/LnIII and OsII/LnIII dyads: Dexter-type energy transfer over a distance of 20 A.
abstract: We have used time-resolved luminescence methods to study rates of photoinduced energy transfer (PEnT) from [M(bipy)3]2+ (M=Ru, Os) chromophores to Ln(III) ions with low-energy f-f states (Ln=Yb, Nd, Er) in d-f dyads in which the metal fragments are separated by a saturated -CH2CH2- spacer, a p-C6H4 spacer, or a p-(C6H4)2 spacer. The finding that d-->f PEnT is much faster across a conjugated p-C6H4 spacer than it is across a shorter CH2CH2 spacer points unequivocally to a Dexter-type energy transfer, involving electronic coupling mediated by the bridging ligand orbitals (superexchange) as the dominant mechanism. Comparison of the distance dependence of the Ru-->Nd energy-transfer rate across different conjugated spacers [p-C6H4 or p-(C6H4)2 groups] is also consistent with this mechanism. Observation of Ru-->Nd PEnT (as demonstrated by partial quenching of the RuII-based 3MLCT emission (MLCT=metal-to-ligand charge transfer), and the growth of sensitised NdIII-based emission at 1050 nm) over approximately 20 A by an exchange mechanism is a departure from the normal situation with lanthanides, in which long-range energy transfer often involves through-space Coulombic mechanisms.
authors.affiliation: Department of Chemistry, University of Sheffield, Sheffield S3 7HF, UK.
authors.forename: Theodore
authors.initials: T
authors.lastname: Lazarides
authors.forename: Daniel
authors.initials: D
authors.lastname: Sykes
authors.forename: Stephen
authors.initials: S
authors.lastname: Faulkner
authors.forename: Andrea
authors.initials: A
authors.lastname: Barbieri
authors.forename: Michael D
authors.initials: MD
authors.lastname: Ward