[Ru(bipy)3]2+ and [Os(bipy)3]2+ chromophores as sensitisers for near-infrared luminescence from Yb(III) and Nd(III) in d/f dyads: contributions from Förster, Dexter, and redox-based energy-transfer mechanisms (Articolo in rivista)

Type
Label
  • [Ru(bipy)3]2+ and [Os(bipy)3]2+ chromophores as sensitisers for near-infrared luminescence from Yb(III) and Nd(III) in d/f dyads: contributions from Förster, Dexter, and redox-based energy-transfer mechanisms (Articolo in rivista) (literal)
Anno
  • 2009-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1039/b901560d (literal)
Alternative label
  • T. Lazarides; N. M. Tart; D. Sykes; S. Faulkner; A. Barbieri; M. D. Ward (2009)
    [Ru(bipy)3]2+ and [Os(bipy)3]2+ chromophores as sensitisers for near-infrared luminescence from Yb(III) and Nd(III) in d/f dyads: contributions from Förster, Dexter, and redox-based energy-transfer mechanisms
    in Dalton transactions (2003. Print)
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • T. Lazarides; N. M. Tart; D. Sykes; S. Faulkner; A. Barbieri; M. D. Ward (literal)
Pagina inizio
  • 3971 (literal)
Pagina fine
  • 3979 (literal)
Rivista
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroFascicolo
  • 20 (literal)
Note
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • 1. CNR, Ist ISOF, I-40129 Bologna, Italy 2. Univ Sheffield, Dept Chem, Sheffield S3 7HF, S Yorkshire, England 3. Univ Manchester, Dept Chem, Manchester M13 9PL, Lancs, England (literal)
Titolo
  • [Ru(bipy)3]2+ and [Os(bipy)3]2+ chromophores as sensitisers for near-infrared luminescence from Yb(III) and Nd(III) in d/f dyads: contributions from Förster, Dexter, and redox-based energy-transfer mechanisms (literal)
Abstract
  • Complexes RuL and OsL contain [M(bipy)3](2+) chromophores with a pendant aza-18-crown-6 macrocycle for binding of lanthanide(III) ions. The photophysical properties of the adducts RuL.Ln and OsL.Ln, prepared by addition of excess Ln(NO(3))(3) (Ln = Nd, Yb) to solutions of RuL and OsL in MeCN, were examined using time-resolved and steady-state luminescence methods. Whereas RuL does not act as an energy-donor to Yb(III), it will transfer energy to (and generate sensitised near-infraredluminescence from) Nd(III) with a Ru(II). Nd(III) energy-transfer rate constant of 6.8 106 s(-1). In contrast, OsL is quenched by both Yb(III) and Nd(II), but with faster energy-transfer to Yb(III) (2.6 x 10(7) s(-1)) than to Nd(III) (1.4 x 10(7) s(-1)). Thus d -> energy transfer is in both cases faster for Os(II) than for Ru(II), but the relative ability of Nd(III) and Yb(III) to act as energy-acceptors is inverted from RuL.Ln to OsL.Ln. Reasons for this are discussed with reference to contributions from the Forster and Dexter mechanism for energy-transfer in RuL.Nd and OsL.Nd, using calculated spectroscopic overlap integrals coupled with molecular modelling to estimate inter-chromophore separations. The particular effectiveness of Os(II) -> Yb(III) energy-transfer in OsL.Yb is explained in terms of the Horrocks redox mechanism involving an initial *Os(II) -> Yb(III) photoinduced electron transfer step generating an Os(III)/Yb(II) state, which is shown to be marginally favourable for OsL.Yb, but not for RuL center dot Yb in which the [Ru(bipy)(3)](2+) unit is a poorer excited- state electron-donor by about 0.1 eV. (literal)
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