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Luminescent PtII(bipyridyl)(diacetylide) Chromophores with Pendant Binding Sites as Energy Donors for Sensitised Near-Infrared Emission from Lanthanides: Structures and Photophysics of PtII/LnIII Assemblies

Ronson, Tanya K., Lazarides, Theodore, Adams, Harry, Pope, Simon J. A., Sykes, Daniel, Faulkner, Stephen, Coles, Simon J., Hursthouse, Michael B., Clegg, William, Harrington, Ross W. and Ward, Michael D. 2006. Luminescent PtII(bipyridyl)(diacetylide) Chromophores with Pendant Binding Sites as Energy Donors for Sensitised Near-Infrared Emission from Lanthanides: Structures and Photophysics of PtII/LnIII Assemblies. Chemistry - a European Journal 12 (36) , pp. 9299-9313. 10.1002/chem.200600698

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Abstract

The complexes [Pt(bipy){CC-(4-pyridyl)}2] (1) and [Pt(tBu2bipy){CC-(4-pyridyl)}2] (2) and [Pt(tBu2-bipy)(CC-phen)2] (3) all contain a Pt(bipy)(diacetylide) core with pendant 4-pyridyl (1 and 2) or phenanthroline (3) units which can be coordinated to {Ln(diketonate)3} fragments (Ln = a lanthanide) to make covalently-linked PtII/LnIII polynuclear assemblies in which the PtII chromophore, absorbing in the visible region, can be used to sensitise near-infrared luminescence from the LnIII centres. For 1 and 2 one-dimensional coordination polymers [1⋅Ln(tta)3]∞ and [2⋅Ln(hfac)3]∞ are formed, whereas 3 forms trinuclear adducts [3⋅{Ln(hfac)3}2] (tta=anion of thenoyl-trifluoroacetone; hfac=anion of hexafluoroacetylacetone). Complexes 1–3 show typical PtII-based 3MLCT luminescence in solution at ≈510 nm, but in the coordination polymers [1⋅Ln(tta)3]∞ and [2⋅Ln(hfac)3]∞ the presence of stacked pairs of PtII units with short Pt⋅⋅⋅Pt distances means that the chromophores have 3MMLCT character and emit at lower energy (≈630 nm). Photophysical studies in solution and in the solid state show that the 3MMLCT luminescence in [1⋅Ln(tta)3]∞ and [2⋅Ln(hfac)3]∞ in the solid state, and the 3MLCT emission of [3⋅{Ln(hfac)3}2] in solution and the solid state, is quenched by Pt→Ln energy transfer when the lanthanide has low-energy f–f excited states which can act as energy acceptors (Ln=Yb, Nd, Er, Pr). This results in sensitised near-infrared luminescence from the LnIII units. The extent of quenching of the PtII-based emission, and the Pt→Ln energy-transfer rates, can vary over a wide range according to how effective each LnIII ion is at acting as an energy acceptor, with YbIII usually providing the least quenching (slowest Pt→Ln energy transfer) and either NdIII or ErIII providing the most (fastest Pt→Ln energy transfer) according to which one has the best overlap of its f–f absorption manifold with the PtII-based luminescence.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Uncontrolled Keywords: crystal structures; energy transfer; lanthanides; luminescence; platinum
Publisher: Wiley-Blackwell
ISSN: 0947-6539
Last Modified: 04 Jun 2017 04:37
URI: http://orca.cf.ac.uk/id/eprint/41626

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