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. ORCID: https://orcid.org/0000-0001-9110-9711, 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

Full text not available from this repository.

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:	21 Oct 2022 10:53
URI:	https://orca.cardiff.ac.uk/id/eprint/41626

Citation Data

Cited 146 times in Scopus. View in Scopus. Powered By Scopus® Data

Actions (repository staff only)

Edit Item