title: Luminescent Pt(II)(bipyridyl)(diacetylide) chromophores with pendant binding sites as energy donors for sensitised near-infrared emission from lanthanides: structures and photophysics of Pt(II)/Ln(III) assemblies.
abstract: The complexes [Pt(bipy){CC-(4-pyridyl)}(2)] (1) and [Pt(tBu(2)bipy){CC-(4-pyridyl)}(2)] (2) and [Pt(tBu(2)-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 Pt(II)/Ln(III) polynuclear assemblies in which the Pt(II) chromophore, absorbing in the visible region, can be used to sensitise near-infrared luminescence from the Ln(III) centres. For 1 and 2 one-dimensional coordination polymers [1Ln(tta)(3)](infinity) and [2Ln(hfac)(3)](infinity) 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 Pt(II)-based (3)MLCT luminescence in solution at approximately 510 nm, but in the coordination polymers [1Ln(tta)(3)](infinity) and [2Ln(hfac)(3)](infinity) the presence of stacked pairs of Pt(II) units with short PtPt distances means that the chromophores have (3)MMLCT character and emit at lower energy ( approximately 630 nm). Photophysical studies in solution and in the solid state show that the (3)MMLCT luminescence in [1Ln(tta)(3)](infinity) and [2Ln(hfac)(3)](infinity) in the solid state, and the (3)MLCT 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 Ln(III) units. The extent of quenching of the Pt(II)-based emission, and the Pt-->Ln energy-transfer rates, can vary over a wide range according to how effective each Ln(III) ion is at acting as an energy acceptor, with Yb(III) usually providing the least quenching (slowest Pt-->Ln energy transfer) and either Nd(III) or Er(III) providing the most (fastest Pt-->Ln energy transfer) according to which one has the best overlap of its f-f absorption manifold with the Pt(II)-based luminescence.
authors.affiliation: Department of Chemistry, University of Sheffield, Sheffield S3 7HF, UK.
authors.forename: Tanya K
authors.initials: TK
authors.lastname: Ronson
authors.forename: Theodore
authors.initials: T
authors.lastname: Lazarides
authors.forename: Harry
authors.initials: H
authors.lastname: Adams
authors.forename: Simon J A
authors.initials: SJ
authors.lastname: Pope
authors.forename: Daniel
authors.initials: D
authors.lastname: Sykes
authors.forename: Stephen
authors.initials: S
authors.lastname: Faulkner
authors.forename: Simon J
authors.initials: SJ
authors.lastname: Coles
authors.forename: Michael B
authors.initials: MB
authors.lastname: Hursthouse
authors.forename: William
authors.initials: W
authors.lastname: Clegg
authors.forename: Ross W
authors.initials: RW
authors.lastname: Harrington
authors.forename: Michael D
authors.initials: MD
authors.lastname: Ward
mesh_terms: D001665:Binding Sites; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D049449:Luminescence; D008958:Models, Molecular; D015394:Molecular Structure; D017671:Platinum Compounds / Q000737:chemistry*; D019265:Spectroscopy, Near-Infrared
chemical_list: D028581:Lanthanoid Series Elements; D017671:Platinum Compounds