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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

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
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
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 (I 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(II) 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 [1.Ln(tta)(3)](infinity) and [2(.)Ln(hfaC)(3)](infinity) are formed, whereas 3 forms trinuclear adducts [3(.){Ln(hfac)(3)}2] (tta anion of thenoyi-trifluoroacetone; hfac = anion of hexafluoroacetylacetone). Com-plexes 1-3 show typical Pt-II-based (MLCT)-M-3 luminescence in solution at approximate to 510 nm, but in the coordination polymers [1(.)Ln(tta)(3)](infinity) and [2(.)Ln(hfaC)(3)]infinity the presence of stacked pairs of Pt-II units with short (PtPt)-Pt-... distances means that the chromophores have (MMLCT)-M-3 character and emit at lower energy (approximate to 630 nm). Photophysical studies in solution and in the solid state show that the (MMLCT)-M-3 luminescence in [1.Ln(tta)(3)](infinity) and [2(.)Ln(htaC)(3)](infinity) in the solid state, and the (MLCT)-M-3 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.
crystal structures, energy transfer, lanthanides, luminescence, platinum, visible-light sensitization, bis-acetylide complexes, diimine complexes, er(iii) complexes, excited-states, spectroscopic properties, emitting materials, crystal-structures, enhanced emission, d-block
0947-6539
9299-9313
Ronson, Tanya K.
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Lazarides, Theodore
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Adams, Harry
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Pope, Simon J.A.
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Sykes, Daniel
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Faulkner, Stephen
f09826b1-0a36-4cf8-bfcf-f1ef98d27cc0
Coles, Simon J.
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Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Clegg, William
5b1994af-8799-4402-9c01-8479959de00b
Harrington, Ross W.
01d1f0bc-fc3e-43ae-a087-6cce0278128e
Ward, Michael D.
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Ronson, Tanya K.
55ed01a8-8ee9-433e-9def-5619e55e6a29
Lazarides, Theodore
02bb4c7b-ced9-43d0-8d57-4c037265f2f3
Adams, Harry
4379cc0a-3ba1-4b32-aa76-14f557e5c010
Pope, Simon J.A.
db9a489c-29ba-41cd-a96a-623bace0889d
Sykes, Daniel
4c302d69-1c7b-43bb-a22e-b60cb0d6b0a2
Faulkner, Stephen
f09826b1-0a36-4cf8-bfcf-f1ef98d27cc0
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Clegg, William
5b1994af-8799-4402-9c01-8479959de00b
Harrington, Ross W.
01d1f0bc-fc3e-43ae-a087-6cce0278128e
Ward, Michael D.
da487000-9f37-440b-a952-e09671f28e3b

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 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. Chemistry - A European Journal, 12 (36), 9299-9313. (doi:10.1002/chem.200600698).

Record type: Article

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 (I 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(II) 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 [1.Ln(tta)(3)](infinity) and [2(.)Ln(hfaC)(3)](infinity) are formed, whereas 3 forms trinuclear adducts [3(.){Ln(hfac)(3)}2] (tta anion of thenoyi-trifluoroacetone; hfac = anion of hexafluoroacetylacetone). Com-plexes 1-3 show typical Pt-II-based (MLCT)-M-3 luminescence in solution at approximate to 510 nm, but in the coordination polymers [1(.)Ln(tta)(3)](infinity) and [2(.)Ln(hfaC)(3)]infinity the presence of stacked pairs of Pt-II units with short (PtPt)-Pt-... distances means that the chromophores have (MMLCT)-M-3 character and emit at lower energy (approximate to 630 nm). Photophysical studies in solution and in the solid state show that the (MMLCT)-M-3 luminescence in [1.Ln(tta)(3)](infinity) and [2(.)Ln(htaC)(3)](infinity) in the solid state, and the (MLCT)-M-3 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.

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Published date: 2006
Keywords: crystal structures, energy transfer, lanthanides, luminescence, platinum, visible-light sensitization, bis-acetylide complexes, diimine complexes, er(iii) complexes, excited-states, spectroscopic properties, emitting materials, crystal-structures, enhanced emission, d-block

Identifiers

Local EPrints ID: 44596
URI: http://eprints.soton.ac.uk/id/eprint/44596
ISSN: 0947-6539
PURE UUID: ba4f52bd-24e5-426d-b95a-1cdcf1489cf2
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 06 Mar 2007
Last modified: 17 Dec 2019 01:54

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Contributors

Author: Tanya K. Ronson
Author: Theodore Lazarides
Author: Harry Adams
Author: Simon J.A. Pope
Author: Daniel Sykes
Author: Stephen Faulkner
Author: Simon J. Coles ORCID iD
Author: William Clegg
Author: Ross W. Harrington
Author: Michael D. Ward

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