Lanthanoid/Alkali Metal ß-Triketonate Assemblies: A Robust Platform for Efficient NIR Emitters.

The reaction of hydrated lanthanoid chlorides with tribenzoylmethane and an alkali metal hydroxide consistently resulted in the crystallization of neutral tetranuclear assemblies with the general formula [Ln(Ae⋅HOEt)(L)4]2 (Ln=Eu3+, Er3+, Yb3+; Ae=Na+, K+, Rb+). Analysis of the crystal structures of...

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Main Authors: Reid, Brodie, Stagni, S., Malicka, J., Cocchi, M., Sobolev, A., Skelton, B., Moore, E., Hanan, G., Ogden, Mark, Massi, Massimiliano
Format: Journal Article
Published: 2015
Online Access:http://hdl.handle.net/20.500.11937/26428
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author Reid, Brodie
Stagni, S.
Malicka, J.
Cocchi, M.
Sobolev, A.
Skelton, B.
Moore, E.
Hanan, G.
Ogden, Mark
Massi, Massimiliano
author_facet Reid, Brodie
Stagni, S.
Malicka, J.
Cocchi, M.
Sobolev, A.
Skelton, B.
Moore, E.
Hanan, G.
Ogden, Mark
Massi, Massimiliano
author_sort Reid, Brodie
building Curtin Institutional Repository
collection Online Access
description The reaction of hydrated lanthanoid chlorides with tribenzoylmethane and an alkali metal hydroxide consistently resulted in the crystallization of neutral tetranuclear assemblies with the general formula [Ln(Ae⋅HOEt)(L)4]2 (Ln=Eu3+, Er3+, Yb3+; Ae=Na+, K+, Rb+). Analysis of the crystal structures of these species revealed a coordination geometry that varied from a slightly distorted square antiprism to a slightly distorted triangular dodecahedron, with the specific geometrical shape being dependent on the degree of lattice solvation and identity of the alkali metal. The near-infrared (NIR)-emitting assemblies of Yb3+ and Er3+ showed remarkably efficient emission, characterized by significantly longer excited-state lifetimes (τobs≈37–47 μs for Yb3+ and τobs≈4–6 μs for Er3+) when compared with the broader family of lanthanoid β-diketonate species, even in the case of perfluorination of the ligands. The Eu3+ assemblies show bright red emission and a luminescence performance (τobs≈0.5 ms, equation image≈35–37 %, ηsens≈68–70 %) more akin to the β-diketonate species. The results highlight that the β-triketonate ligand offers a tunable and facile system for the preparation of efficient NIR emitters without the need for more complicated perfluorination or deuteration synthetic strategies.
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spelling curtin-20.500.11937-264282019-02-19T05:35:39Z Lanthanoid/Alkali Metal ß-Triketonate Assemblies: A Robust Platform for Efficient NIR Emitters. Reid, Brodie Stagni, S. Malicka, J. Cocchi, M. Sobolev, A. Skelton, B. Moore, E. Hanan, G. Ogden, Mark Massi, Massimiliano The reaction of hydrated lanthanoid chlorides with tribenzoylmethane and an alkali metal hydroxide consistently resulted in the crystallization of neutral tetranuclear assemblies with the general formula [Ln(Ae⋅HOEt)(L)4]2 (Ln=Eu3+, Er3+, Yb3+; Ae=Na+, K+, Rb+). Analysis of the crystal structures of these species revealed a coordination geometry that varied from a slightly distorted square antiprism to a slightly distorted triangular dodecahedron, with the specific geometrical shape being dependent on the degree of lattice solvation and identity of the alkali metal. The near-infrared (NIR)-emitting assemblies of Yb3+ and Er3+ showed remarkably efficient emission, characterized by significantly longer excited-state lifetimes (τobs≈37–47 μs for Yb3+ and τobs≈4–6 μs for Er3+) when compared with the broader family of lanthanoid β-diketonate species, even in the case of perfluorination of the ligands. The Eu3+ assemblies show bright red emission and a luminescence performance (τobs≈0.5 ms, equation image≈35–37 %, ηsens≈68–70 %) more akin to the β-diketonate species. The results highlight that the β-triketonate ligand offers a tunable and facile system for the preparation of efficient NIR emitters without the need for more complicated perfluorination or deuteration synthetic strategies. 2015 Journal Article http://hdl.handle.net/20.500.11937/26428 10.1002/chem.201502536 fulltext
spellingShingle Reid, Brodie
Stagni, S.
Malicka, J.
Cocchi, M.
Sobolev, A.
Skelton, B.
Moore, E.
Hanan, G.
Ogden, Mark
Massi, Massimiliano
Lanthanoid/Alkali Metal ß-Triketonate Assemblies: A Robust Platform for Efficient NIR Emitters.
title Lanthanoid/Alkali Metal ß-Triketonate Assemblies: A Robust Platform for Efficient NIR Emitters.
title_full Lanthanoid/Alkali Metal ß-Triketonate Assemblies: A Robust Platform for Efficient NIR Emitters.
title_fullStr Lanthanoid/Alkali Metal ß-Triketonate Assemblies: A Robust Platform for Efficient NIR Emitters.
title_full_unstemmed Lanthanoid/Alkali Metal ß-Triketonate Assemblies: A Robust Platform for Efficient NIR Emitters.
title_short Lanthanoid/Alkali Metal ß-Triketonate Assemblies: A Robust Platform for Efficient NIR Emitters.
title_sort lanthanoid/alkali metal ß-triketonate assemblies: a robust platform for efficient nir emitters.
url http://hdl.handle.net/20.500.11937/26428