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

    234967_234967.pdf (1.110Mb)
    Access Status
    Open access
    Authors
    Reid, Brodie
    Stagni, S.
    Malicka, J.
    Cocchi, M.
    Sobolev, A.
    Skelton, B.
    Moore, E.
    Hanan, G.
    Ogden, Mark
    Massi, Massimiliano
    Date
    2015
    Type
    Journal Article
    
    Metadata
    Show full item record
    Citation
    Reid, B. and Stagni, S. and Malicka, J. and Cocchi, M. and Sobolev, A. and Skelton, B. and Moore, E. et al. 2015. Lanthanoid/Alkali Metal ß-Triketonate Assemblies: A Robust Platform for Efficient NIR Emitters. Chemistry. 21 (50): pp. 18354-18363.
    Source Title
    Chemistry
    DOI
    10.1002/chem.201502536
    School
    Department of Chemistry
    Remarks

    This is the peer reviewed version of the following article: Reid, B. and Stagni, S. and Malicka, J. and Cocchi, M. and Sobolev, A. and Skelton, B. and Moore, E. et al. 2015. Lanthanoid/Alkali Metal ß-Triketonate Assemblies: A Robust Platform for Efficient NIR Emitters. Chemistry. 21 (50): pp. 18354-18363., which has been published in final form at http://doi.org/10.1002/chem.201502536This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving at http://olabout.wiley.com/WileyCDA/Section/id-828039.html#terms

    URI
    http://hdl.handle.net/20.500.11937/26428
    Collection
    • Curtin Research Publications
    Abstract

    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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