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Influence of Sulfur Oxidation State and Substituents on Sulfur-Bridged Luminescent Copper(I) Complexes Showing Thermally Activated Delayed Fluorescence

  • Christopher M. Brown
    Christopher M. Brown
    Department of Chemistry, University of British Columbia, Vancouver, British Columbia V6T 1Z1, Canada
  • Chenfei Li
    Chenfei Li
    Organic Semiconductor Centre, EaStCHEM School of Chemistry, University of St. Andrews, St. Andrews, Fife KY16 9ST, U.K.
    More by Chenfei Li
  • Veronica Carta
    Veronica Carta
    Department of Chemistry, University of British Columbia, Vancouver, British Columbia V6T 1Z1, Canada
  • Wenbo Li
    Wenbo Li
    Organic Semiconductor Centre, SUPA School of Physics and Astronomy, University of St. Andrews, St. Andrews, Fife KY16 9SS, U.K.
    More by Wenbo Li
  • Zhen Xu
    Zhen Xu
    Department of Chemistry, University of British Columbia, Vancouver, British Columbia V6T 1Z1, Canada
    More by Zhen Xu
  • Pedro Henrique Fazza Stroppa
    Pedro Henrique Fazza Stroppa
    Organic Semiconductor Centre, EaStCHEM School of Chemistry, University of St. Andrews, St. Andrews, Fife KY16 9ST, U.K.
  • Ifor D. W. Samuel
    Ifor D. W. Samuel
    Organic Semiconductor Centre, SUPA School of Physics and Astronomy, University of St. Andrews, St. Andrews, Fife KY16 9SS, U.K.
  • Eli Zysman-Colman
    Eli Zysman-Colman
    Organic Semiconductor Centre, EaStCHEM School of Chemistry, University of St. Andrews, St. Andrews, Fife KY16 9ST, U.K.
  • , and 
  • Michael O. Wolf*
    Michael O. Wolf
    Department of Chemistry, University of British Columbia, Vancouver, British Columbia V6T 1Z1, Canada
    *E-mail: [email protected]
Cite this: Inorg. Chem. 2019, 58, 11, 7156–7168
Publication Date (Web):May 22, 2019
https://doi.org/10.1021/acs.inorgchem.8b03500
Copyright © 2019 American Chemical Society

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    Abstract

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    Copper(I) complexes are seen as more sustainable alternatives to those containing metal ions such as iridium and platinum for emitting devices. Copper(I) complexes have the ability to radiatively decay via a thermally activated delayed fluorescence (TADF) pathway, leading to higher photoluminescent quantum yields. In this work we discuss six new heteroleptic Cu(I) complexes of the diphosphine–diimine motif. The diphosphine ligands employed are (oxidi-2,1-phenylene)bis(diphenylphosphine) (DPEPhos), and the diimine fragments are sulfur-bridged dipyridyl ligands (DPS) which are functionalized at the 6,6′-positions of the pyridyl rings (R = H, Me, Ph) and have varying oxidation states at the bridging sulfur atom (S, SO2). The proton (Cu-DPS, Cu-DPSO2) and phenyl (Cu-Ph-DPS, Cu-Ph-DPSO2) substituted species are found to form monometallic complexes, while those with methyl substitution (Cu-Me-DPS, Cu-Me-DPSO2) are found to have a “Goldilocks” degree of steric bulk leading to bimetallic species. All six Cu(I) complexes show emission in the solid state, with the photophysical properties characterized by low temperature steady-state and time-resolved spectroscopies and variable temperature time-correlated single photon counting. Cu-DPS, Cu-DPSO2, Cu-Me-DPS, Cu-Me-DPSO2, and Cu-Ph-DPSO2 were shown to emit via a TADF mechanism, while Cu-Ph-DPS showed photoluminescence properties consistent with triplet ligand-centered (3LC) emission.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b03500.

    • Characterization data (NMR, mass spectrometry, and elemental analysis), crystallographic data, electrochemical data, photophysical data (absorption, TCSPC, and time-resolved emission spectra), and theoretical calculations (PDF)

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    CCDC 18679441867949 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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