Jump to main content
Jump to site search

Issue 29, 2019
Previous Article Next Article

Phosphorus corrole complexes: from property tuning to applications in photocatalysis and triplet–triplet annihilation upconversion

Author affiliations

Abstract

Efficient triplet photosensitizers are important for fundamental photochemical studies and applications such as triplet–triplet annihilation upconversion (TTA UC), photoredox catalytic organic reactions and photovoltaics. We now report a series of phosphorus corrole compounds as efficient visible light-harvesting metal-free triplet photosensitizers. While the heavy-atom-free phosphorus corroles show absorption in the visible spectral region (centered at 573 nm) and have a decent triplet state quantum yield (ΦΔ = 49%), iodo-substitution on the corrole core induces red-shifted absorption (589 nm) and improves intersystem crossing significantly (ΦΔ = 67%). Nanosecond transient absorption spectra confirm triplet state formation upon photoexcitation (τT = 312 μs) and the iodinated derivatives also display near IR phosphorescence in fluid solution at room temperature (λem = 796 nm, τp = 412 μs). Both singlet oxygen (1O2) and superoxide radical anions (O2˙) may be produced with the phosphorus corroles, which are competent photocatalysts for the oxidative coupling of benzylamine (the Aza Henry reaction). Very efficient TTA UC was observed with the phosphorus corroles as triplet photosensitizers and perylene as the triplet acceptor, with upconversion quantum yields of up to ΦUC = 38.9% (a factor of 2 was used in the equation) and a very large anti-Stokes effect of 0.5 eV.

Graphical abstract: Phosphorus corrole complexes: from property tuning to applications in photocatalysis and triplet–triplet annihilation upconversion

Back to tab navigation

Supplementary files

Publication details

The article was received on 25 Mar 2019, accepted on 12 Jun 2019 and first published on 13 Jun 2019


Article type: Edge Article
DOI: 10.1039/C9SC01463B
Chem. Sci., 2019,10, 7091-7103
  • Open access: Creative Commons BY-NC license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

  •   Request permissions

    Phosphorus corrole complexes: from property tuning to applications in photocatalysis and triplet–triplet annihilation upconversion

    A. Mahammed, K. Chen, J. Vestfrid, J. Zhao and Z. Gross, Chem. Sci., 2019, 10, 7091
    DOI: 10.1039/C9SC01463B

    This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material and it is not used for commercial purposes.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements