Delayed fluorescence from a zirconium(iv) photosensitizer with ligand-to-metal charge-transfer excited states

Zhang, Yu; Lee, Tia S.; Favale, Joseph M.; Leary, Dylan C.; Petersen, Jeffrey L.; Scholes, Gregory D.; Castellano, Felix N.; Milsmann, Carsten

doi:10.1038/s41557-020-0430-7

Delayed fluorescence from a zirconium(iv) photosensitizer with ligand-to-metal charge-transfer excited states

Journal Article · Mon Mar 16 00:00:00 EDT 2020 · Nature Chemistry

DOI:https://doi.org/10.1038/s41557-020-0430-7· OSTI ID:1633639

^[1]; ^[2]; Favale, Joseph M. ^[3]; ^[4]; Petersen, Jeffrey L. ^[4]; Scholes, Gregory D. ^[2]; ^[3]; ^[4]

West Virginia Univ., Morgantown, WV (United States); NC State University
Princeton Univ., NJ (United States)
North Carolina State Univ., Raleigh, NC (United States)
West Virginia Univ., Morgantown, WV (United States)

Advances in chemical control of the photophysical properties of transition-metal complexes are revolutionizing a wide range of technologies, particularly photocatalysis and light-emitting diodes, but they rely heavily on molecules containing precious metals such as ruthenium and iridium. While the application of earth-abundant ‘early’ transition metals in photosensitizers is clearly advantageous, a detailed understanding of excited states with ligand-to-metal charge transfer (LMCT) character is paramount to account for their distinct electron configurations. Here we report an air- and moisture-stable, visible lightabsorbing Zr(iv) photosensitizer, Zr(^MesPDP^Ph)₂, where [^MesPDP^Ph]^2- is the doubly deprotonated form of [2,6-bis(5-(2,4,6- trimethylphenyl)-3-phenyl-1H-pyrrol-2-yl)pyridine]. This molecule has an exceptionally long-lived triplet LMCT excited state (τ = 350 μs), featuring highly efficient photoluminescence emission (Ф = 0.45) due to thermally activated delayed fluorescence emanating from the higher-lying singlet configuration with significant LMCT contributions. Zr(^MesPDP^Ph)₂ engages in numerous photoredox catalytic processes and triplet energy transfer. Our exploration offers a blueprint for future photosensitizer development featuring early transition metals and excited states with significant LMCT contributions.

View Accepted Manuscript (DOE)

Research Organization:: North Carolina State Univ., Raleigh, NC (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0011979; SC0015429

OSTI ID:: 1633639

Journal Information:: Nature Chemistry, Journal Name: Nature Chemistry Journal Issue: 4 Vol. 12; ISSN 1755-4330

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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