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

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

Journal Article · 16 March 2020 · Nature Chemistry

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

^[1];

^[2]; Favale, Joseph M. ^[3];

^[1]; Petersen, Jeffrey L. ^[1]; Scholes, Gregory D. ^[2];

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^[1]

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

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

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

Grant/Contract Number:: SC0011979; CHE-1752738; CHE-1336071; CHE-1228336; SC0015429

OSTI ID:: 1633639

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

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 119 works

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