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

Abstract

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(MesPDPPh)2, where [MesPDPPh]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(MesPDPPh)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.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [1];  [1];  [2]; ORCiD logo [3]; ORCiD logo [1]
  1. West Virginia Univ., Morgantown, WV (United States)
  2. Princeton Univ., NJ (United States)
  3. North Carolina State Univ., Raleigh, NC (United States)
Publication Date:
Research Org.:
North Carolina State Univ., Raleigh, NC (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1633639
Grant/Contract Number:  
SC0011979; CHE-1752738; CHE-1336071; CHE-1228336; SC0015429
Resource Type:
Accepted Manuscript
Journal Name:
Nature Chemistry
Additional Journal Information:
Journal Volume: 12; Journal Issue: 4; Journal ID: ISSN 1755-4330
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY

Citation Formats

Zhang, Yu, Lee, Tia S., Favale, Joseph M., Leary, Dylan C., Petersen, Jeffrey L., Scholes, Gregory D., Castellano, Felix N., and Milsmann, Carsten. Delayed fluorescence from a zirconium(iv) photosensitizer with ligand-to-metal charge-transfer excited states. United States: N. p., 2020. Web. doi:10.1038/s41557-020-0430-7.
Zhang, Yu, Lee, Tia S., Favale, Joseph M., Leary, Dylan C., Petersen, Jeffrey L., Scholes, Gregory D., Castellano, Felix N., & Milsmann, Carsten. Delayed fluorescence from a zirconium(iv) photosensitizer with ligand-to-metal charge-transfer excited states. United States. doi:https://doi.org/10.1038/s41557-020-0430-7
Zhang, Yu, Lee, Tia S., Favale, Joseph M., Leary, Dylan C., Petersen, Jeffrey L., Scholes, Gregory D., Castellano, Felix N., and Milsmann, Carsten. Mon . "Delayed fluorescence from a zirconium(iv) photosensitizer with ligand-to-metal charge-transfer excited states". United States. doi:https://doi.org/10.1038/s41557-020-0430-7. https://www.osti.gov/servlets/purl/1633639.
@article{osti_1633639,
title = {Delayed fluorescence from a zirconium(iv) photosensitizer with ligand-to-metal charge-transfer excited states},
author = {Zhang, Yu and Lee, Tia S. and Favale, Joseph M. and Leary, Dylan C. and Petersen, Jeffrey L. and Scholes, Gregory D. and Castellano, Felix N. and Milsmann, Carsten},
abstractNote = {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(MesPDPPh)2, where [MesPDPPh]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(MesPDPPh)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.},
doi = {10.1038/s41557-020-0430-7},
journal = {Nature Chemistry},
number = 4,
volume = 12,
place = {United States},
year = {2020},
month = {3}
}

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