PCET-Based Ligand Limits Charge Recombination with an Ir(III) Photoredox Catalyst

Sayre, Hannah; Ripberger, Hunter H.; Odella, Emmanuel; Zieleniewska, Anna; Heredia, Daniel A.; Rumbles, Garry; Scholes, Gregory D.; Moore, Thomas A.; Moore, Ana L.; Knowles, Robert R.

doi:10.1021/jacs.1c01701

Title: PCET-Based Ligand Limits Charge Recombination with an Ir(III) Photoredox Catalyst

Journal Article · 10 August 2021 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.1c01701 · OSTI ID:1814480

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Princeton Univ., NJ (United States)
Arizona State Univ., Tempe, AZ (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States)

Upon photoinitiated electron transfer, charge recombination limits the quantum yield of photoredox reactions for which the rates for the forward reaction and back electron transfer are competitive. Taking inspiration from a proton-coupled electron transfer (PCET) process in Photosystem II, here a benzimidazole-phenol (BIP) has been covalently attached to the 2,2'-bipyridyl ligand of [Ir(dF(CF₃)ppy)₂(bpy)][PF₆] (dF(CF₃)ppy = 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine; bpy = 2,2'-bipyridyl). Excitation of the [Ir(dF(CF₃)ppy)₂(BIP-bpy)][PF₆] photocatalyst results in intramolecular PCET to form a charge-separated state with oxidized BIP. Subsequent reduction of methyl viologen dication (MV²⁺), a substrate surrogate, by the reducing moiety of the charge separated species demonstrates that the inclusion of BIP significantly slows the charge recombination rate. The effect of ~24-fold slower charge recombination in a photocatalytic phthalimide ester reduction resulted in a greater than 2-fold increase in reaction quantum efficiency.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States); Princeton Univ., NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC36-08GO28308; SC0019370

OSTI ID:: 1814480

Report Number(s):: NREL/JA--5900-79572; MainId:35793; UUID:49b6ae65-e85e-4b7a-bbbd-a51068e7ab91; MainAdminID:59573

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 33 Vol. 143; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
BioLEC
PCET
Photoredox catalysis
charge recombination
photoredox catalysis
proton-coupled electron transfer

Title: PCET-Based Ligand Limits Charge Recombination with an Ir(III) Photoredox Catalyst

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References (46)

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