Direct Evidence for Excited Ligand Field State-based Oxidative Photoredox Chemistry of a Cobalt(III) Polypyridyl Photosensitizer

Alowakennu, Micheal M.; Ghosh, Atanu; McCusker, James K.

doi:10.1021/jacs.3c09374

Direct Evidence for Excited Ligand Field State-based Oxidative Photoredox Chemistry of a Cobalt(III) Polypyridyl Photosensitizer

Journal Article · Wed Sep 13 04:00:00 EDT 2023 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.3c09374· OSTI ID:2280824

Alowakennu, Micheal M. ^[1]; Ghosh, Atanu ^[2]; ^[2]

Michigan State Univ., East Lansing, MI (United States); Michigan State University
Michigan State Univ., East Lansing, MI (United States)

Increasing interest in sustainable chemistry coupled with the quest to explore new reactivity has spurred research on first-row transition metal complexes for potential applications in a variety of settings. One of the more active areas of research is photoredox catalysis, where the synthetically tunable nature of their electronic structures provides a rich palette of options for tailoring their reactivity to a desired chemical transformation. Understanding the mechanism of excited-state reactivity is critical for the informed development of next-generation catalysts, which in turn requires information concerning the propensity of their electronic excited states to engage in the desired electron or energy transfer processes. Herein we provide direct evidence of the highly oxidizing nature of the lowest-energy ligand-field (LF) excited state of a first-row d⁶-low-spin Co(III) photosensitizer [Co(4,4'-Br₂bpy)₃]³⁺ (where 4,4'-Br₂bpy is 4,4'-dibromo-2,2'-bipyridine). The redox potential associated with the LF excited state of the Co(III) complex was bracketed by performing bimolecular quenching studies by using a series of simple organic electron donors. Time-resolved absorption spectroscopy confirmed a dynamic quenching process attributed to reductive quenching of the lowest-energy ligand-field excited state of the Co(III) chromophore. Analysis of the Stern–Volmer plots for each chromophore-quencher pair revealed a limiting value of E_red* ~ 1.25 V vs Fc/Fc⁺ for the metal-centered excited state, which is significantly stronger than that of more commonly employed transition metal-based photoredox agents such as [Ru(bpy)₃]²⁺ (E_red* = 0.32 V vs Fc/Fc⁺) and [Ir(ppy)₂(bpy)]⁺ (E_red* = 0.27 V vs Fc/Fc⁺). Finally, these results suggest that this class of chromophores could find utility in applications requiring the activation of oxidatively resistant organic substrates for photoredox catalysis.

View Accepted Manuscript (DOE)

Research Organization:: Michigan State Univ., East Lansing, MI (United States); Energy Frontier Research Centers (EFRC) (United States). Bioinspired Light-Escalated Chemistry (BioLEC)

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

Grant/Contract Number:: SC0019370

OSTI ID:: 2280824

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 38 Vol. 145; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Direct Evidence for Excited Ligand Field State-based Oxidative Photoredox Chemistry of a Cobalt(III) Polypyridyl Photosensitizer

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