Mechanistic Origin of Photoredox Catalysis Involving Iron(II) Polypyridyl Chromophores

Woodhouse, Matthew D.; McCusker, James K.

doi:10.1021/jacs.0c08389

Mechanistic Origin of Photoredox Catalysis Involving Iron(II) Polypyridyl Chromophores

Journal Article · Fri Sep 11 00:00:00 EDT 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c08389· OSTI ID:1659685

Woodhouse, Matthew D. ^[1]; ^[2]

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

Photoredox catalysis employing ruthenium- and iridium-based chromophores have been the subject of considerable research. However, the natural abundance of these elements are among the lowest on the periodic table, a fact that has led to an interest in developing chromophores based on earth-abundant transition metals that can perform the same function. There have been reports of using Fe^II-based polypyridyl complexes as photocatalysts, but there is limited mechanistic information pertaining to the nature of their reactivity in the context of photoredox chemistry. Herein, we report the results of bimolecular quenching studies between [Fe(tren(py)₃)]²⁺ (where tren(py)₃ = tris(2-pyridyl-methylimino-ethyl)amine) and a series of benzoquinoid acceptors. The data provide direct evidence of electron transfer involving the lowest-energy ligand-field excited state of the Fe(II)-based photosensitizer, definitively establishing that Fe(II) polypyridyl complexes can engage in photoinduced redox reactions but by a mechanism that is fundamentally different than the MLCT-based chemistry endemic to their second- and third-row congeners.

View Accepted Manuscript (DOE)

Research Organization:: Princeton Univ., NJ (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:: 1659685

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 38 Vol. 142; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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