Tuning the Photocatalytic CO2 Reduction through para-Substituents in Bipyridyl Rhenium Complexes

Müller, Andressa V.; Wierzba, Wendel M.; do Nascimento, Luis G. A.; Concepcion, Javier J.; Nikolaou, Sofia; Polyansky, Dmitry E.; Polo, Andre S.

doi:10.1021/aps.4c00026

Tuning the Photocatalytic CO₂ Reduction through para-Substituents in Bipyridyl Rhenium Complexes

Journal Article · Wed Feb 19 00:00:00 EST 2025 · Artificial Photosynthesis

DOI:https://doi.org/10.1021/aps.4c00026· OSTI ID:2520208

^[1]; Wierzba, Wendel M. ^[2]; do Nascimento, Luis G. A. ^[3]; ^[4]; ^[3]; Polyansky, Dmitry E. ^[4]; ^[2]

Federal Univ. of ABC, Santo Andre, SP (Brazil); Brookhaven National Laboratory (BNL), Upton, NY (United States)
Federal Univ. of ABC, Santo Andre, SP (Brazil)
Univ. of São Paulo (Brazil)
Brookhaven National Laboratory (BNL), Upton, NY (United States)

Six fac-[Re(NN)(CO)₃Cl] complexes, where NN is a 2,2'-bipyridine ligand with systematically varied electron donating or withdrawing groups at the 4,4′ positions, were explored as photocatalysts for CO₂ reduction to CO. The light absorption, redox potentials, and excited state dynamics of the complexes, as well as the reactivity and stability of key catalysis intermediates were correlated with the Hammett constants (σ_p) of the substituents, revealing their impact on the photocatalytic activity. Electron donating substituents, such as −OCH₃ and −CH₃, resulted in slower excited-state quenching by sacrificial electron donors in comparison to the unsubstituted complex, but their corresponding one-electron reduced species (OERS) reacted quickly with CO₂. On the other hand, electron-withdrawing substituents, such as −Br, −COOH, and −CO₂CH₃ resulted in more favorable and faster reductive quenching, but at the cost of slower reactivity of the OERS. Finally, comparison of the catalytic activity of the complexes employing two different sacrificial electron donors displayed how the interplay of these factors affects the CO₂ reduction performance, and how photocatalysis can be controlled through strategic manipulation of both the ligand environment and reaction conditions.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0012704

OSTI ID:: 2520208

Alternate ID(s):: OSTI ID: 2570582

Report Number(s):: BNL--228373-2025-JAAM

Journal Information:: Artificial Photosynthesis, Journal Name: Artificial Photosynthesis Journal Issue: 5 Vol. 1; ISSN 2994-0974

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Tuning the Photocatalytic CO2 Reduction through para-Substituents in Bipyridyl Rhenium Complexes

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