Individual Marcus-type kinetics controls singlet and triplet oxygen evolution from superoxide
Mondal S, Nguyen HTK, Hauschild R, Freunberger SA. Individual Marcus-type kinetics controls singlet and triplet oxygen evolution from superoxide. ChemRxiv, 10.26434/chemrxiv-2024-3vrzz.
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Author
Mondal, SoumyadipISTA;
Nguyen, Huyen T.K.;
Hauschild, RobertISTA ;
Freunberger, Stefan AlexanderISTA
Department
Abstract
Oxygen evolution from superoxide is a critical aspect of oxygen redox chemistry. However, the factors determining the formation of often harmful singlet oxygen are unclear. Here, we report that the release of triplet or singlet oxygen is governed by individual Marcus normal and inverted region behavior. Using a wide range of chemical oxidants, we found that as the driving force increases, the initially dominant evolution of triplet oxygen slows down, and singlet oxygen evolution becomes predominant with higher maximum kinetics. This behavior also applies to superoxide disproportionation, the oxidation of one superoxide by another, in both non-aqueous and aqueous systems, where Lewis and Brønsted acidity control driving forces. Our findings suggest ways to understand and control spin states and kinetics in oxygen redox chemistry.
Publishing Year
Date Published
2024-08-28
Journal Title
ChemRxiv
Acknowledgement
S. A. F. is indebted to ISTA for support. The Scientific Service Units of
ISTA supported this research through resources provided by the Imaging & Optics Facility, the
Lab Support Facility, the Miba Machine Shop, and Scientific Computing. This research was
partly funded by the Austrian Science Fund (FWF): 10.55776/P37169 and 10.55776/COE5. For
open access purposes, the author has applied for a CC BY public copyright license to any author accepted manuscript version arising from this submission. R.H. acknowledges funding through
CZI grant DAF2020-225401 (10.37921/120055ratwvi) from the Chan Zuckerberg Initiative
DAF, an advised fund of Silicon Valley Community Foundation (10.13039/100014989). We
thank M. Chinon for discussions about O-redox in Life.
Acknowledged SSUs
IST-REx-ID
Cite this
Mondal S, Nguyen HTK, Hauschild R, Freunberger SA. Individual Marcus-type kinetics controls singlet and triplet oxygen evolution from superoxide. ChemRxiv. doi:10.26434/chemrxiv-2024-3vrzz
Mondal, S., Nguyen, H. T. K., Hauschild, R., & Freunberger, S. A. (n.d.). Individual Marcus-type kinetics controls singlet and triplet oxygen evolution from superoxide. ChemRxiv. https://doi.org/10.26434/chemrxiv-2024-3vrzz
Mondal, Soumyadip, Huyen T.K. Nguyen, Robert Hauschild, and Stefan Alexander Freunberger. “Individual Marcus-Type Kinetics Controls Singlet and Triplet Oxygen Evolution from Superoxide.” ChemRxiv, n.d. https://doi.org/10.26434/chemrxiv-2024-3vrzz.
S. Mondal, H. T. K. Nguyen, R. Hauschild, and S. A. Freunberger, “Individual Marcus-type kinetics controls singlet and triplet oxygen evolution from superoxide,” ChemRxiv. .
Mondal S, Nguyen HTK, Hauschild R, Freunberger SA. Individual Marcus-type kinetics controls singlet and triplet oxygen evolution from superoxide. ChemRxiv, 10.26434/chemrxiv-2024-3vrzz.
Mondal, Soumyadip, et al. “Individual Marcus-Type Kinetics Controls Singlet and Triplet Oxygen Evolution from Superoxide.” ChemRxiv, doi:10.26434/chemrxiv-2024-3vrzz.
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