Nitro‐Group π System Drives the Interaction of RRx‐001 with Electrons in Solution

Reactivity toward low-energy electrons (LEE) has been hypothesized as a cause of radio-modifying properties for various molecules. LEE's transient nature, however, prevents the establishment of clear links between initial processes at the sub-ps time scale and the final products of radiolysis. Here, such links are explored for the radio-modifying compound RRx-001 (1-bromoacetyl-3,3-dinitroazetidine). Picosecond pulse radiolysis demonstrates the high scavenging capacity of the molecule for secondary quasi-free and solvated electrons forming stable parent anions confirmed by studies of microsolvated RRx-001 in clusters. The anions decay either via auto-detachment of an electron or dissociate involving hydrogen transfer from solvent, resulting in NO<sub>2</sub> and 1-(bromoacetyl)-3-nitroazetidine. Surprisingly, no Br dissociation is observed despite its high electron affinity. We assign this behavior to the "inaccessibility" of sigma virtual states for electrons in the solvent, which can be of a general nature.

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Journal
Chemistry - A European Journal
Published
2025-04-22
DOI
https://doi.org/10.1002/chem.202500859
Primary Topic
Crystallography and molecular interactions
Type
article
Field-Weighted Citation Impact
0.00

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article

Nitro‐Group π System Drives the Interaction of RRx‐001 with Electrons in Solution

Milan Ončák, David Chvátil, Stephan Denifl, J. Pinkas et al.
Chemistry - A European Journal
Crystallography and molecular interactions
article

Nitro‐Group π System Drives the Interaction of RRx‐001 with Electrons in Solution

Milan Ončák, David Chvátil, Stephan Denifl, J. Pinkas, Barbora Sedmidubská, Farhad Izadi, Thomas F. M. Luxford, Mehran Mostafavi, Jaroslav Kočišek, Sergey A. Denisov
article en

Abstract

Reactivity toward low-energy electrons (LEE) has been hypothesized as a cause of radio-modifying properties for various molecules. LEE's transient nature, however, prevents the establishment of clear links between initial processes at the sub-ps time scale and the final products of radiolysis. Here, such links are explored for the radio-modifying compound RRx-001 (1-bromoacetyl-3,3-dinitroazetidine). Picosecond pulse radiolysis demonstrates the high scavenging capacity of the molecule for secondary quasi-free and solvated electrons forming stable parent anions confirmed by studies of microsolvated RRx-001 in clusters. The anions decay either via auto-detachment of an electron or dissociate involving hydrogen transfer from solvent, resulting in NO<sub>2</sub> and 1-(bromoacetyl)-3-nitroazetidine. Surprisingly, no Br dissociation is observed despite its high electron affinity. We assign this behavior to the "inaccessibility" of sigma virtual states for electrons in the solvent, which can be of a general nature.

Chemistry - A European JournalVol. 31(31)
Centre National de la Recherche Scientifique (FR), Texas State University (US), Universität Innsbruck (AT), Université Paris-Saclay (FR), Laboratoire de Chimie Physique (FR), Czech Academy of Sciences, J. Heyrovský Institute of Physical Chemistry (CZ), Czech Academy of Sciences, Nuclear Physics Institute (CZ), Institut de Chimie Moléculaire et des Matériaux d'Orsay (FR), Czech Technical University in Prague (CZ)
European Commission, Grantová Agentura České Republiky, Universität Innsbruck
Affordable and clean energy
Openalex Percentile: Top 91%
Crystallography and molecular interactions
DOIOpen Access PDFOpenAlex
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