In situ simultaneous electrochemical ESR study of radicals generated from 2,2-dinitroethene-1,1-diamine (FOX-7). Intramolecular chemical exchange resulting in an alternation line-width effect

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F21%3A00541203" target="_blank" >RIV/61388955:_____/21:00541203 - isvavai.cz</a>

Result on the web

<a href="http://hdl.handle.net/11104/0318799" target="_blank" >http://hdl.handle.net/11104/0318799</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.jmr.2020.106895" target="_blank" >10.1016/j.jmr.2020.106895</a>

Result language

angličtina

Original language name

In situ simultaneous electrochemical ESR study of radicals generated from 2,2-dinitroethene-1,1-diamine (FOX-7). Intramolecular chemical exchange resulting in an alternation line-width effect

Original language description

The molecule of 2,2-dinitroethene-1,1-diamine (FOX-7) is one of the most interesting molecules with multiple redox centres stabilized by push-pull effect. To reveal the detailed mechanism of its electrochemical process radical intermediates formed in the course of its electrochemical reduction in organic aprotic media have been studied by in situ simultaneous electrochemical ESR measurements (SEESR). The radical generated on the second reduction step possesses an alternating line-width (AL) effect in the ESR spectra as a result of intramolecular dynamic processes in the timescale of ESR splitting constants. The spectra measured at different temperatures (230-335 K) were analysed with the help of a fitting program which includes a molecular dynamics. Observed dynamics describes well an asymmetric 2 site exchange model for the whole temperature range. With help of the optimized parameters and quantum chemical calculations this radical has been identified as 2,2-dinitroethane-1-amine-1-imine radical dianion, [(H2N)(HN)C=C(NO2)(2)](2-). The dynamic process responsible for the AL effect consists of mutual turning (changing of dihedral angle) of the both nitro groups, resulting in an intramolecular spin-density (electron) transfer. The dynamic parameters of the process have been established. (C) 2021 Elsevier Inc. All rights reserved.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

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OECD FORD branch

10405 - Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis)

Project

—

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2021

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Journal of Magnetic Resonance

ISSN

1090-7807

e-ISSN

1096-0856

Volume of the periodical

323

Issue of the periodical within the volume

FEB 2021

Country of publishing house

GB - UNITED KINGDOM

Number of pages

9

Pages from-to

106895

UT code for WoS article

000615916500002

EID of the result in the Scopus database

2-s2.0-85098995316