Electron Transfer Mechanism of Substituted Benzimidazoles: Dimer Switching, Oscillations, and Search for Singlet Fission Properties

Reduction and oxidation of 4,7-dimethyl-1,3-dimethoxybenzimidazolium cation (1) and the related dihydroxy analogue (2) were investigated by electrochemical and in situ spectroelectrochemical methods. Quantum chemical methods were applied to UV–vis spectra in native, reduced, and oxidized forms. Comp...

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Published inJournal of physical chemistry. C Vol. 121; no. 18; pp. 9963 - 9969
Main Authors Plutnar, Jan, Hromadová, Magdaléna, Fanelli, Nicolangelo, Ramešová, Šárka, Havlas, Zdeněk, Pospíšil, Lubomír
Format Journal Article
LanguageEnglish
Published American Chemical Society 11.05.2017
Subjects
benzimidazoles
cations
dimerization
electrochemistry
electron transfer
oxidation
physical chemistry
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ISSN1932-7447
1932-7455
1932-7455
DOI10.1021/acs.jpcc.7b02028

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Abstract Reduction and oxidation of 4,7-dimethyl-1,3-dimethoxybenzimidazolium cation (1) and the related dihydroxy analogue (2) were investigated by electrochemical and in situ spectroelectrochemical methods. Quantum chemical methods were applied to UV–vis spectra in native, reduced, and oxidized forms. Compounds were searched for possible formation of a cation radical and a dication radical suitable for the singlet fission effect. Indeed 1 yields by oxidation the target quinoidal structure. However, the reduction step for both compounds is coupled with very fast dimerization and prevents obtaining a stable target form. The complex mechanism of the reduction process yields electrochemical current oscillation. Estimation of the maximum Ljapunov exponent proves characteristics of the deterministic chaos.
AbstractList Reduction and oxidation of 4,7-dimethyl-1,3-dimethoxybenzimidazolium cation (1) and the related dihydroxy analogue (2) were investigated by electrochemical and in situ spectroelectrochemical methods. Quantum chemical methods were applied to UV–vis spectra in native, reduced, and oxidized forms. Compounds were searched for possible formation of a cation radical and a dication radical suitable for the singlet fission effect. Indeed 1 yields by oxidation the target quinoidal structure. However, the reduction step for both compounds is coupled with very fast dimerization and prevents obtaining a stable target form. The complex mechanism of the reduction process yields electrochemical current oscillation. Estimation of the maximum Ljapunov exponent proves characteristics of the deterministic chaos.
Author Havlas, Zdeněk
Pospíšil, Lubomír
Hromadová, Magdaléna
Plutnar, Jan
Fanelli, Nicolangelo
Ramešová, Šárka
AuthorAffiliation Academy of Sciences of the Czech Republic
Institute of Chemistry of Organometallic Compounds
J. Heyrovský Institute of Physical Chemistry
CNR Pisa
Intstitue of Organic Chemistry and Biochemistry
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SubjectTerms benzimidazoles
cations
dimerization
electrochemistry
electron transfer
oxidation
physical chemistry
Title Electron Transfer Mechanism of Substituted Benzimidazoles: Dimer Switching, Oscillations, and Search for Singlet Fission Properties
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