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Protonated paramagnetic redox forms of di-o-quinone bridged with p-phenylene-extended TTF: A EPR spectroscopy study.


ABSTRACT: The chemical oxidation and reduction processes of deprotonated, direduced o-quinone-exTTF-o-quinone in protic solvents were studied by EPR spectroscopy. The formation of relatively stable paramagnetic protonated redox forms of the parent triad was very surprising. The character of spin-density distribution in the semiquinone-quinone and semiquinone-catechol redox forms indicates that the p-phenylene-extended tetrathiafulvalene connector provides a quite effective electronic communication channel between dioxolene coordination sites. It was found that the deprotonated, direduced o-quinone-exTTF-o-quinone is capable to reduction of the metal copper in solution. The radical anion species formed in this reaction exists in solution as a solvent-separated ion pair with a copper cation. A character of spin-density distribution in a radical anion species leads to the conclusion that the ligand corresponds to type III of the Robin-Day classification.

SUBMITTER: Chalkov NO 

PROVIDER: S-EPMC5238573 | biostudies-literature | 2016

REPOSITORIES: biostudies-literature

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Protonated paramagnetic redox forms of di-<i>o</i>-quinone bridged with <i>p</i>-phenylene-extended TTF: A EPR spectroscopy study.

Chalkov Nikolay O NO   Cherkasov Vladimir K VK   Abakumov Gleb A GA   Starikov Andrey G AG   Kuropatov Viacheslav A VA  

Beilstein journal of organic chemistry 20161117


The chemical oxidation and reduction processes of deprotonated, direduced <i>o</i>-quinone-exTTF-<i>o</i>-quinone in protic solvents were studied by EPR spectroscopy. The formation of relatively stable paramagnetic protonated redox forms of the parent triad was very surprising. The character of spin-density distribution in the semiquinone-quinone and semiquinone-catechol redox forms indicates that the <i>p</i>-phenylene-extended tetrathiafulvalene connector provides a quite effective electronic  ...[more]

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