Single-Step versus Stepwise Two-Electron Reduction of Polyarylpyridiniums: Insights from the Steric Switching of Redox Potential Compression
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F12%3A00376013" target="_blank" >RIV/61388955:_____/12:00376013 - isvavai.cz</a>
Result on the web
<a href="http://dx.doi.org/10.1021/ja210024y" target="_blank" >http://dx.doi.org/10.1021/ja210024y</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/ja210024y" target="_blank" >10.1021/ja210024y</a>
Alternative languages
Result language
angličtina
Original language name
Single-Step versus Stepwise Two-Electron Reduction of Polyarylpyridiniums: Insights from the Steric Switching of Redox Potential Compression
Original language description
Contrary to 4,4'-dipyridinium (i.e., archetypal methyl viologen), which is reduced by two single-electron transfers (stepwise reduction), the 4,1'-dipyridinium isomer (so-called "head-to-tail" isomer) undergoes two electron transfers at apparently the same potential (single-step reduction). A combined theoretical and experimental study has been undertaken to establish that the latter electrochemical behavior, also observed for other polyarylpyridinium electrophores, is due to potential compression originating in a large structural rearrangement. Three series of branched expanded pyridiniums (EPs) were prepared: N-aryl-2,4,6-triphenylpyridiniums (Ar-TP), N-aryl-2,3,4,5,6-pentaphenylpyridiniums (Ar-XP), and N-aryl-3,5-dimethyl-2,4,6-triphenylpyridinium (Ar-DMTP). The intramolecular steric strain was tuned via N-pyridinio aryl group (Ar) phenyl (Ph), 4-pyridyl (Py), and 4-pyridylium (qPy) and their bulky 3,5-dimethyl counterparts, xylyl (Xy), lutidyl (Lu), and lutidylium (qLu), respective
Czech name
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Czech description
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Classification
Type
J<sub>x</sub> - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
CG - Electrochemistry
OECD FORD branch
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Result continuities
Project
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Continuities
Z - Vyzkumny zamer (s odkazem do CEZ)
Others
Publication year
2012
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of the American Chemical Society
ISSN
0002-7863
e-ISSN
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Volume of the periodical
134
Issue of the periodical within the volume
5
Country of publishing house
US - UNITED STATES
Number of pages
15
Pages from-to
2691-2705
UT code for WoS article
000300460600042
EID of the result in the Scopus database
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