Are Redox-Active Centers Bridged by Saturated Flexible Linkers Systematically Electrochemically Independent?
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F24%3A00587603" target="_blank" >RIV/61388955:_____/24:00587603 - isvavai.cz</a>
Result on the web
<a href="https://hdl.handle.net/11104/0354735" target="_blank" >https://hdl.handle.net/11104/0354735</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/anie.202406299" target="_blank" >10.1002/anie.202406299</a>
Alternative languages
Result language
angličtina
Original language name
Are Redox-Active Centers Bridged by Saturated Flexible Linkers Systematically Electrochemically Independent?
Original language description
The extent to which electrophores covalently bridged by a saturated linker are electrochemically independent was investigated considering the charge/spin duality of the electron and functionality of the electrophore as a spin carrier upon reduction. By combining computational modeling with electrochemical experiments, we investigated the mechanism by which tethered electrophores react together within 4,4′-oligo[n]methylene-bipyridinium assemblies (with n=2 to 5). We show that native dicationic electrophores (redox state Z=+2) are folded prior to electron injection into the system, allowing the emergence of supra-molecular orbitals (supra-MOs) likely to support the process of the reductive σ bond formation giving cyclomers. Indeed, for Z=+2, London Dispersion (LD) forces contribute to flatten the potential energy surface such that all-trans and folded conformers are approximately isoenergetic. Then, upon one-electron injection, for radical cations (Z=+1), LD forces significantly stabilize the folded conformers, except for the ethylene derivative deprived of supra-MOs. For radical cations equipped with supra-MOs, the unpaired electron is delocalized over both heterocycles through space. Cyclomer completion (Z=0) upon the second electron transfer occurs according to the inversion of redox potentials. This mechanism explains why intramolecular reactivity is favored and why pyridinium electrophores are not independent.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - 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)
Result continuities
Project
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2024
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Angewandte Chemie - International Edition
ISSN
1433-7851
e-ISSN
1521-3773
Volume of the periodical
63
Issue of the periodical within the volume
31
Country of publishing house
DE - GERMANY
Number of pages
11
Pages from-to
e202406299
UT code for WoS article
001257886400001
EID of the result in the Scopus database
2-s2.0-85197393309