Electrochemical Reduction and Intramolecular Electron Communication of Nitro Substituted Thiacalix[4]arenes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F16%3A43902666" target="_blank" >RIV/60461373:22310/16:43902666 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388955:_____/16:00462368 RIV/00216208:11310/16:10326312

Výsledek na webu

<a href="http://dx.doi.org/10.1002/elan.201600342" target="_blank" >http://dx.doi.org/10.1002/elan.201600342</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/elan.201600342" target="_blank" >10.1002/elan.201600342</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Electrochemical Reduction and Intramolecular Electron Communication of Nitro Substituted Thiacalix[4]arenes

Popis výsledku v původním jazyce

This contribution is focused on the question, what is the influence of the sulphur bridging units in thiacalix[4]arenes on their electrochemical response. For this reason, two series of oligonitro thiacalix[4]arenes were investigated, where the classic methylene groups are replaced by the sulphur bridge. The reduction pattern of p-tetranitro-1,3-alt-thiacalix[4]arenes (2+2+12 electrons) resembles that of the p-tetranitro-cone-calix[4]arenes and refers to the presence of two different couples of non-interacting nitro groups in the molecule. In contrast, m-oligonitro-1,3-alt-thiacalix[4]arenes exhibit a mutual intramolecular communication between multiple redox centers (nitro groups) due to the combination of two circumstances: nitro groups in the m-positions towards the lower rim are in fact in para- and/or ortho position towards the thia-bridges enabling thus 1,2- and 1,4-quinoid resonance structure, and larger sulphur bridging atom forms two adjacent C-S bonds, which are able to exhibit a hyperconjugative effect. In any case, the intramolecular electron communication takes place via the skeleton, not through space. Consequently, the substituent (inductive, mesomeric) and charge effects are observable, additive and partly quantifiable. Classic polarography proved to be the optimal technique for such investigations.

Název v anglickém jazyce

Electrochemical Reduction and Intramolecular Electron Communication of Nitro Substituted Thiacalix[4]arenes

Popis výsledku anglicky

This contribution is focused on the question, what is the influence of the sulphur bridging units in thiacalix[4]arenes on their electrochemical response. For this reason, two series of oligonitro thiacalix[4]arenes were investigated, where the classic methylene groups are replaced by the sulphur bridge. The reduction pattern of p-tetranitro-1,3-alt-thiacalix[4]arenes (2+2+12 electrons) resembles that of the p-tetranitro-cone-calix[4]arenes and refers to the presence of two different couples of non-interacting nitro groups in the molecule. In contrast, m-oligonitro-1,3-alt-thiacalix[4]arenes exhibit a mutual intramolecular communication between multiple redox centers (nitro groups) due to the combination of two circumstances: nitro groups in the m-positions towards the lower rim are in fact in para- and/or ortho position towards the thia-bridges enabling thus 1,2- and 1,4-quinoid resonance structure, and larger sulphur bridging atom forms two adjacent C-S bonds, which are able to exhibit a hyperconjugative effect. In any case, the intramolecular electron communication takes place via the skeleton, not through space. Consequently, the substituent (inductive, mesomeric) and charge effects are observable, additive and partly quantifiable. Classic polarography proved to be the optimal technique for such investigations.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CG - Elektrochemie

OECD FORD obor

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Projekt

<a href="/cs/project/GA13-21704S" target="_blank" >GA13-21704S: Elektrochemicky aktivní kalix[4]areny a jejich využití pro přípravu nových receptorů a (bio)senzorů</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2016

Kód důvěrnosti údajů

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

Název periodika

Electroanalysis

ISSN

1040-0397

e-ISSN

—

Svazek periodika

28

Číslo periodika v rámci svazku

11

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

5

Strana od-do

2861-2865

Kód UT WoS článku

000387891400031

EID výsledku v databázi Scopus

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