Chiroptical Redox Switching of Tetra-Cationic Derivatives of Azoniahelicenes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F19%3A00511906" target="_blank" >RIV/61388955:_____/19:00511906 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388963:_____/19:00505705

Výsledek na webu

<a href="http://hdl.handle.net/11104/0302143" target="_blank" >http://hdl.handle.net/11104/0302143</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/celc.201900204" target="_blank" >10.1002/celc.201900204</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Chiroptical Redox Switching of Tetra-Cationic Derivatives of Azoniahelicenes

Popis výsledku v původním jazyce

New tetra- and di-cationic azoniahelicenes provide electrochemical, spectroelectrochemical and electronic circular dichroism (ECD) data reflecting their differences in electron transfer (ET) kinetics. Di-cationic helquats containing two seven-membered rings are irreversibly reduced in two ET steps. Substitution by redox-active ethenylpyridinium in the alpha or gamma position with respect to nitrogen atoms of the helquat core yields tetra-cationic derivatives with reversible ET steps and communicating redox centres. Redox-inactive substituents in di-cationic azoniahelicenes retain ET irreversibility. Redox switching of ECD of tetra-cationic enantiomers was observed. Unlike fully aromatic helquat, the ECD response of tetra-cationic helquats to periodic reduction-oxidation cycles is slower, owing to a strong adsorption on electrodes. Quantum chemical calculations (DFT) indicate that the first ET step of tetra-cationic derivative substituted in the gamma position yields a folded structure, which favours the internal donor-acceptor interaction. This explains the spectroelectrochemical differences between both tetra-cations.

Název v anglickém jazyce

Chiroptical Redox Switching of Tetra-Cationic Derivatives of Azoniahelicenes

Popis výsledku anglicky

New tetra- and di-cationic azoniahelicenes provide electrochemical, spectroelectrochemical and electronic circular dichroism (ECD) data reflecting their differences in electron transfer (ET) kinetics. Di-cationic helquats containing two seven-membered rings are irreversibly reduced in two ET steps. Substitution by redox-active ethenylpyridinium in the alpha or gamma position with respect to nitrogen atoms of the helquat core yields tetra-cationic derivatives with reversible ET steps and communicating redox centres. Redox-inactive substituents in di-cationic azoniahelicenes retain ET irreversibility. Redox switching of ECD of tetra-cationic enantiomers was observed. Unlike fully aromatic helquat, the ECD response of tetra-cationic helquats to periodic reduction-oxidation cycles is slower, owing to a strong adsorption on electrodes. Quantum chemical calculations (DFT) indicate that the first ET step of tetra-cationic derivative substituted in the gamma position yields a folded structure, which favours the internal donor-acceptor interaction. This explains the spectroelectrochemical differences between both tetra-cations.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10405 - Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis)

Projekt

<a href="/cs/project/GA18-04682S" target="_blank" >GA18-04682S: Studium mechanismu transportu elektronů v jednotlivých molekulách pomocí vodivostních a termoelektrických měření.</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2019

Kód důvěrnosti údajů

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

Název periodika

ChemElectroChem

ISSN

2196-0216

e-ISSN

—

Svazek periodika

6

Číslo periodika v rámci svazku

12

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

7

Strana od-do

3002-3008

Kód UT WoS článku

000475465600004

EID výsledku v databázi Scopus

2-s2.0-85065910174