A macrocyclic receptor containing two viologen species connected by conjugated terphenyl groups

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F18%3A43916903" target="_blank" >RIV/60461373:22310/18:43916903 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388955:_____/18:00499064

Výsledek na webu

<a href="https://pubs.rsc.org/en/content/articlepdf/2018/ob/c8ob00919h" target="_blank" >https://pubs.rsc.org/en/content/articlepdf/2018/ob/c8ob00919h</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/c8ob00919h" target="_blank" >10.1039/c8ob00919h</a>

Jazyk výsledku

angličtina

Název v původním jazyce

A macrocyclic receptor containing two viologen species connected by conjugated terphenyl groups

Popis výsledku v původním jazyce

A macrocyclic receptor molecule containing two viologen species connected by conjugated terphenyl groups has been designed and synthesised. The single-crystal X-ray structure shows that the two viologen residues have a transannular N center dot center dot center dot N separation of ca. 7.4 angstrom. Thus, the internal cavity dimensions are suitable for the inclusion of pi-electron-rich species. The macrocycle is redox active, and can accept electrons from suitable donor species including triethylamine, resulting in a dramatic colour change from pale yellow to dark green as a consequence of the formation of a paramagnetic bis(radical cationic) species. Cyclic voltammetry shows that the macrocycle can undergo two sequential and reversible reduction processes (E-1/2 = -0.65 and -0.97 V vs. Fc/Fc(+)). DFT and TD-DFT studies accurately replicate the structure of the tetracationic macrocycle and the electronic absorption spectra of the three major redox states of the system. These calculations also showed that during electrochemical reduction, the unpaired electron density of the radical cations remained relatively localised within the heterocyclic rings. The ability of the macrocycle to form supramolecular complexes was confirmed by the formation of a pseudorotaxane with a guest molecule containing a p-electron-rich 1,5-dihydroxynaphthalene derivative. Threading and dethreading of the pseudorotaxane was fast on the NMR timescale, and the complex exhibited an association constant of 150 M-1 (+/- 30 M-1) as calculated from H-1 NMR titration studies.

Název v anglickém jazyce

A macrocyclic receptor containing two viologen species connected by conjugated terphenyl groups

Popis výsledku anglicky

A macrocyclic receptor molecule containing two viologen species connected by conjugated terphenyl groups has been designed and synthesised. The single-crystal X-ray structure shows that the two viologen residues have a transannular N center dot center dot center dot N separation of ca. 7.4 angstrom. Thus, the internal cavity dimensions are suitable for the inclusion of pi-electron-rich species. The macrocycle is redox active, and can accept electrons from suitable donor species including triethylamine, resulting in a dramatic colour change from pale yellow to dark green as a consequence of the formation of a paramagnetic bis(radical cationic) species. Cyclic voltammetry shows that the macrocycle can undergo two sequential and reversible reduction processes (E-1/2 = -0.65 and -0.97 V vs. Fc/Fc(+)). DFT and TD-DFT studies accurately replicate the structure of the tetracationic macrocycle and the electronic absorption spectra of the three major redox states of the system. These calculations also showed that during electrochemical reduction, the unpaired electron density of the radical cations remained relatively localised within the heterocyclic rings. The ability of the macrocycle to form supramolecular complexes was confirmed by the formation of a pseudorotaxane with a guest molecule containing a p-electron-rich 1,5-dihydroxynaphthalene derivative. Threading and dethreading of the pseudorotaxane was fast on the NMR timescale, and the complex exhibited an association constant of 150 M-1 (+/- 30 M-1) as calculated from H-1 NMR titration studies.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2018

Kód důvěrnosti údajů

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

Název periodika

Organic and Biomolecular Chemistry

ISSN

1477-0520

e-ISSN

—

Svazek periodika

16

Číslo periodika v rámci svazku

27

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

10

Strana od-do

5006-5015

Kód UT WoS článku

000438393200012

EID výsledku v databázi Scopus

2-s2.0-85049890088