Cooperative Interaction of Hydronium Ion with an Ethereally Fenced Hexaarylbenzene-Based Receptor: An NMR and Theoretical Study

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F10%3A00023066" target="_blank" >RIV/60461373:22310/10:00023066 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61389013:_____/10:00342393 RIV/49777513:23520/10:00503380

Výsledek na webu

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DOI - Digital Object Identifier

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Jazyk výsledku

angličtina

Název v původním jazyce

Cooperative Interaction of Hydronium Ion with an Ethereally Fenced Hexaarylbenzene-Based Receptor: An NMR and Theoretical Study

Popis výsledku v původním jazyce

Using H-1 and C-13 NMR and DFT calculations, the structure and interactions of the symmetric ethereally fenced hexaarylbenzene receptor 1 with hydronium ions were studied. Both 1 and its equimolecular complex 1 H3O+ exhibit C-3v symmetry. According to DFT, two similar optimal structures of the complex exist, the more stable one being 15.4 kJ/mol lower in energy. The equilibrium between 1 and 1 (HO+)-O-3 complexes is characterized by the stabilization constant K = 1.97 x 10(6) (i.e., the binding constantn = 6.3) according to both proton and carbon NMR spectra. The exchange dynamics between 1 and the complex measured by the delay-varied CPMG sequence had to be corrected for the internal exchange processes in both 1 (conformation change) and the complex(vacillation between the two minima). After this correction, the correlation time of exchange was found to be 4.76 x 10(-5) s. Such relatively fast exchange can be explained only by it being mediated by the excess water molecules present

Název v anglickém jazyce

Cooperative Interaction of Hydronium Ion with an Ethereally Fenced Hexaarylbenzene-Based Receptor: An NMR and Theoretical Study

Popis výsledku anglicky

Using H-1 and C-13 NMR and DFT calculations, the structure and interactions of the symmetric ethereally fenced hexaarylbenzene receptor 1 with hydronium ions were studied. Both 1 and its equimolecular complex 1 H3O+ exhibit C-3v symmetry. According to DFT, two similar optimal structures of the complex exist, the more stable one being 15.4 kJ/mol lower in energy. The equilibrium between 1 and 1 (HO+)-O-3 complexes is characterized by the stabilization constant K = 1.97 x 10(6) (i.e., the binding constantn = 6.3) according to both proton and carbon NMR spectra. The exchange dynamics between 1 and the complex measured by the delay-varied CPMG sequence had to be corrected for the internal exchange processes in both 1 (conformation change) and the complex(vacillation between the two minima). After this correction, the correlation time of exchange was found to be 4.76 x 10(-5) s. Such relatively fast exchange can be explained only by it being mediated by the excess water molecules present

Druh

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

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

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Projekt

<a href="/cs/project/GA203%2F09%2F1478" target="_blank" >GA203/09/1478: Poloxamery a jejich modifikace - mechanismus micelace a gelace</a><br>

Návaznosti

Z - Vyzkumny zamer (s odkazem do CEZ)

Rok uplatnění

2010

Kód důvěrnosti údajů

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

Název periodika

Journal of Physical Chemistry A

ISSN

1089-5639

e-ISSN

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Svazek periodika

114

Číslo periodika v rámci svazku

16

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

8

Strana od-do

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Kód UT WoS článku

000276888800013

EID výsledku v databázi Scopus

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