Publication: Formation of a supramolecular charge-transfer complex. Ultrafast excited state dynamics and quantum-chemical calculations
Дата
2019
Авторы
Volchkov, Valery V.
Khimich, Mikhail N.
Rusalov, Mikhail V.
Gostev, Fedor E.
Freidzon, Alexandra Ya.
Фрейдзон, Александра Яковлевна
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Аннотация
The formation of a supramolecular complex of bis(18-crown-6) stilbene (1) and 4,4'-bipyridine with two ammoniopropyl N-substituents (3) and the substitution reaction between 1 center dot 3 and alkali and alkaline-earth metal perchlorates have been studied using absorption, steady-state fluorescence, and femtosecond transient absorption spectroscopy. The formation of 1 center dot(Mn+)(2) complexes in acetonitrile was demonstrated. The weak long-wavelength charge-transfer absorption band of 1 center dot 3 completely vanishes upon complexation with metal cations because of disruption of the pseudocyclic structure. The spectroscopic and luminescence parameters, stability and substitution constants were calculated. The relaxation scheme of the 1 center dot 3 singlet state excited by a 25 fs laser pulse was proposed. It includes very fast vibrational relaxation and direct (tau(CT-d) = 0.32 ps) and back (tau(CT-b) = 0.51 ps) electron transfer resulting in complete fluorescence quenching. The quantum-chemistry calculations revealed the species taking part in the ET process and elucidated the mechanism of relaxation of the excited complex.
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Formation of a supramolecular charge-transfer complex. Ultrafast excited state dynamics and quantum-chemical calculations / Volchkov, ValeryV [et al.] // Photochemical and Photobiological Sciences. - 2019. - 18. - № 1. - P. 232-241;. - 10.1039/c8pp00328a
URI
https://www.doi.org/10.1039/c8pp00328a
https://www.scopus.com/record/display.uri?eid=2-s2.0-85058406970&origin=resultslist
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https://openrepository.mephi.ru/handle/123456789/16509
https://www.scopus.com/record/display.uri?eid=2-s2.0-85058406970&origin=resultslist
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=Alerting&SrcApp=Alerting&DestApp=WOS_CPL&DestLinkType=FullRecord&UT=WOS:000457260400022
https://openrepository.mephi.ru/handle/123456789/16509