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Tuning Molecular Electron Affinities against Atomic Electronegativities by Spatial Expansion of a π-System Научная публикация

Журнал ChemPhysChem
ISSN: 1439-4235 , E-ISSN: 1439-7641
Вых. Данные Год: 2023, Номер статьи : e202200876, Страниц : 8 DOI: 10.1002/cphc.202200876
Авторы Chulanova Elena A. 1,3 , Radiush Ekaterina A. 1 , Semenov Nikolay A. 1 , Hupf Emanuel 2 , Irtegova Irina G. 1 , Kosenkova Yulia S 1 , Bagryanskaya Irina Yu. 1 , Shundrin Leonid A. 1 , Beckmann Jens 2 , Zibarev Andrey V. 1
Организации
1 Novosibirsk Institute of Organic Chemistry Siberian Branch of the Russian Academy of Sciences
2 Institute for Inorganic Chemistry and Crystallography University of Bremen
3 Institute for Applied Physics University of Tübingen

Информация о финансировании (2)

1 Российский Научный Фонд 22-13-00108
2 Российский Научный Фонд 21-73-10291

Реферат: 2,1,3-Benzochalcogenadiazoles C6R4N2E (E/R; E=S, Se, Te; R=H, F, Cl, Br, I) and C6H2R2N2E (E/R’; E=S, Se, Te; R=Br, I) are 10π-electron hetarenes. By CV/EPR measurements, DFT calculations, and QTAIM and ELI-D analyses, it is shown that their molecular electron affinities (EAs) increase with decreasing Allen electronegativities and electron affinities of the E and non-hydrogen R (except Cl) atoms. DFT calculations for E/R+e⋅−→[E/R]⋅− electron capture reveal negative ΔG values numerically increasing with increasing atomic numbers of the E and R atoms; positive ΔS has a minor influence. It is suggested that the EA increase is caused by more effective charge/spin delocalization in the radical anions of heavier derivatives due to contributions from diffuse (a real-space expanded) p-AOs of the heavier E and R atoms; and that this counterintuitive effect might be of the general character.
Библиографическая ссылка: Chulanova E.A. , Radiush E.A. , Semenov N.A. , Hupf E. , Irtegova I.G. , Kosenkova Y.S. , Bagryanskaya I.Y. , Shundrin L.A. , Beckmann J. , Zibarev A.V.
Tuning Molecular Electron Affinities against Atomic Electronegativities by Spatial Expansion of a π-System
ChemPhysChem. 2023. e202200876 :1-8. DOI: 10.1002/cphc.202200876 WOS РИНЦ OpenAlex
Даты:
Опубликована в печати: 11 янв. 2023 г.
Опубликована online: 20 янв. 2023 г.
Поступила в редакцию: 23 нояб. 2023 г.
Идентификаторы БД:
Web of science: WOS:000936339500001
РИНЦ: 60560494
OpenAlex: W4317567975
Цитирование в БД:
БД Цитирований
OpenAlex 8
Web of science 10
Альметрики: