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

Autor: Chulanova EA; Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090, Novosibirsk, Russian Federation.; Current address: Institute for Applied Physics, University of Tübingen, 72076, Tübingen, Germany., Radiush EA; Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090, Novosibirsk, Russian Federation., Semenov NA; Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090, Novosibirsk, Russian Federation., Hupf E; Institute for Inorganic Chemistry and Crystallography, University of Bremen, 28359, Bremen, Germany., Irtegova IG; Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090, Novosibirsk, Russian Federation., Kosenkova YS; Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090, Novosibirsk, Russian Federation., Bagryanskaya IY; Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090, Novosibirsk, Russian Federation., Shundrin LA; Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090, Novosibirsk, Russian Federation., Beckmann J; Institute for Inorganic Chemistry and Crystallography, University of Bremen, 28359, Bremen, Germany., Zibarev AV; Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090, Novosibirsk, Russian Federation.
Jazyk: angličtina
Zdroj: Chemphyschem : a European journal of chemical physics and physical chemistry [Chemphyschem] 2023 May 02; Vol. 24 (9), pp. e202200876. Date of Electronic Publication: 2023 Feb 20.
DOI: 10.1002/cphc.202200876
Abstrakt: 2,1,3-Benzochalcogenadiazoles C 6 R 4 N 2 E (E/R; E=S, Se, Te; R=H, F, Cl, Br, I) and C 6 H 2 R 2 N 2 E (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.
(© 2023 Wiley-VCH GmbH.)
Databáze: MEDLINE
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