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

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

Journal

ChemPhysChem
ISSN: 1439-4235 , E-ISSN: 1439-7641

Output data

Year: 2023, Article number : e202200876, Pages count : 8 DOI: 10.1002/cphc.202200876

Authors

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

Affiliations

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

Funding (2)

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

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.

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

Published print:	Jan 11, 2023
Published online:	Jan 20, 2023
Submitted:	Nov 23, 2023

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