电负性
化学
离域电子
电子顺磁共振
亲缘关系
电子亲和性(数据页)
结晶学
计算化学
原子物理学
立体化学
分子
物理
核磁共振
有机化学
作者
Elena A. Chulanova,Ekaterina A. Radiush,Nikolay A. Semenov,Emanuel Hupf,Irina G. Irtegova,Yulia S Kosenkova,I. Yu. Bagryanskaya,Leonid A. Shundrin,Jens Beckmann,Andrey V. Zibarev
标识
DOI:10.1002/cphc.202200876
摘要
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.
科研通智能强力驱动
Strongly Powered by AbleSci AI