Abstract
The geometries and electronic structures of a series of electron donor-acceptor radical molecules have been studied theoretically. The computational results show that the introduction of substituents with strong electron donating ability into tri-(2,4,6-trichlorophenyl) methyl(TTM) radicals enables the radical molecules to form the non-Aufbau electronic structure. The difficulty of forming the non-Aufbau electronic structure decreases with the enhancement of the electron donating ability of the substituent, but the expansion of the molecular conjugated system is not conducive to the formation. The hybridization of different fragments in molecular orbitals results in the disproportionation of orbital energy level and forms a staggered energy level structure. The electronic structure of radical molecules can be adjusted by substituents and molecular skeleton profoundly, which is a very effective means for molecular design.
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This work was supported by the ‘14th Five-Year’ Science and Technology Project of the Education Department of Jilin Province, China(No. JJKH20220966KJ), the Open Fund of the State Key Laboratory of Luminescent Materials and Devices of South China University of Technology, China(No.2022-skllmd-09), and the LIXIN Outstanding Young Scholar Training Program of Jilin University, China.
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Effects of Electron Donating Ability of Substituents and Molecular Conjugation on the Electronic Structures of Organic Radicals
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Li, P., Feng, L., Li, G. et al. Effects of Electron Donating Ability of Substituents and Molecular Conjugation on the Electronic Structures of Organic Radicals. Chem. Res. Chin. Univ. 39, 202–207 (2023). https://doi.org/10.1007/s40242-023-2364-2
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DOI: https://doi.org/10.1007/s40242-023-2364-2