Effects of Electron Donating Ability of Substituents and Molecular Conjugation on the Electronic Structures of Organic Radicals

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.

Keywords

Radical emitter / Non-Aufbau electronic structure / Molecular orbital characteristics / Density functional theory and time-dependent density functional theory(DFT and TDDFT)

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