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高等学校化学研究 ›› 2023, Vol. 39 ›› Issue (2): 202-207.doi: 10.1007/s40242-023-2364-2

• Article • 上一篇    下一篇

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

LI Pengyuan1,2, FENG Lu1, LI Guangyue2, BAI Fuquan1,3   

  1. 1. International Joint Research Laboratory of Nano-Micro Architecture Chemistry, Institute of Theoretical Chemistry and College of Chemistry, Jilin University, Changchun 130021, P. R. China;
    2. College of Chemical Engineering, North China University of Science and Technology, Tangshan 063210, P. R. China;
    3. International Innovation Center for Forest Chemicals and Materials, Nanjing Forestry University, Nanjing 210037, P. R. China
  • 收稿日期:2022-12-31 出版日期:2023-04-01 发布日期:2023-03-16
  • 通讯作者: BAI Fuquan, LI Guangyue E-mail:baifq@jlu.edu.cn;gyli@ncst.edu.cn
  • 基金资助:
    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.

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

LI Pengyuan1,2, FENG Lu1, LI Guangyue2, BAI Fuquan1,3   

  1. 1. International Joint Research Laboratory of Nano-Micro Architecture Chemistry, Institute of Theoretical Chemistry and College of Chemistry, Jilin University, Changchun 130021, P. R. China;
    2. College of Chemical Engineering, North China University of Science and Technology, Tangshan 063210, P. R. China;
    3. International Innovation Center for Forest Chemicals and Materials, Nanjing Forestry University, Nanjing 210037, P. R. China
  • Received:2022-12-31 Online:2023-04-01 Published:2023-03-16
  • Contact: BAI Fuquan, LI Guangyue E-mail:baifq@jlu.edu.cn;gyli@ncst.edu.cn
  • Supported by:
    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.

摘要： 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.

关键词: Radical emitter, Non-Aufbau electronic structure, Molecular orbital characteristic, Density functional theory and time-dependent density functional theory(DFT and TDDFT)

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.

Key words: Radical emitter, Non-Aufbau electronic structure, Molecular orbital characteristic, Density functional theory and time-dependent density functional theory(DFT and TDDFT)