Acta Chimica Sinica ›› 2023, Vol. 81 ›› Issue (6): 613-619.DOI: 10.6023/A23030071 Previous Articles     Next Articles



杨磊a, 葛娇阳a, 王访丽a, 吴汪洋a, 郑宗祥a, 曹洪涛a, 王洲c, 冉雪芹b,*(), 解令海a,*()   

  1. a 南京邮电大学 信息材料与纳米技术研究院/材料科学与工程学院 有机电子与信息显示国家重点实验室 南京 210023
    b 南京工业大学 柔性电子(未来技术)学院 南京 211816
    c 南京邮电大学 计算机学院 南京 210023
  • 投稿日期:2023-03-06 发布日期:2023-05-19
  • 基金资助:
    中国博士后科学基金面上项目(2022M711684); 江苏省高等学校基础科学(自然科学)研究面上项目(22KJB430036); 国家自然科学基金(21503114); 国家自然科学基金(21774061); 国家自然科学基金(61605090); 国家自然科学基金(61604076); 南京邮电大学科学基金(NY215056); 南京邮电大学科学基金(NY214176); 南京邮电大学科学基金(NY215172); 南京邮电大学科学基金(2016XSG03)

A Theoretical Study on the Effective Reduction of Internal Reorganization Energy Based on the Macrocyclic Structure of Fluorene

Lei Yanga, Jiaoyang Gea, Fangli Wanga, Wangyang Wua, Zongxiang Zhenga, Hongtao Caoa, Zhou Wangc, Xueqin Ranb(), Linhai Xiea()   

  1. a State Key Laboratory for Organic Electronics and Information Displays, Institute of Information Materials and Nanotechnology, College of Materials Science and Engineering, Nanjing University of Posts &Telecommunications, Nanjing 210023, China
    b School of Flexible Electronics (Future Technologies), Nanjing Tech University (Nanjing Tech), Nanjing 211816, China
    c College of Computer, Nanjing University of Posts and Telecommunications, Nanjing 210023, China
  • Received:2023-03-06 Published:2023-05-19
  • Contact: *E-mail:;
  • Supported by:
    China Postdoctoral Science Foundation(2022M711684); Natural Science Foundation of the Jiangsu Higher Education Institutions(22KJB430036); National Natural Science Foundation of China(21503114); National Natural Science Foundation of China(21774061); National Natural Science Foundation of China(61605090); National Natural Science Foundation of China(61604076); Nanjing University of Posts and Telecommunications Scientific Foundation NUPTSF, China(NY215056); Nanjing University of Posts and Telecommunications Scientific Foundation NUPTSF, China(NY214176); Nanjing University of Posts and Telecommunications Scientific Foundation NUPTSF, China(NY215172); Nanjing University of Posts and Telecommunications Scientific Foundation NUPTSF, China(2016XSG03)

Organic semiconductor materials are widely used in organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), and organic solar cells (OSCs), but their low mobility is not conducive to electron transport. In this work, a novel class of grid structures based on fluorene (OF) with a “口” structure has been designed and calculated, which has a geometric structure that can extend laterally compared with ordinary macrocyclic molecules. Density functional theory was utilized to study its molecular structure, ring strain energy, and various electronic properties, including molecular orbitals, adiabatic ionization potential, adiabatic electron affinity potentials, and reorganization energies. In addition, the weak interactions within molecules and the contribution of each vibration mode to the reorganization energy of OF were investigated by using non-covalent interaction analysis and Normal Mode (NM) analysis, respectively. The results show that OF has a weak ring strain energy (8.20 kJ/mol) which will be easily synthesized. Through intramolecular weak interaction analysis, it is found that in cis-OF the two fluorene elements on the beam are close and produce a certain angle, the π-π interaction is generated. Compared with Bis-Fl1, Bis-Fl2, Quarter-Fl1 and Quarter-Fl2, the energy gap of OF molecules decreases, the highest occupied molecular orbital (HOMO) energy level increases, and the lowest unoccupied molecular orbital (LUMO) energy level decreases, corresponding to adiabatic ionization potential (IPa) and adiabatic electron affinity(EAa), that is, the IPa of OF molecules decreases and EAa increases, which proves that the lattice effect can improve the hole and electron injection ability of molecules. At the same time, OF has a lower IPa which would be a very potential p-type molecular material. Interestingly, the reorganization energy of both OF molecules decreased compared with BF and QF, indicating that the lattice effect is an effective way to reduce the hole and electron reorganization energy which provides a strategy for the design of organic semiconductor materials with excellent charge transport properties.

Key words: fluorine, density functional theory, weak interactions, reorganization energy, electron transport