Acta Chimica Sinica ›› 2023, Vol. 81 ›› Issue (7): 717-724.DOI: 10.6023/A23040134 Previous Articles     Next Articles


共价有机框架COF66/COF366的电子结构: 从单体到二维平面聚合物

梁雪峰, 荆剑, 冯昕, 赵勇泽, 唐新员, 何燕, 张立胜, 李慧芳*()   

  1. 青岛科技大学机电工程学院 山东省高性能碳材料制备及应用工程实验室 青岛 266061
  • 投稿日期:2023-04-13 发布日期:2023-06-05
  • 基金资助:
    国家自然科学基金(51676103); 国家自然科学基金(21403037); 山东省泰山学者项目(ts20190937); 及山东省自然科学基金面上项目(ZR2020MB045)

Electronic Structure of Covalent Organic Frameworks COF66 and COF366: from Monomers to Two-Dimensional Framework

Xuefeng Liang, Jian Jing, Xin Feng, Yongze Zhao, Xinyuan Tang, Yan He, Lisheng Zhang, Huifang Li()   

  1. Shandong Engineering Laboratory for Preparation and Application of High-performance Carbon-Materials, College of Electromechanical Engineering, Qingdao University of Science & Technology, Qingdao 266061
  • Received:2023-04-13 Published:2023-06-05
  • Contact: *E-mail:
  • Supported by:
    National Natural Science Foundation of China(51676103); National Natural Science Foundation of China(21403037); Shandong Province Taishan Scholars Program(ts20190937); Natural Science Foundation of Shandong Province(ZR2020MB045)

Two-dimensional covalent organic frameworks (COFs) are an emerging important class of porous materials with periodically ordered structures consisting of core and linker units held together by strong covalent bonds. Their well-designed architecture, tunable functional properties and good thermal stabilities provide great potential for applications in photoenergy conversion and semiconductors. For the aim to explore the relationship between the structure and properties of COFs, which should be very useful for the design of new type of such attractive photo functional materials, the energy character of organic building units, fragment molecules and periodic two-dimensional planar structures are analyzed for COF66 and COF366. The results show that the structure of periodic planar frameworks will be influenced by the geometry of organic building units. Moreover, the relative energy level of the frontier orbitals of the organic building blocks will affect the ionization potential and electron affinity. And the electronic properties of the COFs are also in the same case. Therefore, the electronic property of organic building units is a key factor for determining the electronic structure of periodic structure of COFs. In addition, the electronic coupling of COFs will be larger if the conjugation of the organic building blocks is better. Then, the valence band maximum and conduction band minimum will be more dispersive, and the charge carrier mobility will get larger.

Key words: organic units available, two-dimensional covalent organic framework, electronic structure, density functional theory