Boosting Covalent Organic Framework Luminescence by Suppressing Nonradiative Pathways  

作　　者：Minghao Liu Yuan-Zhe Cheng Yubin Fu Shuai Bi Xuesong Ding Bao-Hang Han Qing Xu Gaofeng Zeng 

机构地区：[1]CAS Key Laboratory of Low-Carbon Conversion Science and Engineering,Shanghai Advanced Research Institute,Chinese Academy of Sciences,Shanghai,201210 China [2]Department of Chemistry,Laboratory of Advanced Materials,State Key Laboratory of Molecular Engineering of Polymers,Fudan University,Shanghai,200433 China [3]CAS Key Laboratory of Nanosystem and Hierarchical Fabrication,CAS Center for Excellence in Nanoscience,National Center for Nanoscience and Technology,Beijing,100190 China [4]University of Chinese Academy of Sciences,Beijing,100049 China [5]Center for Advancing Electronics Dresden(CFAED)and Faculty of Chemistry and Food Chemistry,Technische Universität Dresden,01062 Dresden,Germany [6]Max Planck Institute of Microstructure Physics,Weinberg 2,06120 Halle,Germany [7]Department of Chemistry,City University of Hong Kong,Kowloon,Hong Kong,China

出　　处：《Chinese Journal of Chemistry》2025年第6期633-640,共8页中国化学(英文版)

基　　金：the National Natural Science Foundation of China(52303288,22075309,22378413,22161132010);National Key R&D Program of China Ministry of Science and Technology(2024YFE0206900);Science and Technology Innovation Plan of the Science and Technology Commission of Shanghai Municipality(22ZR1470100,23DZ1202600,23DZ1201804);the Youth Innovation Promotion Association of Chinese Academy of Sciences(E324441401);Biomaterials and Regenerative Medicine Institute Cooperative Research Project Shanghai Jiao Tong University School of Medicine(2022LHA09);Dr.Y.Fu gratefully acknowledge the GWK support for funding this project by providing computing time through the Center for Information Services and HPC(ZIH)at TU Dresden;Dr.S.Bi thanks the financial support by a fellowship award from the Research Grants Council of the Hong Kong Special Administrative Region,China(Project No.CityU PDFS2324-1S08).

摘　　要：Comprehensive Summary The construction of luminescent two-dimensional(2D)imine-linked covalent organic frameworks(COFs)is a formidable challenge due to the strong interlayer stacking and bond rotations that typically suppress intramolecular charge transfer(ICT),leading to nonradiative energy dissipation.Herein,three COFs with tailored interlayer distances and bond rotations are designed to modulate the ICT behaviours.The targeted COF(TPAZ-TPE-COF)achieved a significantly enhanced photoluminescence quantum yield(PLQY)of 21.22%in the solid state by restricting bond rotation and enlarging the layer distance.This represents a 3.5-fold and 530.5-fold improvement over TPAZ-PYTA-COF(6.15%),which has a shortened interlayer space,and TPAZ-PATA-COF(0.04%),which exhibits strong bond rotations,respectively.Importantly,TPAZ-TPE-COF also exhibits exceptional sensing performance for iron ions,with a detection limit at the ppb level.Both experimental and theoretical analyses reveal that the prominent luminescent performance of TPAZ-TPE-COF is assigned to the effective suppression of nonradiative pathways,especially those arising from interlayer stacking and bond vibrations.These findings pave the way for deliberate construction of imine-linked 2D COFs with high PL intensity,thereby expanding the portfolio of luminescent COFs with potential applications in sensing and optoelectronics.

关 键 词：Covalent organic frameworks PHOTOLUMINESCENCE Intramolecular charge transfer Nonradiative pathways Light-emitting diodes Porous polymers Sensors Molecular recognition 

分 类 号：O62[理学—有机化学]