Tian Ye, Si Duanhui, Li Jingjun, Lin Wenlie, Yang Xue, Gao Shuiying, Cao Rong
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, China.
University of the Chinese Academy of Sciences, Beijing, 100049, China.
Small Methods. 2025 Mar;9(3):e2401083. doi: 10.1002/smtd.202401083. Epub 2024 Aug 28.
Covalent organic frameworks (COFs), with their accessible nanoscale porosity, selectable building blocks, and precisely engineered topology, offer unique benefits in the design of room-temperature phosphorescent (RTP) materials. However, their potential has been limited by phosphorescence quenching caused by interlayer π-π stacking interactions. This paper presents a novel strategy to enhance RTP in heavy-atom-free COFs by employing a donor-acceptor (D-A) system that leverages the Förster resonance energy transfer (FRET) and Dexter energy transfer (DET) mechanisms. Among the materials investigated, the best-performing COF exhibits a phosphorescence lifetime of 4.35 ms at room temperature. Spectral analysis, structural analysis, and theoretical calculations indicate the presence of intralayer FRET processes as well as interlayer DET processes within the D-A COF system. Potential anti-counterfeiting applications are explored by exploiting the unique phosphorescent properties of these materials. Additionally, the inherent permanent porosity of COFs presents new opportunities for future development and application. This strategy offers many promising prospects for advancing the RTP technology in COF materials and broadens their potential applications in various fields.
共价有机框架（COFs）具有可及的纳米级孔隙率、可选择的结构单元以及精确设计的拓扑结构，在室温磷光（RTP）材料设计中具有独特优势。然而，其潜力受到层间π-π堆积相互作用导致的磷光猝灭限制。本文提出一种新策略，通过采用供体-受体（D-A）体系利用福斯特共振能量转移（FRET）和德克斯特能量转移（DET）机制来增强无重原子COFs中的RTP。在所研究的材料中，性能最佳的COF在室温下磷光寿命为4.35毫秒。光谱分析、结构分析和理论计算表明，D-A COF体系内存在层内FRET过程以及层间DET过程。通过利用这些材料独特的磷光特性探索了潜在的防伪应用。此外，COFs固有的永久孔隙率为未来的发展和应用带来了新机遇。该策略为推进COF材料中的RTP技术提供了许多有前景的前景，并拓宽了它们在各个领域的潜在应用。
