Reticular Synthesis of One‐Dimensional Covalent Organic Frameworks with 4‐c sql Topology for Enhanced Fluorescence Emission

Covalent organic frameworks (COFs) have been extensively investigated due to their unique structure, porosity, and functionality. However, at the topological level, COFs remain as two‐dimensional (2D) or three‐dimensional (3D) structures, while COFs with one‐dimensional (1D) topology have not been systematically explored. In this work, we proposed a synthetic strategy for the construction of 1D‐COFs based on non‐linear edges and suitable high‐symmetry vertices. Compared with their 2D‐COFs counterparts, the 1D‐COFs with AIEgens located at the vertex of the frame exhibited enhanced fluorescence. The density functional theory (DFT) calculations revealed that the dimensional‐induced rotation restriction (DIRR) effect could spontaneously introduce additional non‐covalent interactions between the strip frames, which could substantially diminish non‐radiative transitions. This work also provides protocols for the design of 1D‐COFs and a guidance scheme for the synthesis of emitting COFs. A series of 1D‐COFs were synthesized by combining vertices with different symmetries and matching the nonlinear edges. The 1D‐COFs, which employed AIEgens as the vertex, showed enhanced fluorescence emission properties compared with their 2D analogs.