Construction of Interlayer Conjugated Links in 2D Covalent Organic Frameworks via Topological Polymerization.

Yuhao Zhu,Linyu Hu,Chao Sun,Jie Li,Xiao Feng,Bo Wang

Published 2021 in Journal of the American Chemical Society

ABSTRACT

Two-dimensional covalent organic frameworks (2D COFs) are well-defined polymeric sheets that usually stack in an eclipsed mode via van der Waals forces. Extensive efforts have been made to manipulate interlayer interactions, yet there still lack a way to construct conjugated connections between adjacent layers, which is important for (opto)electronic-related applications. Herein, we report an interlayer topological polymerization strategy to transform the well-organized diacetylene columnar arrays in three different 2D COFs (TAPFY-COF, TAPB-COF, and TAPP-COF) into conjugated enyne chains upon heating in the solid state. The resultant COFs (COF-P) with retained high crystallinity possess broadened absorption bands and narrowed band gaps. The newly formed conjugated chains provide extra charge carrier pathways through direct π-electron delocalization. As a proof-of-concept, after topological polymerization, the conductivity of the TAPFY-COF film achieves 2.8 × 10-4 S/cm without doping, and the photothermal, photoacoustic, and oxygen reduction catalytic performance of TAPP-COF is significantly improved.

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