Outstanding Charge Mobility by Band Transport in Two-Dimensional Semiconducting Covalent Organic Frameworks

[Image: see text] Two-dimensional covalent organic frameworks (2D COFs) represent a family of crystalline porous polymers with a long-range order and well-defined open nanochannels that hold great promise for electronics, catalysis, sensing, and energy storage. To date, the development of highly conductive 2D COFs has remained challenging due to the finite π-conjugation along the 2D lattice and charge localization at grain boundaries. Furthermore, the charge transport mechanism within the crystalline framework remains elusive. Here, time- and frequency-resolved terahertz spectroscopy reveals intrinsically Drude-type band transport of charge carriers in semiconducting 2D COF thin films condensed by 1,3,5-tris(4-aminophenyl)benzene (TPB) and 1,3,5-triformylbenzene (TFB). The TPB–TFB COF thin films demonstrate high photoconductivity with a long charge scattering time exceeding 70 fs at room temperature which resembles crystalline inorganic materials. This corresponds to a record charge carrier mobility of 165 ± 10 cm(2) V(–1) s(–1), vastly outperforming that of the state-of-the-art conductive COFs. These results reveal TPB–TFB COF thin films as promising candidates for organic electronics and catalysis and provide insights into the rational design of highly crystalline porous materials for efficient and long-range charge transport.