Nonplanar Rhombus and Kagome 2D Covalent Organic Frameworks from Distorted Aromatics for Electrical Conduction

Two-dimensional (2D) covalent organic frameworks (COFs) are an emerging class of promising 2D materials with high crystallinity and tunable structures. However, the low electrical conductivity impedes their applications in electronics and optoelectronics. Integrating large π-conjugated building blocks into 2D lattices to enhance efficient π-stacking and chemical doping is an effective way to improve the conductivity of 2D COFs. Herein, two nonplanar 2D COFs with kagome (DHP-COF) and rhombus (c-HBC-COF) lattices have been designed and synthesized from distorted aromatics with different π-conjugated structures (flexible and rigid structure, respectively). DHP-COF shows a highly distorted 2D lattice that hampers stacking, consequently limiting its charge carrier transport properties. Conversely, c-HBC-COF, with distorted although concave–convex self-complementary nodes, shows a less distorted 2D lattice that does not interfere with interlayer π-stacking. Employing time- and frequency-resolved terahertz spectroscopy, we unveil a high charge-carrier mobility up to 44 cm² V^–1 s^–1, among the highest reported for 2D COFs.