High Charge Carrier Mobility in Non-Conjugated 3D Covalent Organic Frameworks

π-Conjugation, π-π stacking, and long-range order play a central role in determining charge transport efficiency in organic materials. Covalent organic frameworks (COFs), which uniquely integrate these key structural and electronic features, have emerged as a promising platform for the development of novel electrically conductive organic materials. Intraframework π-conjugation has shown to play a key role in improving charge carrier mobility. Here, we report Joa-COF-2, a 3D COF lacking extended intraframework π-conjugation, yet exhibiting a remarkable charge carrier mobility of 14 ± 1  cm² V^-1 s^-1. Joa-COF-2 adopts an 11-fold interpenetrated dia topology, featuring a tight interframework π-π stacking, which enables efficient charge transport in the absence of intraframework π-conjugation.