Joaquín Almarza, Karol Strutyński, Shuai Fu, Y Chen, Natalia M. Padial, Isabel del Barrio Gómez, Carlos Martí‐Gastaldo, Andrei N. Khlobystov, M. Bonn, Hai I. Wang, Manuel Melle‐Franco, Aurelio Mateo‐Alonso
ABSTRACT 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 cm 2 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.