Abstract
Covalent organic frameworks (COFs) are materials of growing interest for electronic applications due to their tunable structures, chemical stability, and layered architectures that support extended π-systems and directional charge transport. While their electronic properties are strongly influenced by the choice of molecular building blocks and the stacking arrangement, experimental control over these features remains limited, and the number of well-characterized COFs is still relatively small. Here, we explore two alternative strategies, hydrostatic pressure and metal intercalation, to tune the electronic structure of COFs. Using periodic density functional theory (DFT) calculations, we show that the band gap of pristine COF-1 decreases by ∼1 eV under compression up to 10 GPa. Metal intercalation induces an even greater reduction, in some cases leading to metallic behavior. We demonstrate that pressure and intercalation offer effective, continuous control over COF electronic properties, providing powerful means to complement and extend conventional design approaches.