Engineering the electrostatic potential in a COF's pore by selecting quadrupolar building blocks and linkages

Abstract The electrostatic potential within porous materials critically influences applications like gas storage, catalysis, sensors and semiconductor technology. Precise control of this potential in covalent organic frameworks (COFs) is essential for optimizing these applications. We propose a straightforward method to achieve this by employing electric quadrupolar building blocks. Our comprehensive models accurately reproduce the electrostatic potential in 2D-COFs, requiring only a few parameters that depend solely on local electrostatic properties, independent of the COF’s lattice structure and topology. This approach has been validated across various systems, including conjugated and non-conjugated building blocks with different symmetries. We explore single-layer, few-layer, and bulk systems, achieving changes in the potential which exceed one electronvolt. Stacking configurations such as eclipsed AA, serrated AA’, and inclined stacking all exhibit the tuning effect with minor variations. Finally, we discuss the impact of these potential manipulations on applications like ion and gas uptake.