Incorporation of a Boron–Nitrogen Covalent Bond Improves the Charge-Transport and Charge-Transfer Characteristics of Organoboron Small-Molecule Acceptors for Organic Solar Cells

An organoboron small-molecular acceptor (OSMA) M_B←N containing a boron–nitrogen coordination bond (B←N) exhibits good light absorption in organic solar cells (OSCs). In this work, based on M_B←N, OSMA M_B-N, with the incorporation of a boron–nitrogen covalent bond (B-N), was designed. We have systematically investigated the charge-transport properties and interfacial charge-transfer characteristics of M_B-N, along with M_B←N, using the density functional theory (DFT) and the time-dependent density functional theory (TD-DFT). Theoretical calculations show that M_B-N can simultaneously boost the open-circuit voltage (from 0.78 V to 0.85 V) and the short-circuit current due to its high-lying lowest unoccupied molecular orbital and the reduced energy gap. Moreover, its large dipole shortens stacking and greatly enhances electron mobility by up to 5.91 × 10⁻³ cm²·V⁻¹·s⁻¹. Notably, the excellent interfacial properties of PTB7-Th/M_B-N, owing to more charge transfer states generated through the direct excitation process and the intermolecular electric field mechanism, are expected to improve OSCs performance. Together with the excellent properties of M_B-N, we demonstrate a new OSMA and develop a new organoboron building block with B-N units. The computations also shed light on the structure–property relationships and provide in-depth theoretical guidance for the application of organoboron photovoltaic materials.