First-principles Theoretical Designing of Planar Non-fullerene Small Molecular Acceptors for Organic Solar Cells: Manipulation of Noncovalent Interactions

Non-fullerene small molecular acceptors (NFSMAs) exhibit promising photovoltaic performance; however, their electron mobilities are still relatively lower than those of fullerene derivatives. The construction of a highly planar conjugated system is an important strategy to achieve high charge mobility. In chemical parlance, it is tedious and costly to synthesize planar compounds by restricting the rotation at a specific bond. Recently, nonbonding intramolecular interactions, also termed "conformational locks," have been considered as an alternative way to achieve planar geometry. The successful implementation of this approach for designing polymers has been extensively reported. Recently, several examples of NFSMAs containing conformational locks have been presented in the literature. This situation encourages us to perform a detailed theoretical investigation in designing planar small molecular acceptors. Various nonbonding interactions were studied using accurate computational methods, and molecules with multiple nonbonding interactions showed high planarity. Planar acceptors showed red-shifted absorption with high oscillator strengths. In addition, backbone planarity plays a very important role in tuning the charge transport properties and decreasing reorganization energy. Our results could provide important information to guide the further design of promising NFSMA materials.