Intramolecular Chloro–Sulfur Interaction and Asymmetric Side‐Chain Isomerization to Balance Crystallinity and Miscibility in All‐Small‐Molecule Solar Cells

Intramolecular Cl-S non-covalent interaction is introduced to modify molecular backbone of a benzodithiophene terthiophene rhodamine (BTR) benchmark structure, helping planarize and rigidify the molecular framework for improving charge transport. Theoretical simulations and temperature-variable NMR experiments clearly validate the existence of Cl-S non-covalent interaction in two designed chlorinated donors and explain its important role in enhancing planarity and rigidity of the molecules for enhancing their crystallinity. The asymmetric isomerization of side-chains further optimizes the molecular orientation and surface energy to strike a balance between its crystallinity and miscibility. This carefully manipulated molecular design helps result in increased carrier mobility and suppressed charge recombination to obtain simultaneously enhanced short-circuit current (Jsc ) and fill factor (FF) and a very high efficiency of 15.73 % in binary all-small-molecule organic solar cells.