Chlorinated Benzo[1,2‐b:4,5‐c′]dithiophene‐4,8‐dione Polymer Donor: A Small Atom Makes a Big Difference

The position of a chlorine atom in a charge carrier of polymer solar cells (PSCs) is important to boost their photovoltaic performance. Herein, two chlorinated D-A conjugated polymers PBBD-Cl-α and PBBD-Cl-β are synthesized based on two new building blocks (TTO-Cl-α and TTO-Cl-β) respectively by introducing the chlorine atom into α or β position of the upper thiophene of the highly electron-deficient benzo[1,2-b:4,5-c']dithiophene-4,8-dione moiety. Single-crystal analysis demonstrates that the chlorine-free TTO shows a π-π stacking distance (dπ-π) of 3.55 A. When H atom at the α position of thiophene of TTO is replaced by Cl, both π-π stacking distance (dπ-π = 3.48 A) and Cl···S distance (dCl-S = 4.4 A) are simultaneously reduced for TTO-Cl-α compared with TTO. TTO-Cl-β then showed the Cl···S non-covalent interaction can further shorten the intermolecular π-π stacking separation to 3.23 A, much smaller than that of TTO-Cl-α and TTO. After blending with BTP-eC9, PBBD-Cl-β:BTP-eC9-based PSCs achieved an outstanding power conversion efficiency (PCE) of 16.20%, much higher than PBBD:BTP-eC9 (10.06%) and PBBD-Cl-α:BTP-eC9 (13.35%) based devices. These results provide an effective strategy for design and synthesis of highly efficient donor polymers by precise positioning of the chlorine substitution.