Heavy‐Atom‐Free Room‐Temperature Phosphorescent Rylene Imide for High‐Performing Organic Photovoltaics

Abstract Organic phosphorescence, originating from triplet excitons, has potential for the development of new generation of organic optoelectronic materials. Herein, two heavy‐atom‐free room‐temperature phosphorescent (RTP) electron acceptors with inherent long lifetime triplet exctions are first reported. These two 3D‐fully conjugated rigid perylene imide (PDI) multimers, as the best nonfullerene wide‐bandgap electron acceptors, exhibit a significantly elevated T₁ of ≈2.1 eV with a room‐temperature phosphorescent emission (τ = 66 µs) and a minimized singlet–triplet splitting as low as ≈0.13 eV. The huge spatial congestion between adjacent PDI skeleton endows them with significantly modified electronic characteristics of S₁ and T₁. This feature, plus with the fully‐conjugated rigid molecular configuration, balances the intersystem crossing rate and fluorescence/phosphorescence rates, and therefore, elevating E_T1 to ≈2.1 from 1.2 eV for PDI monomer. Meanwhile, the highly delocalized feature enables the triplet charge‐transfer excitons at donor–acceptor interface effectively dissociate into free charges, endowing the RTP electron acceptor based organic solar cells (OSCs) with a high internal quantum efficiency of 84% and excellent charge collection capability of 94%. This study introduces an alternative strategy for designing PDI derivatives with high‐triplet state‐energy and provides revelatory insights into the fundamental electronic characteristics, photophysical mechanism, and photo‐to‐current generation pathway.