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

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 ET1 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.