Fast transfer of triplet to doublet excitons from organometallic host to organic radical semiconductors

Abstract Spin triplet exciton formation sets limits on technologies using organic semiconductors that are confined to singlet‐triplet photophysics. In contrast, excitations in the spin doublet manifold in organic radical semiconductors can show efficient luminescence. Here the dynamics of the spin allowed process of intermolecular energy transfer from triplet to doublet excitons are explored. A carbene‐metal‐amide (CMA‐CF 3 ) is employed as a model triplet donor host, since following photoexcitation it undergoes extremely fast intersystem crossing to generate a population of triplet excitons within 4 ps. This enables a foundational study for tracking energy transfer from triplets to a model radical semiconductor, TTM‐3PCz. Over 74% of all radical luminescence originates from the triplet channel in this system under photoexcitation. It is found that intermolecular triplet‐to‐doublet energy transfer can occur directly and rapidly, with 12% of triplet excitons transferring already on sub‐ns timescales. This enhanced triplet harvesting mechanism is utilized in efficient near‐infrared organic light‐emitting diodes, which can be extended to other opto‐electronic and ‐spintronic technologies by radical‐based spin control in molecular semiconductors.