Highly Efficient Near‐Infrared Luminescent Radicals with Emission Peaks over 750 nm

Purely organic molecules exhibiting near‐infrared (NIR) emission possess considerable potential for applications in both biological and optoelectronic technological domains, owing to their inherent advantages such as cost‐effectiveness, biocompatibility, and facile chemical modifiability. However, the repertoire of such molecules with emission peaks exceeding 750 nm and concurrently demonstrating high photoluminescence quantum efficiency (PLQE) remains relatively scarce due to the energy gap law. Herein, we report two open‐shell NIR radical emitters, denoted as DMNA‐Cz‐BTM and DMNA‐PyID‐BTM, achieved through the strategic integration of a donor group (DMNA) onto the Cz‐BTM and PyID‐BTM frameworks, respectively. We found that the donor‐acceptor molecular structure allows the two designed radical emitters to exhibit a charge‐transfer excited state and spatially separated electron and hole levels with non‐bonding characteristics. Thus, the high‐frequency vibrations are effectively suppressed. Besides, the reduction of low‐frequency vibrations is observed. Collectively, the non‐radiative decay channel is significantly suppressed, leading to exceptional NIR PLQE values. Specifically, DMNA‐Cz‐BTM manifests an emission peak at 758 nm alongside a PLQE of 55 %, whereas DMNA‐PyID‐BTM exhibits an emission peak at 778 nm with a PLQE of 66 %. Notably, these represent the pinnacle of PLQE among metal‐free organic NIR emitters with emission peaks surpassing 750 nm. We developed two near‐infrared (NIR) radical emitters with record‐high photoluminescence quantum efficiency among metal‐free organic NIR emitters with emission peaks exceeding 750 nm. The donor‐acceptor molecular structure allows the designed radical emitter to exhibit charge‐transfer excited state and spatially separated electron and hole levels with non‐bonding character. Both the high‐frequency and low‐frequency vibrations coupling in D1 are effectively reduced, leading to significantly suppressed non‐radiative decay rate. As a result, the “energy gap law” is violated and exceptional luminescence efficiency is achieved.