Harnessing the near-infrared (NIR) region of the electromagnetic spectrum is exceedingly important for photovoltaics, telecommunications, and the biomedical sciences. While thermally activated delayed fluorescent (TADF) materials have attracted much interest due to their intense luminescence and narrow exchange energies (ΔEST), they are still greatly inferior to conventional fluorescent dyes in the NIR, which precludes their application. This is because securing a sufficiently strong donor–acceptor (D–A) interaction for NIR emission alongside the narrow ΔEST required for TADF is highly challenging. Here, we demonstrate that by abandoning the common polydonor model in favor of a D–A dyad structure, a sufficiently strong D–A interaction can be obtained to realize a TADF emitter capable of photoluminescence (PL) close to 1000 nm. Electroluminescence (EL) at a peak wavelength of 904 nm is also reported. This strategy is both conceptually and synthetically simple and offers a new approach to the development of future NIR TADF materials.

Multiple donor–acceptor‐type carbazole–benzonitrile derivatives that exhibit thermally activated delayed fluorescence (TADF) are the state of the art in efficiency and stability in sky‐blue organic light‐emitting diodes. However, such a motif still suffers from low reverse intersystem crossing rates (kRISC) with emission peaks <470 nm. Here, a weak acceptor of cyanophenyl is adopted to replace the stronger cyano one to construct blue emitters with multiple donors and acceptors. Both linear donor–π–donor and acceptor–π–acceptor structures are observed to facilitate delocalized excited states for enhanced mixing between charge‐transfer and locally excited states. Consequently, a high kRISC of 2.36 × 106 s−1 with an emission peak of 456 nm and a maximum external quantum efficiency of 22.8% is achieved. When utilizing this material to sensitize a blue multiple‐resonance TADF emitter, the corresponding device simultaneously realizes a maximum external quantum efficiency of 32.5%, CIEy ≈ 0.12, a full width at half maximum of 29 nm, and a T80 (time to 80% of the initial luminance) of > 60 h at an initial luminance of 1000 cd m−2.

Conformationally flexible “Carbene–Metal–Amide” (CMA) complexes of copper and gold show photoemissions across the visible spectrum, including mechanochromic behavior which led to the first CMA-based white light-emitting OLED.