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Organic near‐infrared (NIR) emissive materials integrating the intrinsic NIR light advantages and organic semiconductor characters have generated immense scientific interest in fundamental science and practical application, including optical communications, night vision, surveillance, and biomedical applications. Nevertheless, the intrinsic energy gap law engenders a huge challenge to simultaneously meet longer emission wavelength and higher luminescence efficiency for organic NIR emitters. Herein, it is suggested that the purposefully molecular design and crystal engineering for novel organic NIR materials are urgently studied and explored. Herein, recent advances in novel organic NIR materials, mainly focusing on the hybridized local and charge transfer (HLCT) compounds, thermally activated delayed fluorescence (TADF) emitters, CT cocrystals, neutral π‐radicals, and excited‐state intramolecular proton transfer (ESIPT)‐active materials, are summarized. It is hoped that this perspective can afford a new insight into the fine design and synthesis of the desired organic NIR emitters. [ABSTRACT FROM AUTHOR]

Near‐infrared (NIR) organic solid‐state lasers play an essential role in applications ranging from laser communication to infrared night vision, but progress in this area is restricted by the lack of effective excited‐state gain processes. Herein, we originally proposed and demonstrated the cascaded occurrence of excited‐state intramolecular proton transfer for constructing the completely new energy‐level systems. Cascading by the first ultrafast proton transfer of <430 fs and the subsequent irreversible second proton transfer of ca. 1.6 ps, the stepwise proton transfer process favors the true six‐level photophysical cycle, which supports efficient population inversion and thus NIR single‐mode lasing at 854 nm. This work realizes longest wavelength beyond 850 nm of organic single‐crystal lasing to date and originally exploits the cascaded excited‐state molecular proton transfer energy‐level systems for organic solid‐state lasers. [ABSTRACT FROM AUTHOR]