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Photogenerated quartet excitons are an extensively studied platform, but their applications are limited by the absence of optical read\u2010out via luminescence. Here, a new class of synthetically accessible molecules with quartet\u2010derived luminescence is demonstrated, formed by appending a non\u2010luminescent TEMPO radical to thermally activated delayed fluorescence (TADF) chromophores previously used in OLEDs. The low singlet\u2010triplet energy gap of the chromophore opens a luminescence channel from radical\u2010triplet coupled states. A set of design rules is established by tuning the energetics in a series of compounds based on a naphthalimide (NAI) core. Generation of quartet states is observed and the strength of radical\u2010triplet exchange is measured. In DMAC\u2010TEMPO, up to 72% of detected photons emerge after reverse intersystem crossing from the quartet state repopulates the state with singlet character. This design strategy does not rely on a luminescent radical to provide an emission pathway from the high\u2010spin state. The large library of TADF chromophores promises a greater pallet of achievable emission colours.<\/jats:p>","DOI":"10.1002\/adma.202501164","type":"journal-article","created":{"date-parts":[[2025,5,15]],"date-time":"2025-05-15T03:44:25Z","timestamp":1747280665000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":14,"title":["Radical TADF: Quartet\u2010Derived Luminescence with Dark TEMPO"],"prefix":"10.1002","volume":"37","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-1361-1973","authenticated-orcid":false,"given":"Sebastian","family":"Gorgon","sequence":"first","affiliation":[{"name":"Cavendish Laboratory University of Cambridge JJ Thomson Ave Cambridge CB3 0US UK"},{"name":"Centre for Advanced Electron Spin Resonance Department of Chemistry University of Oxford Inorganic Chemistry Laboratory  S Parks Rd Oxford OX1 3QR 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