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In the present work, we overcome this challenge by coassembling a series of tricarbonyl\u2010substituted benzene molecules with polyvinyl alcohol (PVA). The strong hydrogen bonds between the guest dopants and the PVA host matrix protect the free radicals of carbonyl compounds after light irradiation, leading to strong solid state free radical emission. Changing temperature and peripheral functional groups of the tricarbonyl\u2010substituted benzenes can influence the intensity of the radical emission. Quantum\u2010chemical calculations predict that such free radical fluorescence originates from anti\u2010Kasha D<jats:sub>2<\/jats:sub>\u2192D<jats:sub>0<\/jats:sub>vertical emission by the anion radicals. 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