Some π-molecular radicals typically exist in solution as π-dimers with metastable characteristics. Therefore, attempting to improve the stability of radical π-dimers is a fascinating endeavor. Herein, a series of hydroxyl-functionalised isolated perylene bisimide anionic radical π-dimers were obtained by using intramolecular hydrogen bond assistance in a one-step process for the first time. It is also found that these radical π-dimers exhibit solvatochromism and acid-base discoloration, when the intermolecular hydrogen bonds are disrupted. Perylene bisimide anionic radical π-dimers exhibit unique properties such as solvatochromism and acid-base discoloration. These characteristics make them suitable for ultra-sensitive colorimetric and fluorescent dual-signal detection of amines. Among them the π-dimer 3 achievable the lowest detection limits of 0.13 ppb, 0.02 ppb and 0.049 ppb for primary, secondary and tertiary amines, respectively. Additionally, colorimetric films prepared using these radical π-dimers demonstrate high sensitivity, enabling detection of amines at ppb levels. We believe that this class of radical π-dimers could be develop into a new class of environmental stimuli-responsive materials.
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