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The construction of artificial structures through hierarchical self-assembly based on noncovalent interactions, as well as monitoring during the self-assembly process, are important aspects of dynamic supramolecular chemistry. Herein we describe the complex dynamics of chiral N,N'-diphenyl dihydrodibenzo[a,c]phenazine derivatives (S)/(R)-DPAC, whose different assemblies were found to have distinct optical and morphological characteristics. With ratiometric fluorescence originating from vibration-induced emission (VIE), the self-assembly p