Effective Internal and External Modulation of Nontraditional Intrinsic Luminescence

Abstract The rational modulation of the nontraditional intrinsic luminescence (NTIL) of nonconventional luminophores remains difficult, on account of the limited understanding on the structure–property relationships and emission mechanisms. Herein, the effective modulation of NTIL is demonstrated based on a group of nonaromatic anhydrides and imides. Mutual bridging of isolated subgroups effectively promotes intramolecular through‐space conjugation (TSC), leading to red‐shifted emission, enhanced efficiency, and prolonged persistent room‐temperature phosphorescence (p‐RTP). The substitution of heteroatoms from oxygen to nitrogen drastically changes the TSC and enhances intermolecular interactions, resulting in enhanced emission efficiency. In addition, upon freezing, compression, or embedding into polymer matrices, the emission intensity and color remain well regulated. These results shed new light on the rational modulation of the NTIL and p‐RTP of nonconventional luminophores.