Ultralong room temperature phosphorescence and reversible mechanochromic luminescence in ionic crystals with structural isomerism

• New organic ionic crystals are studied by using structural isomerization strategy. • The longest RTP lifetime of 732.8 ms is observed in meta-isomer ion crystal. • The ortho-isomer displays mechano-responsive luminescence with redder emissions. • The molecular geometries and stacking modes are related to the above properties. • Potential applications including data encryption and decoration are demonstrated. Photofunctional ionic crystals have become more and more appealing in the applications of light-emitting devices, optical imaging, and anti-counterfeiting. However, it is still limited to achieve ultralong room temperature phosphorescence (RTP) and stimuli-responsive property in ionic crystals due to the lack of valid design principles. Herein, we developed a new class of organic ionic crystals (sodium o- , m- , p- carboxyphenylborate, o- , m- , p- Nacpb) by a structural isomerization strategy, which could exhibit ultralong RTP and mechanochromic emission. Among the three isomers, m- Nacpb crystal exhibits the longest RTP lifetime up to 732.8 ms, which is ca. 120 times longer than that (6.1 ms) of o -Nacpb crystal. Interestingly, o- Nacpb could display mechano-responsive luminescence with tunable fluorescence-phosphorescence emissions and longer phosphorescence lifetime (increased by about 20-fold). Both experimental and theoretical studies indicate that the distinct RTP and mechanochromic luminescence properties of the organic ionic crystals are attributed to the alternation of molecular conformations and spatial packing modes. Moreover, potential applications including data encryption and decoration are demonstrated, benefiting from the varied phosphorescence lifetimes and good processability. Therefore, this work not only provides a rational isomerization route to prepare various organic ionic crystals with ultralong RTP and stimuli-responsive emission, but also supplies a facile way to develop the advanced information encryption applications.