Abstract
One stimulus-induced two-step photophysical response, especially with tunable switching time, is a great challenge for organic chromophores. Herein, a polymorphic material 2,7-DCF could undergo in situ two sequential dual-channel responses upon dichloromethane fuming. Both the appearance color and the fluorescence change from red to yellow to deep red with high contrast. The first step corresponds to a fast amorphous-to-crystalline transformation, while the second is a slow solid-state cocrystallization process. Based on single crystal structures and theoretical calculations, such distinct color changes are mainly attributed to conformation twisting and the electron coupling with incorporated solvent molecule through C-H⋅⋅⋅O interaction. Importantly, the second slow photophysical response could be drastically sped up by seeding strategy, or be totally inhibited. Such characteristics pave a way for the potential applications in dynamic anti-counterfeiting and data encryption. Based on the two-step transformation, polymorph 2,7-DCF-a could achieve a successive four-level response to external stimuli. In contrast, polymorph 2,7-DCF-d exhibits a stepwise hypsochromic fluorescence shift over 100 nm. This study would significantly promote the development of stimuli-sensitive systems from “one stimulus, one-step response” to “one stimulus, two or multi-step response”.
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More From: Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
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