Untangling the Mechanochromic Properties of Benzothiadiazole-Based Luminescent Polymorphs through Supramolecular Organic Framework Topology.

Two new luminophore polymorphs of 4-bromo-7-(4-nonylphenyl)benzo[][1,2,5]thiadiazole ( and ) exhibiting different color emissions, which switch into each other in response to shear force and solvent vapors, are presented and their X-ray structure is determined. Supramolecular organic framework topology (SOFT) studies on the two polymorphic structures led us to conclude that the mechanochromic phase transformation can be explained on the basis of modifications in their respective topological nets: and for and , respectively, as a result of the breaking and restoration of a number of weak supramolecular interactions. The color changes accompanying this transformation have been rationalized with the help of time-dependent density functional theory. We firmly believe that our findings will inspire future research on the design of novel stimuli-responsive organic materials with switchable properties based on their supramolecular interactions by establishing clear SOFT-property relationships.