Pressure-Induced Transition of Bisamide-Substituted Diacetylene Crystals from Nonphotopolymerizable to Photopolymerizable State

Mechanoresponsive diacetylenes (DAs) exhibiting a transition of crystalline orientation from light-inert to light-active state upon applied force are reported. Amide units are introduced to DAs where hydrogen bonding is utilized to control intermolecular interactions. Application of external pressure (2-150 MPa) to DAs results in an emergence of new crystal phases with changing the d-spacing which possibly reduces the reaction barrier. Accordingly, the dramatic crystalline transition from perfectly off to on state to undergo the light-induced topochemical polymerization of bulk DA crystals is obtained. Subsequent UV irradiation at a wavelength of 254 nm enables the polymerization of the pressed region, changing its color from white to blue which suggests the selective formation of polydiacetylene (PDA) polymorphs. In addition, by utilizing the mechanoresponsive crystallinity with low-enough activation pressure, a new strategy for PDA patterning is demonstrated based on the selective transfer of information by means of force to a DA film. This phenomenon can be applicable to a new nanoimprinting technique where no mechanical deformation of resist materials but phase transition is induced by the mold.