A novel stimuli-responsive room-temperature photoluminescent liquid 1 based on the N-heteroacene framework is developed and analyzed by several experiments such as differential scanning calorimetry, X-ray diffraction, dynamic viscoelasticity measurement, in situ observation by optical and polarized optical microscopes, UV-vis absorption and fluorescence spectroscopy, and by theoretical methods such as ab initio calculation and molecular dynamics (MD) computer simulation techniques. In contrast to stimuli-responsive solid materials reported previously, liquid 1 in response to HCl vapor as a single stimulus can involve dramatically multiple changes in physical properties such as rheological behavior, morphology, as well as photoluminescence. The present ab initio calculation and microsecond-timescale MD simulations reveal that the complexation of 1 and HCl molecules induces a large dipole moment, leading to the formation of stacking structures because of their dipole-dipole interaction. Upon exposure to HCl vapor, in situ microscopic observation of the stimuli-responsive liquid elucidates a self-assembling process involving the formation of the wrinkle structure in a micrometer scale, indicating disorder-order phase transition. Further exposure of 1 to HCl vapor from seconds to hours has an influence on the macroscopic physical properties such as viscosity, viscoelasticity, and photoluminescent colors. The synergy between the experimental and theoretical investigations opens a new strategy to develop a novel class of stimuli-responsive materials showing multiple changes in physical properties.
Keywords: N-heteroacene; molecular dynamics simulation; molecular modeling; quantum chemical calculation; room-temperature photoluminescent liquid; stimuli-responsive liquid.