Field-Effect Crystal Engineering in Proton–π-Electron Correlated Systems

Dielectric crystals with switchable electric polarizations represent the key functional materials utilized for a broad range of practical applications. They allow for academically intriguing platforms, where the use of a strong external electric field can potentially unveil hidden crystal phases. Proton–π-electron correlated bistable systems turn out to be promising for exploring such electrically induced crystal polymorphisms, mainly because strong π-electronic polarization can be sensitively switched depending on mobile hydrogen locations. Pseudo-symmetry and hydrogen disorder are utilized as clues for the data mining of the Cambridge Structural Database in the search for molecular candidates with novel switchable dielectrics. The polarization hysteresis, electrostriction, and second harmonic generation of the candidates were experimentally evaluated, together with the re-inspection of crystal structure. This feature article highlights the rich variation and competition of some candidate polarization configurations and switching modes in close relation to high and efficient electrical energy storage/discharge, large electrostriction effects, polarization rotations, and multistage switching phenomena. The experimental findings are well-reproduced by the computational optimization of crystal structure and the simulation of the switchable polarization, piezoelectric coefficients, and relative stability for each of the real or hypothetical hydrogen-ordered crystal phases. Effective prediction and strategic design are thereby guaranteed by systematically understanding the appropriate integration of experimental, computational, and data sciences.