Solvent Selective Effect Occurs in Iodinated Adamantanone Ferroelectrics

Organic ferroelectrics, as a type of crystalline compound, are generally solution processing. However, for most crystalline compounds, the changing of solvent would not influence the crystalline phase, let alone their physical performance. Here, the solvent selective effect occurs in the iodinated adamantanone ferroelectrics. By changing the solvent with different polarities, the ferroelectric crystals can be induced in two different phases, which is unprecedented to the knowledge. More strikingly, this solvent‐induced transformation could realize the physical performance optimization in the orthorhombic phase (orth‐I‐OA, obtained from ethanol) with a stronger second harmonic generation (SHG) response, greater piezoelectric coefficient d (33) of 5 pC N(−1), and larger spontaneous polarization (P (s)) of 3.43 µC cm(−2) than those of monoclinic one (mono‐I‐OA, obtained from ethyl acetate). Such an intriguing phenomenon might be closely related to solvent polarity. Based on the quantitative and qualitative analyses, the similar interaction energies of these two phases suggest that their transformation could be easily realized via changing the solvent. This work provides new insights into the chemical design and performance optimization of organic ferroelectrics.