Halogen substitution strategy for exploiting high‐performance molecular ferroelectrics

Abstract Molecular ferroelectrics are emerging as a robust family of electric‐ordered materials due to their distinct structural flexibility, molecular tunability, and versatility. In recent years, diverse chemical design approaches have significantly contributed to discovering and optimizing ferroelectric performances of molecule‐based ferroelectric systems. Notably, halogen substitution is one of the most effective strategies for inducing symmetry breaking and optimizing the dipole moments and potential energy barriers. In this minireview, we have summarized recent significant advances of halogen substitution strategy in molecule‐based ferroelectrics, including organic‐inorganic hybrids and metal‐free molecular systems. Subsequently, we discuss the underlying mechanism of halogen substitution to improve ferroelectric performances, including the generation of spontaneous polarization, enhancement of Curie temperature, and bandgap engineering. Finally, the future directions in designing and modulating molecular ferroelectrics by halogen substitution strategy are also highlighted.