Accelerating Molecular Ferroelectrics: From Rapid Mapping to Scalable High‐Yield Synthesis

ABSTRACT

Molecular ferroelectrics (MFs) represent a transformative class of functional materials, which offer mechanical flexibility, low‐density architectures, and chemical tunability. However, their development is bottlenecked by empirical, “trial‐and‐error” crystallization methods that impede both structural determination and scalable synthetic routes. Here, we present an integrated flow‐assisted crystallization screening framework that could transform the discovery and processing of MFs from an empirical approach into a quantitative, data‐driven workflow. Using the molecular ferroelectric [Co( n ‐BuDABCO)Br ₃ ] ( 1 ) as a robust MF reference, we demonstrate the rapid mapping of multidimensional crystallization space. We establish a scalable framework for the accelerated synthesis, to identify conditions that yield single‐crystal‐quality XRD material within minutes. This methodology is subsequently translated to continuous‐flow synthesis in ethanol, further intensified by the introduction of CO ₂ as a sustainable anti‐solvent. Across the screened CO ₂ /EtOH operating conditions, phase‐pure crystalline powders are recovered in consistently high yields up to 97%. While the high thermodynamic stability of 1 precludes the formation of new polymorphs for this system, this proof‐of‐concept highlights the viability of accessing crystallization regimes in non‐classical media, providing an adaptable strategy for the future screening and development of MFs and related multifunctional materials.