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

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)Br₃] (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 CO₂ as a sustainable anti-solvent. Across the screened CO₂/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.