Divergent catalysis powered by external thermal fluctuations: A novel molecular ferroelectric approach

Converting ambient thermal fluctuations into selective chemical transformations represents an emerging strategy in sustainable catalysis. Unlike conventional thermocatalysis that requires continuous high-temperature input, we report a molecular ferroelectric platform that harnesses low-grade temperature fluctuations, spanning industrial, environmental, biological, and mechanical sources, to drive efficient and tunable catalytic reactions. Two copper-based molecular ferroelectrics, [Cu(L-His)(bpy)]ClO₄ (Cu-FE-1) and [Cu(L-phe)(bpy)(H₂O)]PF₆·H₂O (Cu-FE-2), were rationally designed to elucidate the impact of coordination environment and the dipolar orientation on catalytic performance. For example, under simulated industrial waste heat cycling, both compounds exhibited pronounced pyroelectric responses and efficiently catalyzed the cycloaddition of CO₂ with propargylamine, with Cu-FE-1 achieving a turnover number (TON) of 5064 (a yield of 98%) and Cu-FE-2 reaching 4876 (a yield of 94%). Notably, Cu-FE-2 further enabled the C–O cross-coupling of phenol with aryl bromides under conditions mimicking diurnal temperature variations, delivering diphenyl ether in a yield of 98% (TON = 4742), whereas Cu-FE-1 was inactive. This divergent reactivity underscores the critical role of structural polarization and coordination flexibility in dictating thermally induced catalytic pathways. Overall, this work introduces a new paradigm of thermal fluctuation-driven catalysis based on molecular ferroelectrics, offering programmable and tunable access to multiple reaction types under mild and field-free conditions.