Peixin Fan, Shunjie Liu*, Ruoyu Zhang, Chunwei Zhuo, Fengxiang Gao, Xuan Pang, Xuesi Chen and Xianhong Wang*,
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Rigid-Flexible Binuclear Catalysts: Boosting Activity for Copolymerization of CO2 and Propylene Oxide
Inspired by natural enzymes, synergy is widely utilized in small molecule recognition and transformation, but has not been fully explored in polymer synthesis. Herein, we present an enzyme-mimicking catalyst design strategy for constructing rigid-flexible binuclear catalysts (RFBCs), aiming to boost the copolymerization of CO2 and propylene oxide (PO). The key design strategy of RFBCs is to boost intramolecular synergy by spatial proximity of active sites imposed by rigid skeleton, while a flexible linker affords dynamic interactions of active centers. The optimal catalyst Nap-Al2, featured with rigid naphthalene skeleton grafting two adjacent aluminum porphyrins through soft alkyl chains, exhibits outstanding catalytic performance (5000 h–1) outperforming the previously reported polymeric catalysts (3100 h–1) under similar conditions. Moreover, Nap-Al2 exhibits great thermal stability at high temperatures up to 140 °C. A comprehensive catalytic cycle based on dynamic synergy has been proposed, taking into account the key intermediates involved in the copolymerization of CO2/PO. Overall, we present that the construction of RFBCs for designing enzyme-mimicking catalysts is not only suitable for the ROCOP of CO2/PO but also conducive to future investigation for related polymerization processes, such as the ring-opening of lactones.
期刊介绍:
Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.