Cyclic Ether Triggers for Polymeric Frustrated Lewis Pair Gels

Sterically hindered Lewis acid and base centers are unable to form Lewis adducts, instead forming frustrated Lewis pairs (FLPs), where latent reactivity can be utilized for the activation of small molecules. Applying FLP chemistry into polymeric frameworks transforms this chemistry into responsive and functional materials. Here, we report a versatile synthesis strategy for the preparation of macromolecular FLPs and explore its potential with the ring-opening reactions of cyclic ethers. Addition of the cyclic substrates triggered polymer network formation, where the extent of cross-linking, strength of network, and reactivity are tuned by the steric and electronic properties of the ethers. The resultant networks behave like covalently cross-linked polymers, demonstrating the versatility of FLPs to simultaneously tune both small-molecule capture and mechanical properties of materials.

Automated summary

Sterically hindered Lewis acid and base centers form frustrated Lewis pairs (FLPs) instead of Lewis adducts, allowing for activation of small molecules. By applying FLP chemistry to polymeric frameworks, responsive and functional materials can be created. A versatile synthesis strategy for macromolecular FLPs has been developed, with potential demonstrated through ring-opening reactions of cyclic ethers in polymer networks. The steric and electronic properties of the ethers can tune the cross-linking, strength, and reactivity of the networks, showcasing the versatility of FLPs in simultaneously controlling small-molecule capture and mechanical properties of materials.