Abstract
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.
Highlights
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
When applied to Lewis acids (LAs) and bases (LBs), frustrated Lewis pairs (FLPs) are formed (Figure 1A), promoting activation of small molecules and subsequent applications in catalysis.[1−5] Incorporating FLPs into polymer frameworks has the profound potential to extend this concept into responsive materials, as the dynamic nature of these bonds translates into functionality
The FLP-mediated ring-openings of cyclic substrates (Figure 1B) are of particular interest; activation of these molecules has been reported for small-molecule LA/LB pairs for tetrahydrofuran, dioxane, and 1,4-thioxane ethers.[12−17] In general, the activation of these cyclic substrates proceeds via heteroatom coordination to the Lewis acidic center, followed by attack of a Lewis basic species to form a zwitterionic product
Summary
The authors thank Dr Elisabeth Francis for the SEM images
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