Yolsal Utku, Horton Thomas A R, Wang Meng, Shaver Michael P
Department of Materials, School of Natural Sciences, University of Manchester, Oxford Road, Manchester, M1 3BB, United Kingdom.
Sustainable Materials Innovation Hub, Henry Royce Institute, University of Manchester, Oxford Road, Manchester, M13 9BL, United Kingdom.
J Am Chem Soc. 2021 Aug 25;143(33):12980-12984. doi: 10.1021/jacs.1c06408. Epub 2021 Aug 13.
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.
空间位阻较大的路易斯酸和碱中心无法形成路易斯加合物，而是形成受阻路易斯对（FLP），其中潜在的反应活性可用于小分子的活化。将FLP化学应用于聚合物框架可将这种化学转化为响应性和功能性材料。在此，我们报道了一种用于制备大分子FLP的通用合成策略，并通过环醚的开环反应探索了其潜力。环状底物的加入引发了聚合物网络的形成，其中交联程度、网络强度和反应活性可通过醚的空间和电子性质进行调节。所得网络的行为类似于共价交联聚合物，证明了FLP在同时调节材料的小分子捕获和机械性能方面的通用性。
