Anderson Christopher L, Li He, Jones Christopher G, Teat Simon J, Settineri Nicholas S, Dailing Eric A, Liang Jiatao, Mao Haiyan, Yang Chongqing, Klivansky Liana M, Li Xinle, Reimer Jeffrey A, Nelson Hosea M, Liu Yi
The Molecular Foundry, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, CA, 94720, USA.
Department of Chemistry, University of California, Berkeley, Berkeley, CA, 94720, USA.
Nat Commun. 2021 Nov 24;12(1):6818. doi: 10.1038/s41467-021-27090-1.
Topochemical polymerization reactions hold the promise of producing ultra-high molecular weight crystalline polymers. However, the totality of topochemical polymerization reactions has failed to produce ultra-high molecular weight polymers that are both soluble and display variable functionality, which are restrained by the crystal-packing and reactivity requirements on their respective monomers in the solid state. Herein, we demonstrate the topochemical polymerization reaction of a family of para-azaquinodimethane compounds that undergo facile visible light and thermally initiated polymerization in the solid state, allowing for the first determination of a topochemical polymer crystal structure resolved via the cryoelectron microscopy technique of microcrystal electron diffraction. The topochemical polymerization reaction also displays excellent functional group tolerance, accommodating both solubilizing side chains and reactive groups that allow for post-polymerization functionalization. The thus-produced soluble ultra-high molecular weight polymers display superior capacitive energy storage properties. This study overcomes several synthetic and characterization challenges amongst topochemical polymerization reactions, representing a critical step toward their broader application.
拓扑化学聚合反应有望制备超高分子量的结晶聚合物。然而，拓扑化学聚合反应整体上未能制备出既可溶又具有可变功能的超高分子量聚合物，这受到固态下各自单体的晶体堆积和反应性要求的限制。在此，我们展示了一类对氮杂醌二甲烷化合物的拓扑化学聚合反应，该反应在固态下能通过可见光和热引发轻松聚合，首次实现了通过微晶电子衍射这一低温电子显微镜技术解析拓扑化学聚合物晶体结构。拓扑化学聚合反应还表现出优异的官能团耐受性，既能容纳增溶侧链，又能容纳可实现聚合后功能化的反应性基团。由此制备的可溶性超高分子量聚合物展现出卓越的电容储能性能。本研究克服了拓扑化学聚合反应中的若干合成和表征挑战，是朝着其更广泛应用迈出的关键一步。
