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Distance-Selected Topochemical Dehydro-Diels–Alder Reaction of 1,4-Diphenylbutadiyne toward Crystalline Graphitic Nanoribbons

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posted on 23.09.2020 by Peijie Zhang, Xingyu Tang, Yida Wang, Xuan Wang, Dexiang Gao, Yapei Li, Haiyan Zheng, Yajie Wang, Xinxin Wang, Riqiang Fu, Mingxue Tang, Kazutaka Ikeda, Ping Miao, Takanori Hattori, Asami Sano-Furukawa, Christopher A. Tulk, Jamie J. Molaison, Xiao Dong, Kuo Li, Jing Ju, Ho-kwang Mao
Solid-state topochemical polymerization (SSTP) is a promising method to construct functional crystalline polymeric materials, but in contrast to various reactions that happen in solution, only very limited types of SSTP reactions are reported. Diels–Alder (DA) and dehydro-DA (DDA) reactions are textbook reactions for preparing six-membered rings in solution but are scarcely seen in solid-state synthesis. Here, using multiple cutting-edge techniques, we demonstrate that the solid 1,4-diphenylbutadiyne (DPB) undergoes a DDA reaction under 10–20 GPa with the phenyl as the dienophile. The crystal structure at the critical pressure shows that this reaction is “distance-selected”. The distance of 3.2 Å between the phenyl and the phenylethynyl facilitates the DDA reaction, while the distances for other DDA and 1,4-addition reactions are too large to allow the bonding. The obtained products are crystalline armchair graphitic nanoribbons, and hence our studies open a new route to construct the crystalline carbon materials with atomic-scale control.

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