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Pressure‐Induced Diels–Alder Reactions in C 6 H 6 ‐C 6 F 6 Cocrystal towards Graphane Structure
Author(s) -
Wang Yajie,
Dong Xiao,
Tang Xingyu,
Zheng Haiyan,
Li Kuo,
Lin Xiaohuan,
Fang Leiming,
Sun Guang'ai,
Chen Xiping,
Xie Lei,
Bull Craig L.,
Funnell Nicholas P.,
Hattori Takanori,
SanoFurukawa Asami,
Chen Jihua,
Hensley Dale K.,
Cody George D.,
Ren Yang,
Lee Hyun Hwi,
Mao Hokwang
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201813120
Subject(s) - graphane , hexafluorobenzene , benzene , chemistry , crystal structure , cocrystal , polymerization , crystallography , materials science , polymer , organic chemistry , molecule , hydrogen , hydrogen bond
Pressure‐induced polymerization (PIP) of aromatics is a novel method for constructing sp 3 ‐carbon frameworks, and nanothreads with diamond‐like structures were synthesized by compressing benzene and its derivatives. Here by compressing a benzene‐hexafluorobenzene cocrystal (CHCF), H‐F‐substituted graphane with a layered structure in the PIP product was identified. Based on the crystal structure determined from the in situ neutron diffraction and the intermediate products identified by gas chromatography‐mass spectrum, we found that at 20 GPa CHCF forms tilted columns with benzene and hexafluorobenzene stacked alternatively, and leads to a [4+2] polymer, which then transforms to short‐range ordered H‐F‐substituted graphane. The reaction process involves [4+2] Diels–Alder, retro‐Diels–Alder, and 1‐1′ coupling reactions, and the former is the key reaction in the PIP. These studies confirm the elemental reactions of PIP of CHCF for the first time, and provide insight into the PIP of aromatics.