Pressure-Induced Diels-Alder Reactions in C6 H6 -C6 F6 Cocrystal towards Graphane Structure.
Yajie WangXiao DongXingyu TangHaiyan ZhengKuo LiXiaohuan LinLeiming FangGuang'ai SunXiping ChenLei XieCraig L BullNicholas P FunnellTakanori HattoriAsami Sano-FurukawaJihua ChenDale K HensleyGeorge D CodyYang RenHyun Hwi LeeHo-Kwang MaoPublished in: Angewandte Chemie (International ed. in English) (2019)
Pressure-induced polymerization (PIP) of aromatics is a novel method for constructing sp3 -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.
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