Pressure-Induced Diels–Alder Reactions in C                         6                         H                         6                         -C                         6                         F                         6                          Cocrystal towards Graphane Structure

Yajie Wang; Xiao Dong; Xingyu Tang; Haiyan Zheng; Kuo Li; Xiaohuan Lin; Leiming Fang; Guang'ai Sun; Xiping Chen; Lei Xie; Craig L. Bull; Nicholas P. Funnell; Takanori Hattori; Asami Sano-Furukawa; Jihua Chen; Dale K. Hensley; George D. Cody; Yang Ren; Hyun Hwi Lee; Ho kwang Mao

doi:10.1002/anie.201813120

Pressure-Induced Diels–Alder Reactions in C ₆ H ₆ -C ₆ F ₆ Cocrystal towards Graphane Structure

Yajie Wang, Xiao Dong, Xingyu Tang, Haiyan Zheng, Kuo Li, Xiaohuan Lin, Leiming Fang, Guang'ai Sun, Xiping Chen, Lei Xie, Craig L. Bull, Nicholas P. Funnell, Takanori Hattori, Asami Sano-Furukawa, Jihua Chen, Dale K. Hensley, George D. Cody, Yang Ren, Hyun Hwi Lee, Ho kwang Mao

Research output: Contribution to journal › Article › peer-review

45 Scopus citations

Abstract

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.

Original language	English
Pages (from-to)	1468-1473
Number of pages	6
Journal	Angewandte Chemie - International Edition
Volume	58
Issue number	5
DOIs	https://doi.org/10.1002/anie.201813120
State	Published - Jan 28 2019

Funding

The authors acknowledge the support of the National Natural Science Foundation of China (NSFC) (Grant Nos.: 21601007, 21771011 and 21875006). The authors also acknowledge the support from Science Challenge Project, No. TZ2016001 and the Top 1000-Talents Award. Experiments at the ISIS Neutron and Muon Source were supported by a beamtime allocation from the Science and Technology Facilities Council. Neutron diffraction experiments at J-PARC were performed through the J-PARC user programs (No. 2016A0191). The research at Oak Ridge National Lab's Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy (DOE). Electron microscopy experiments were conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility. The research used resources of the Advanced Photon Source, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. The calculations were performed on the TianheII supercomputer at the Chinese National Supercomputer Center in Guangzhou. The authors thank Dr. Joerg C. Neuefeind for his helps in neutron PDF measurement and thank Dr. Qiaoshi Zeng and Dr. Yufei Meng for their helps on the reduction of X-ray PDF data and IR measurements. X.D. thanks the support of NSFC (Grant No.: 21803033). The authors acknowledge the support of the National Natural Science Foundation of China (NSFC) (Grant Nos.: 21601007, 21771011 and 21875006). The authors also acknowledge the support from Science Challenge Project, No. TZ2016001 and the Top 1000-Talents Award. Experiments at the ISIS Neutron and Muon Source were supported by a beamtime allocation from the Science and Technology Facilities Council.[22]Neutron diffraction experiments at J-PARC were performed through the J-PARC user programs (No. 2016A0191). The research at Oak Ridge National Lab≫s Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy (DOE). Electron microscopy experiments were conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility. The research used resources of the Advanced Photon Source, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. The calculations were performed on the TianheII supercomputer at the Chinese National Supercomputer Center in Guangzhou. The authors thank Dr. Joerg C. Neuefeind for his helps in neutron PDF measurement and thank Dr. Qiaoshi Zeng and Dr. Yufei Meng for their helps on the reduction of X-ray PDF data and IR measurements. X.D. thanks the support of NSFC (Grant No.: 21803033).

Funders	Funder number
DOE Office of Science
ISIS
J-PARC	2016A0191
Office of Basic Energy Sciences
Scientific User Facilities Division
U.S. Department of Energy
Argonne National Laboratory	21803033
Argonne National Laboratory
Science and Technology Facilities Council
National Natural Science Foundation of China	21601007, 21875006, 21771011
National Natural Science Foundation of China
Science Challenge Project	TZ2016001
Science Challenge Project

Keywords

cycloaddition
graphane
polymerization
solid-state reactions
structure determination

Access to Document

10.1002/anie.201813120

Cite this

Wang, Y., Dong, X., Tang, X., Zheng, H., Li, K., Lin, X., Fang, L., Sun, G., Chen, X., Xie, L., Bull, C. L., Funnell, N. P., Hattori, T., Sano-Furukawa, A., Chen, J., Hensley, D. K., Cody, G. D., Ren, Y., Lee, H. H., & Mao, H. K. (2019). Pressure-Induced Diels–Alder Reactions in C ₆ H ₆ -C ₆ F ₆ Cocrystal towards Graphane Structure Angewandte Chemie - International Edition, 58(5), 1468-1473. https://doi.org/10.1002/anie.201813120

Wang, Yajie ; Dong, Xiao ; Tang, Xingyu et al. / Pressure-Induced Diels–Alder Reactions in C ₆ H ₆ -C ₆ F ₆ Cocrystal towards Graphane Structure In: Angewandte Chemie - International Edition. 2019 ; Vol. 58, No. 5. pp. 1468-1473.

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title = " Pressure-Induced Diels–Alder Reactions in C 6 H 6 -C 6 F 6 Cocrystal towards Graphane Structure ",

abstract = " 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.",

keywords = "cycloaddition, graphane, polymerization, solid-state reactions, structure determination",

author = "Yajie Wang and Xiao Dong and Xingyu Tang and Haiyan Zheng and Kuo Li and Xiaohuan Lin and Leiming Fang and Guang'ai Sun and Xiping Chen and Lei Xie and Bull, {Craig L.} and Funnell, {Nicholas P.} and Takanori Hattori and Asami Sano-Furukawa and Jihua Chen and Hensley, {Dale K.} and Cody, {George D.} and Yang Ren and Lee, {Hyun Hwi} and Mao, {Ho kwang}",

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Wang, Y, Dong, X, Tang, X, Zheng, H, Li, K, Lin, X, Fang, L, Sun, G, Chen, X, Xie, L, Bull, CL, Funnell, NP, Hattori, T, Sano-Furukawa, A, Chen, J , Hensley, DK, Cody, GD, Ren, Y, Lee, HH & Mao, HK 2019, ' Pressure-Induced Diels–Alder Reactions in C ₆ H ₆ -C ₆ F ₆ Cocrystal towards Graphane Structure ', Angewandte Chemie - International Edition, vol. 58, no. 5, pp. 1468-1473. https://doi.org/10.1002/anie.201813120

Pressure-Induced Diels–Alder Reactions in C ₆ H ₆ -C ₆ F ₆ Cocrystal towards Graphane Structure . / Wang, Yajie; Dong, Xiao; Tang, Xingyu et al.
In: Angewandte Chemie - International Edition, Vol. 58, No. 5, 28.01.2019, p. 1468-1473.

Research output: Contribution to journal › Article › peer-review

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T1 - Pressure-Induced Diels–Alder Reactions in C 6 H 6 -C 6 F 6 Cocrystal towards Graphane Structure

AU - Wang, Yajie

AU - Dong, Xiao

AU - Tang, Xingyu

AU - Zheng, Haiyan

AU - Li, Kuo

AU - Lin, Xiaohuan

AU - Fang, Leiming

AU - Sun, Guang'ai

AU - Chen, Xiping

AU - Xie, Lei

AU - Bull, Craig L.

AU - Funnell, Nicholas P.

AU - Hattori, Takanori

AU - Sano-Furukawa, Asami

AU - Chen, Jihua

AU - Hensley, Dale K.

AU - Cody, George D.

AU - Ren, Yang

AU - Lee, Hyun Hwi

AU - Mao, Ho kwang

PY - 2019/1/28

Y1 - 2019/1/28

N2 - 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.

AB - 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.

KW - cycloaddition

KW - graphane

KW - polymerization

KW - solid-state reactions

KW - structure determination

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Wang Y, Dong X, Tang X, Zheng H, Li K, Lin X et al. Pressure-Induced Diels–Alder Reactions in C ₆ H ₆ -C ₆ F ₆ Cocrystal towards Graphane Structure Angewandte Chemie - International Edition. 2019 Jan 28;58(5):1468-1473. doi: 10.1002/anie.201813120