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

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

62 Citations (Scopus)

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
Journal	Angewandte Chemie - International Edition
Volume	58
Issue number	5
DOIs	https://doi.org/10.1002/anie.201813120
Publication status	Published - 28 Jan 2019
Externally published	Yes

Bibliographical note

Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to [email protected].

Research Keywords

cycloaddition
graphane
polymerization
solid-state reactions
structure determination

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10.1002/anie.201813120

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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. (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

@article{4abaea782c184322a0fd2e424b9c6998,

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 Ho-kwang Mao",

note = "Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to [email protected].",

year = "2019",

month = jan,

day = "28",

doi = "10.1002/anie.201813120",

language = "English",

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journal = "Angewandte Chemie - International Edition",

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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, H 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

TY - JOUR

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

N1 - Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to [email protected].

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

UR - https://www.scopus.com/pages/publications/85059523882

UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-85059523882&origin=recordpage

U2 - 10.1002/anie.201813120

DO - 10.1002/anie.201813120

M3 - RGC 21 - Publication in refereed journal

C2 - 30488662

SN - 1433-7851

VL - 58

SP - 1468

EP - 1473

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 5

ER -