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Title: Pressure-Induced Diels-Alder Reactions in C6H6-C6F6 Cocrystal towards Graphane Structure

Abstract

Pressure-induced polymerization (PIP) of aromatics is a novel method to construct sp3-carbon frameworks, and nanothreads with diamond-like structures were synthesized by compressing benzene and its derivatives. Here, by compressing benzene-hexafluorobenzene cocrystal (CHCF), we identified H-F-substituted graphane with a layered structure in the PIP product. Based on the crystal structure determined from the in situ neutron diffraction and the intermediate products identified by the gas chromatography-mass spectrum, we found that at 20 GPa CHCF forms tilted columns with benzene and hexafluorobenzene stacked alternatively, which leads to a [4+2] polymer, and then transfers to short-range ordered hydrogenated-fluorinated graphane. The reaction process contains [4+2] Diels-Alder, retro-Diels-Alder, and 1-1' coupling, and the former is the key reaction in the PIP. In conclusion, our studies confirmed the elemental reactions of the CHCF for the first time, which provides a novel insight into the PIP of aromatics.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1];  [2];  [2];  [2];  [2]; ORCiD logo [3];  [3];  [4];  [4]; ORCiD logo [5]; ORCiD logo [5];  [6];  [7];  [8];  [9]
+ Show Author Affiliations
  1. Center for High Pressure Science and Technology Advanced Research, Beijing (China)
  2. China Academy of Engineering Physics, Mianyang (China). Key Lab. of Neutron Physics and Inst. of Nuclear Physics and Chemistry
  3. Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Rutherford Appleton Lab., ISIS Neutron Source
  4. Japan Atomic Energy Agency (JAEA), Tokai (Japan). J-PARC Center
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
  6. Carnegie Inst. of Washington, Washington, DC (United States). Geophysical Lab.
  7. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  8. Pohang Accelerator Lab. (PAL) (Korea, Republic of). POSTECH
  9. Center for High Pressure Science and Technology Advanced Research, Beijing (China); Carnegie Inst. of Washington, Washington, DC (United States). Geophysical Lab.
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS) and Center for Nanophase Materials Science (CNMS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Natural Science Foundation of China (NSFC); Science and Technology Facilities Council (STFC)
OSTI Identifier:
1489507
Alternate Identifier(s):
OSTI ID: 1606944
Grant/Contract Number:  
AC02-06CH11357; 21601007; 21771011; 21875006; 21803033; AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 58; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; cycloaddition; graphane; polymerization; solid-state reactions; structure determination

Citation Formats

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, Sano-Furukawa, Asami, Chen, Jihua, Hensley, Dale K., Cody, George D., Ren, Yang, Lee, Hyun Hwi, and Mao, Ho-kwang. Pressure-Induced Diels-Alder Reactions in C6H6-C6F6 Cocrystal towards Graphane Structure. United States: N. p., 2018. Web. doi:10.1002/anie.201813120.
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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, Sano-Furukawa, Asami, Chen, Jihua, Hensley, Dale K., Cody, George D., Ren, Yang, Lee, Hyun Hwi, & Mao, Ho-kwang. Pressure-Induced Diels-Alder Reactions in C6H6-C6F6 Cocrystal towards Graphane Structure. United States. https://doi.org/10.1002/anie.201813120
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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, Sano-Furukawa, Asami, Chen, Jihua, Hensley, Dale K., Cody, George D., Ren, Yang, Lee, Hyun Hwi, and Mao, Ho-kwang. Thu . "Pressure-Induced Diels-Alder Reactions in C6H6-C6F6 Cocrystal towards Graphane Structure". United States. https://doi.org/10.1002/anie.201813120. https://www.osti.gov/servlets/purl/1489507.
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@article{osti_1489507,
title = {Pressure-Induced Diels-Alder Reactions in C6H6-C6F6 Cocrystal towards Graphane Structure},
author = {Wang, Yajie and Dong, Xiao and Tang, Xingyu and Zheng, Haiyan and Li, Kuo and Lin, Xiaohuan and Fang, Leiming and Sun, Guang'ai and Chen, Xiping and Xie, Lei and Bull, Craig L. and Funnell, Nicholas P. and Hattori, Takanori and Sano-Furukawa, Asami and Chen, Jihua and Hensley, Dale K. and Cody, George D. and Ren, Yang and Lee, Hyun Hwi and Mao, Ho-kwang},
abstractNote = {Pressure-induced polymerization (PIP) of aromatics is a novel method to construct sp3-carbon frameworks, and nanothreads with diamond-like structures were synthesized by compressing benzene and its derivatives. Here, by compressing benzene-hexafluorobenzene cocrystal (CHCF), we identified H-F-substituted graphane with a layered structure in the PIP product. Based on the crystal structure determined from the in situ neutron diffraction and the intermediate products identified by the gas chromatography-mass spectrum, we found that at 20 GPa CHCF forms tilted columns with benzene and hexafluorobenzene stacked alternatively, which leads to a [4+2] polymer, and then transfers to short-range ordered hydrogenated-fluorinated graphane. The reaction process contains [4+2] Diels-Alder, retro-Diels-Alder, and 1-1' coupling, and the former is the key reaction in the PIP. In conclusion, our studies confirmed the elemental reactions of the CHCF for the first time, which provides a novel insight into the PIP of aromatics.},
doi = {10.1002/anie.201813120},
journal = {Angewandte Chemie (International Edition)},
number = ,
volume = 58,
place = {United States},
year = {Thu Nov 29 00:00:00 EST 2018},
month = {Thu Nov 29 00:00:00 EST 2018}
}
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https://doi.org/10.1002/anie.201813120
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    From Molecules to Carbon Materials—High Pressure Induced Polymerization and Bonding Mechanisms of Unsaturated Compounds
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    Glycerol and Q-Tubes: Green Catalyst and Technique for Synthesis of Polyfunctionally Substituted Heteroaromatics and Anilines
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