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Title: Pressure-induced polymerization of acetylene: Structure-directed stereoselectivity and a possible route to graphane

Abstract

Geometric isomerism in polyacetylene is a basic concept in chemistry textbooks. Polymerization to cis-isomer is kinetically preferred at low temperature, not only in the classic catalytic reaction in solution but also, unexpectedly, in the crystalline phase when it is driven by external pressure without a catalyst. Until now, no perfect reaction route has been proposed for this pressure-induced polymerization. Using in situ neutron diffraction and meta-dynamic simulation, we discovered that under high pressure, acetylene molecules react along a specific crystallographic direction that is perpendicular to those previously proposed. Moreover, following this route produces a pure cis-isomer and more surprisingly, predicts that graphane is the final product. Experimentally, polycyclic polymers with a layered structure were identified in the recovered product by solid-state nuclear magnetic resonance and neutron pair distribution functions, which indicates the possibility of synthesizing graphane under high pressure.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [2];  [3];  [3];  [1];  [1];  [4];  [5];  [6];  [1];  [4];  [4]
+ Show Author Affiliations
  1. Center for High Pressure Science and Technology Advanced Research, Beijing (People's Republic of China)
  2. Carnegie Institution of Washington, Washington D.C. (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. (United States)
  5. Chinese Academy of Sciences, Beijing (China)
  6. (China)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1361379
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 23; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; acetylene; graphane; neutron diffraction; pressure-induced polymerization; solid-state reactions

Citation Formats

Sun, Jiangman, Dong, Xiao, Wang, Yajie, Li, Kuo, Zheng, Haiyan, Wang, Lijuan, Cody, George D., Tulk, Christopher A., Molaison, Jamie J., Lin, Xiaohuan, Meng, Yufei, Carnegie Institution of Washington, Washington, D.C., Jin, Changqing, Collaborative Innovation Center of Quantum Matter, Beijing, Mao, Ho-kwang, Carnegie Institution of Washington, Washington, D.C., and Carnegie Institution of Washington, Argonne, IL. Pressure-induced polymerization of acetylene: Structure-directed stereoselectivity and a possible route to graphane. United States: N. p., 2017. Web. doi:10.1002/anie.201702685.
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Sun, Jiangman, Dong, Xiao, Wang, Yajie, Li, Kuo, Zheng, Haiyan, Wang, Lijuan, Cody, George D., Tulk, Christopher A., Molaison, Jamie J., Lin, Xiaohuan, Meng, Yufei, Carnegie Institution of Washington, Washington, D.C., Jin, Changqing, Collaborative Innovation Center of Quantum Matter, Beijing, Mao, Ho-kwang, Carnegie Institution of Washington, Washington, D.C., & Carnegie Institution of Washington, Argonne, IL. Pressure-induced polymerization of acetylene: Structure-directed stereoselectivity and a possible route to graphane. United States. https://doi.org/10.1002/anie.201702685
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Sun, Jiangman, Dong, Xiao, Wang, Yajie, Li, Kuo, Zheng, Haiyan, Wang, Lijuan, Cody, George D., Tulk, Christopher A., Molaison, Jamie J., Lin, Xiaohuan, Meng, Yufei, Carnegie Institution of Washington, Washington, D.C., Jin, Changqing, Collaborative Innovation Center of Quantum Matter, Beijing, Mao, Ho-kwang, Carnegie Institution of Washington, Washington, D.C., and Carnegie Institution of Washington, Argonne, IL. Tue . "Pressure-induced polymerization of acetylene: Structure-directed stereoselectivity and a possible route to graphane". United States. https://doi.org/10.1002/anie.201702685. https://www.osti.gov/servlets/purl/1361379.
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@article{osti_1361379,
title = {Pressure-induced polymerization of acetylene: Structure-directed stereoselectivity and a possible route to graphane},
author = {Sun, Jiangman and Dong, Xiao and Wang, Yajie and Li, Kuo and Zheng, Haiyan and Wang, Lijuan and Cody, George D. and Tulk, Christopher A. and Molaison, Jamie J. and Lin, Xiaohuan and Meng, Yufei and Carnegie Institution of Washington, Washington, D.C. and Jin, Changqing and Collaborative Innovation Center of Quantum Matter, Beijing and Mao, Ho-kwang and Carnegie Institution of Washington, Washington, D.C. and Carnegie Institution of Washington, Argonne, IL},
abstractNote = {Geometric isomerism in polyacetylene is a basic concept in chemistry textbooks. Polymerization to cis-isomer is kinetically preferred at low temperature, not only in the classic catalytic reaction in solution but also, unexpectedly, in the crystalline phase when it is driven by external pressure without a catalyst. Until now, no perfect reaction route has been proposed for this pressure-induced polymerization. Using in situ neutron diffraction and meta-dynamic simulation, we discovered that under high pressure, acetylene molecules react along a specific crystallographic direction that is perpendicular to those previously proposed. Moreover, following this route produces a pure cis-isomer and more surprisingly, predicts that graphane is the final product. Experimentally, polycyclic polymers with a layered structure were identified in the recovered product by solid-state nuclear magnetic resonance and neutron pair distribution functions, which indicates the possibility of synthesizing graphane under high pressure.},
doi = {10.1002/anie.201702685},
journal = {Angewandte Chemie (International Edition)},
number = 23,
volume = 56,
place = {United States},
year = {2017},
month = {5}
}
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https://doi.org/10.1002/anie.201702685
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    Works referencing / citing this record:

    The Effect of Pressure on Organic Reactions in Fluids-a New Theoretical Perspective
    journal, July 2017

    • Chen, Bo; Hoffmann, Roald; Cammi, Roberto
    • Angewandte Chemie International Edition, Vol. 56, Issue 37
    • DOI: 10.1002/anie.201705427

    Chemistry through cocrystals: pressure-induced polymerization of C 2 H 2 ·C 6 H 6 to an extended crystalline hydrocarbon
    journal, January 2018

    • Ward, Matthew D.; Huang, Haw-Tyng; Zhu, Li
    • Physical Chemistry Chemical Physics, Vol. 20, Issue 10
    • DOI: 10.1039/c7cp07852h

    Pressure-induced amorphization and reactivity of solid dimethyl acetylene probed by in situ FTIR and Raman spectroscopy
    journal, May 2018

    • Guan, Jiwen; Daljeet, Roshan; Kieran, Arielle
    • Journal of Physics: Condensed Matter, Vol. 30, Issue 22
    • DOI: 10.1088/1361-648x/aabeac

    From Molecules to Carbon Materials—High Pressure Induced Polymerization and Bonding Mechanisms of Unsaturated Compounds
    journal, September 2019

    Pressure-Induced Polymorphism of Caprolactam: A Neutron Diffraction Study
    journal, June 2019

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