skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Tetracyanomethane under Pressure: Extended CN Polymers from Precursors with Built-in sp 3 Centers

Abstract

Tetracyanomethane, C(CN) 4, is a tetrahedral molecule containing a central sp 3 carbon that is coordinated by reactive nitrile groups that could potentially transform to an extended CN network with a significant fraction of sp 3 carbon. High-purity C(CN) 4 was synthesized, and its physiochemical behavior was studied using in situ synchrotron angle-dispersive powder X-ray diffraction (PXRD) and Raman and infrared (IR) spectroscopies in a diamond anvil cell (DAC) up to 21 GPa. The pressure dependence of the fundamental vibrational modes associated with the molecular solid was determined, and some low-frequency Raman modes are reported for the first time. Crystalline molecular C(CN) 4 starts to polymerize above ~7 GPa and transforms into an interconnected disordered network, which is recoverable to ambient conditions. Lastly, the results demonstrate feasibility for the pressure-induced polymerization of molecules with premeditated functionality.

Authors:
 [1];  [2];  [3]; ORCiD logo [4]; ORCiD logo [4];  [1];  [3]; ORCiD logo [1]; ORCiD logo [3]
  1. Pennsylvania State Univ., University Park, PA (United States)
  2. Carnegie Inst. of Washington, Washington, DC (United States); Center for High Pressure Science and Technology Advanced Research, Beijing (China)
  3. Carnegie Inst. of Washington, Washington, DC (United States)
  4. Naval Research Lab., Washington, D.C. (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1430339
Grant/Contract Number:  
AC02-06CH11357; NA0001974
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 122; Journal Issue: 11; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; polymerization; carbon; lattices; materials; molecules

Citation Formats

Keefer, Derek W., Gou, Huiyang, Wang, Qianqian, Purdy, Andrew, Epshteyn, Albert, Juhl, Stephen J., Cody, George D., Badding, John, and Strobel, Timothy A. Tetracyanomethane under Pressure: Extended CN Polymers from Precursors with Built-in sp3 Centers. United States: N. p., 2018. Web. doi:10.1021/acs.jpca.7b10729.
Keefer, Derek W., Gou, Huiyang, Wang, Qianqian, Purdy, Andrew, Epshteyn, Albert, Juhl, Stephen J., Cody, George D., Badding, John, & Strobel, Timothy A. Tetracyanomethane under Pressure: Extended CN Polymers from Precursors with Built-in sp3 Centers. United States. https://doi.org/10.1021/acs.jpca.7b10729
Keefer, Derek W., Gou, Huiyang, Wang, Qianqian, Purdy, Andrew, Epshteyn, Albert, Juhl, Stephen J., Cody, George D., Badding, John, and Strobel, Timothy A. Mon . "Tetracyanomethane under Pressure: Extended CN Polymers from Precursors with Built-in sp3 Centers". United States. https://doi.org/10.1021/acs.jpca.7b10729. https://www.osti.gov/servlets/purl/1430339.
@article{osti_1430339,
title = {Tetracyanomethane under Pressure: Extended CN Polymers from Precursors with Built-in sp3 Centers},
author = {Keefer, Derek W. and Gou, Huiyang and Wang, Qianqian and Purdy, Andrew and Epshteyn, Albert and Juhl, Stephen J. and Cody, George D. and Badding, John and Strobel, Timothy A.},
abstractNote = {Tetracyanomethane, C(CN)4, is a tetrahedral molecule containing a central sp3 carbon that is coordinated by reactive nitrile groups that could potentially transform to an extended CN network with a significant fraction of sp3 carbon. High-purity C(CN)4 was synthesized, and its physiochemical behavior was studied using in situ synchrotron angle-dispersive powder X-ray diffraction (PXRD) and Raman and infrared (IR) spectroscopies in a diamond anvil cell (DAC) up to 21 GPa. The pressure dependence of the fundamental vibrational modes associated with the molecular solid was determined, and some low-frequency Raman modes are reported for the first time. Crystalline molecular C(CN)4 starts to polymerize above ~7 GPa and transforms into an interconnected disordered network, which is recoverable to ambient conditions. Lastly, the results demonstrate feasibility for the pressure-induced polymerization of molecules with premeditated functionality.},
doi = {10.1021/acs.jpca.7b10729},
url = {https://www.osti.gov/biblio/1430339}, journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
issn = {1089-5639},
number = 11,
volume = 122,
place = {United States},
year = {2018},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referencing / citing this record:

Pressure effect on the mechanical and electronic properties of orthorhombic-C20
journal, November 2018