Tetracyanomethane under Pressure: Extended CN Polymers from Precursors with Built-in sp3 Centers

Keefer, Derek W.; Gou, Huiyang; Wang, Qianqian; Purdy, Andrew; Epshteyn, Albert; Juhl, Stephen J.; Cody, George D.; Badding, John; Strobel, Timothy A.

doi:10.1021/acs.jpca.7b10729

Title: Tetracyanomethane under Pressure: Extended CN Polymers from Precursors with Built-in sp³ Centers

Journal Article · Mon Feb 12 00:00:00 EST 2018 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.7b10729· OSTI ID:1430339

Keefer, Derek W. ^[1]; Gou, Huiyang ^[2]; Wang, Qianqian ^[3];

^[4];

^[4]; Juhl, Stephen J. ^[1]; Cody, George D. ^[3];

^[1];

^[3]

Pennsylvania State Univ., University Park, PA (United States)
Carnegie Inst. of Washington, Washington, DC (United States); Center for High Pressure Science and Technology Advanced Research, Beijing (China)
Carnegie Inst. of Washington, Washington, DC (United States)
Naval Research Lab., Washington, D.C. (United States)

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.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC02-06CH11357; NA0001974

OSTI ID:: 1430339

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 122, Issue 11; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Cited by: 8 works

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Title: Tetracyanomethane under Pressure: Extended CN Polymers from Precursors with Built-in sp³ Centers