Chemistry through cocrystals: pressure-induced polymerization of C2H2·C6H6 to an extended crystalline hydrocarbon

Literature Information

Publication Date 2018-02-02
DOI 10.1039/C7CP07852H
Impact Factor 3.676
Authors

Matthew D. Ward, Haw-Tyng Huang, Li Zhu, Arani Biswas, Dmitry Popov, Timothy A. Strobel


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Abstract

The 1 : 1 acetylene–benzene cocrystal, C2H2·C6H6, was synthesized under pressure in a diamond anvil cell (DAC) and its evolution under pressure was studied with single-crystal X-ray diffraction and Raman spectroscopy. C2H2·C6H6 is stable up to 30 GPa, nearly 10× the observed polymerization pressure for molecular acetylene to polyacetylene. Upon mild heating at 30 GPa, the cocrystal was observed to undergo an irreversible transition to a mixture of amorphous hydrocarbon and a crystalline phase with similar diffraction to i-carbon, a nanodiamond polymorph currently lacking a definitive structure. Characterization of this i-carbon-like phase suggests that it remains hydrogenated and may help explain previous observations of nanodiamond polymorphs. Potential reaction pathways in C2H2·C6H6 are discussed and compared with other theoretical extended hydrocarbons that may be obtained through crystal engineering. The cocrystallization of benzene with other more inert gases may provide a novel pathway to selectively control the rich chemistry of these materials.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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