Phase Transitions and Polymerization of C6H6–C6F6 Cocrystal under Extreme Conditions
2016
Pressure-induced polymerization (PIP) of aromatic molecules can generate saturated carbon nanostructures. As a strongly interacted π–π stacking unit, the C6H6–C6F6 adduct is widely applied in supramolecular chemistry, and it provides a good preorganization for the PIP. Here we investigated the structural variation of C6H6–C6F6 cocrystal and the subsequent PIP process under high pressure. Four new molecular-complex phases V, VI, VII, and VIII have been identified and characterized by the in situ Raman, IR, synchrotron X-ray, and neutron diffraction. The phase V is different from the phases observed at low temperature, which has a tilted column structure. Phases VI and VII have a structure similar to phase V. Phase VIII polymerizes irreversibly upon compression above 25 GPa without any catalyst, producing sp3(CH/F)n materials. The π–π interaction is still dominant below 0.5 GPa but is most likely to be overstepped under further compression, which is important for discussing the supramolecular phase transiti...
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