文摘
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 transition and the polymerization process.