Polymorphism of pyrene on compression to 35 GPa in a diamond anvil cell

Abstract Structural studies of pyrene have been limited to below 2 GPa. Here, we report on investigations of pyrene up to ~35 GPa using in situ single-crystal synchrotron X-ray diffraction in diamond anvil cells and ab initio calculations. They reveal the phase transitions from pyrene-I to pyrene-II (0.7 GPa), and to the previously unreported pyrene-IV (2.7 GPa), and pyrene-V (7.3 GPa). The structure and bonding analysis shows that gradual compression results in continuous compaction of molecular packing, eventually leading to curvature of molecules, which has never been observed before. Large organic molecules exhibit unexpectedly high conformational flexibility preserving pyrene-V up to 35 GPa. Ab initio calculations suggest that the phases we found are thermodynamically metastable compared to pyrene-III previously reported at 0.3 and 0.5 GPa. Our study contributes to the fundamental understanding of the polymorphism of polycyclic aromatic hydrocarbons and calls for further theoretical exploration of their structure–property relationships.