Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) is one of the most important energetic materials. Investigations on its phase transitions and chemical reactions under extreme conditions are very important to understand the explosion process and design new energetic materials. By using a diamond anvil cell combined with in situ Raman, IR and X-ray diffraction techniques up to a pressure of ∼40 GPa, we found that β-HMX undergoes four reversible phase transitions without any chemical reaction under external pressure at room temperature. Isostructural phase transitions emerge around 5 GPa (ζ-HMX) and 10–13 GPa (ε-HMX), and another two phases emerge at 16 GPa (η-HMX) and 27 GPa (ϕ-HMX). The unit cells of ζ-HMX and ε-HMX were determined as a = 6.215 Å, b = 10.417 Å, c = 8.272 Å, β = 124.88°, P2₁/c at 6.2 GPa and a = 6.130 Å, b = 9.846 Å, c = 8.258 Å, β = 125.06°, P2₁/c at 12.6 GPa, respectively. The crystal structures of β, ζ, and ε-HMX were obtained by Rietveld refinement, based on which the rotations of NO₂ groups were found to be related to the phase transition at 5 GPa. Additionally, HMX decomposes at 8.7 GPa and 300 °C. Carbon dioxide, hydroxyl, imino and hydroxyimino groups were detected in the IR spectrum, which indicates that the reaction contains a hydrogen transfer process. Our investigation uncovers the structural variation of β-HMX under external pressure and identifies the decomposition products under extreme conditions, which provides new insight to understand the detonation process of energetic materials.

Under pressure of 1–100 GPa, unsaturated organic molecules tend to form covalent bond to each other for a negative enthalpy change, which often produces polymeric materials with extended carbon skeleton. The polymerization reactions typically happen in crystal, which promotes the topochemical process. This review summarized the topochemical polymerization processes of several alkynes, aromatics, and alkynylphenyl compounds, including the critical crystal structures before the reaction, bonding process, and the structure of the products. Secondly, this review also summarized the condensation reaction identified in the polymerization process, including the elimination of small molecules such as NH₃, etc.

Nonbenzenoid graphene nanoribbons such as biphenylene networks have gained increasing attention owing to their promising electronic and transport properties, but their scalable synthesis is still a huge challenge. Pressure-induced topochemical polymerization is an effective method to assemble molecular units into extended carbon materials, and the structure and properties of the carbon material can be tuned by modifying its molecular precursors. Herein, by directly compressing biphenylene at room temperature, we successfully synthesized crystalline biphenylene nanoribbons in milligram scale. By combining the spectroscopy and single crystal X-ray diffraction methods as well as theoretical calculation, we found that biphenylene experiences a minor phase transition above 3 GPa, and two phenyls in biphenylene undergo sequential para-polymerization along the a-axis to form a ribbon structure at 14 GPa. Our work provides an important reference for the high-pressure reaction of aromatics and the synthesis of complex nanoribbons.