Effects of high pressure on azobenzene and hydrazobenzene probed by Raman spectroscopy

In this study, two hydrazine derivatives, azobenzene and hydrazobenzene, were compressed in a diamond anvil cell at room temperature up to 28 GPa followed by decompression. In situ Raman spectroscopy was employed to monitor the pressure-induced structural evolutions. Azobenzene was found to undergo a phase transition at ~10 GPa. Further compression to 18 GPa resulted in an irreversible breakdown of the molecular structure. Although hydrazobenzene exhibited a structural transition at a similar pressure of 10 GPa, it was found to sustain a compression pressure as high as 28 GPa without chemical reactions. The transition sequence of hydrazobenzene upon compression and decompression was thus entirely reversible in the pressure region studied, in strong contrast to that of azobenzene. The high-pressure structures of these two molecules were examined based on the spectroscopic data, and their drastically different high-pressure behaviors were analyzed and interpreted with the aid of ab initio molecular orbital calculations.