Mechanochemistry
has become a sustainable and attractive cost-effective
synthetic technique, largely used within the frame of crystal engineering.
Cocrystals, namely, crystalline compounds made of different chemical
entities within the same crystal structure, are typically synthesized
in bulk via mechanochemistry; however, whereas the macroscopic aspects
of grinding are becoming clear, the fundamental principles that underlie
mechanochemical cocrystallization at the microscopic level remain
poorly understood. Time-resolved in situ (TRIS) monitoring approaches
have opened the door to exceptional detail regarding mechanochemical
reactions. We here report a clear example of cocrystallization between
two solid coformers that proceeds through the formation of a metastable
low melting binary eutectic phase. The overall cocrystallization process
has been monitored by time-resolved in situ (TRIS) synchrotron X-ray
powder diffraction with a customized ball milling setup, currently
available at μSpot beamline at BESSY-II, Helmholtz-Zentrum Berlin.
The binary system and the low melting eutectic phase were further
characterized via DSC, HSM, and VT-XRPD.