Critical Size of Secondary Nuclei Determined via Nucleation Theorem Reveals Selective Nucleation in Three-Component Co-Crystals

The critical size of the secondary nuclei plays an important role in determining the crystal growth rate. In the past, the Nucleation Theorem has been applied to determine the number of molecules in the critical nuclei of a single-component crystal via variation of the crystal growth rate with dilution by the non-crystallizable component. In this work, we extend the method to the three-component co-crystal poly (ethylene oxide)/urea/thiourea inclusion compound. The theoretical crystal growth kinetics were deduced and the dependence of the radial growth rate of the inclusion compound spherulites on the mass fraction of urea in urea/thiourea was measured. The results reveal that the secondary nuclei of the poly (ethylene oxide)/urea/thiourea inclusion compound consist mainly of ethylene oxide repeating units and urea molecules. We propose that only urea molecules and ethylene oxide repeating units are selected to form the secondary nuclei while co-crystallization of the three components happens at the lateral spreading stage. As a result, the composition of the critical secondary nuclei is different from that of the bulk inclusion compound crystals. The work is expected to deepen our understanding of the nucleation of multi-component co-crystals.