Solvent-Switched Schiff-Base Macrocycles: Self-Sorting and Self-Assembly-Dependent Unconventional Organic Particles

Organic reaction is a powerful and versatile tool for the creation of various new substrates and materials. However, there have been few reports of the direct fabrication of organic particles by organic reactions. Herein, we report that water as a co-solvent can efficiently switch a [2 + 2] macrocycle (3) to a [1 + 1] macrocycle (4) in a Schiff-base reaction from the same precursors at room temperature. Unexpectedly, a series of tunable organic micro/nanoparticles, including solid microspheres, core-shell spheres, and vesicles, could be directly precipitated in one-step from the reaction medium with high yield. X-ray structure analysis and other characterizations indicated that social self-sorting and narcissistic self-sorting of the macrocyclic frameworks of 3 and 4 through noncovalent interactions play crucial roles in the formation of such organic particles. Most interestingly, the facile and mild vesicle fabrication conditions of the particles allowed us to accurately and in situ monitor their intermediate formation by controlling the reaction time. This work thus provides an advancement of the fabrication of tunable organic particles.