Trimacrocyclic hexasubstituted benzene linked by labile octahedral [X(CHCl)] clusters.

Crystalline supramolecular architectures mediated by cations, anions, ion pairs or neutral guest species are well established. However, the robust crystallization of a well-designed receptor mediated by labile anionic solvate clusters remains unexplored. Herein, we describe the synthesis and crystalline behaviors of a trimacrocyclic hexasubstituted benzene in the presence of guanidium halide salts and chloroform. Halide hexasolvate clusters, [Cl(CHCl)], [Br(CHCl)], and [I(CHCl)], were found to be critical to the crystallization process, as suggested by the single-crystal structures, X-ray powder diffraction (XRPD), thermogravimetric analysis (TGA), scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS), and NMR spectroscopy. This study demonstrates the hitherto unexpected role that labile ionic solvate clusters can play in stabilizing supramolecular architectures.