Trimacrocyclic hexasubstituted benzene linked by labile octahedral [X(CHCl 3 ) 6 ] - 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 2 in the presence of guanidium halide salts and chloroform. Halide hexasolvate clusters, viz. [Cl(CHCl ₃ ) ₆ ] ^- , [Br(CHCl ₃ ) ₆ ] ^- , and [I(CHCl ₃ ) ₆ ] ^- , 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.
Competing Interests: There are no conflicts to declare.
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