Cucurbit[n]urils (n= 5–8): A Comprehensive Solid State Study

Cucurbit[ n ]urils (CB[ n ], n = 5–8) have been prepared, separated, and purified, and the structure of their solid state assemblies has been addressed. A number of general features were identified which are of interest to understand some peculiar properties of cucurbiturils (solubility, aggregation, assembly, transformation to porous crystals, influence of air humidity). CB[5], CB[6], and CB[8] were isolated as hydrate crystals whose structures were found to show a strong tendency of the macrocycles to interpenetrate. A self-closing effect was rationalized in terms of multiple weak CH···O interactions between the macrocycles, the degree of which is discussed in detail. Solid state cross polarization magic angle spinning (CP-MAS) 13 C NMR spectra obtained at 900 MHz were correlated with the crystal structures. An odd–even effect in the crystallinity of thermally treated CB samples (CB[5] and CB[7] amorphous, CB[6] and CB[8] crystalline) was observed, which is reflected in differences in water solubility (CB[5] and CB[7] are water-soluble, whereas CB[6] and CB[8] are only very scarcely so). This may be explained by a less efficient self-association for CB[5] and CB[7] as compared with CB[6] and CB[8], which is reflected in the number of inter-cucurbituril CH···O interactions per cucurbituril. This leads to a more favorable solvation for the CBs having an odd symmetry, whereas those with even symmetry prefer to self-associate in a manner ultimately leading to crystallization. We also propose an explanation for the presence of anions (Cl – ) inside some cucurbituril materials, whose cavity is often considered hydrophobic. Furthermore, it is demonstrated that large quantities of the very stable microporous CB[6] crystals (which have the R 3̅ channel structure) can be obtained very easily by a simple thermal treatment of the hexagonal crystals of CB[6] ( P 6/ mmm structure) obtained directly from the initial reaction used to synthesize the various CB[ n ]. The micromorphology of the CB[ n ] powders was established using scanning electron microscopy (SEM), and the tendency of each material to absorb water from the atmosphere was demonstrated by thermogravimetric analyses (TGA).