The self-assembly behavior of mono(6-phenolic-6-deoxy)-β-cyclodextrin bothin solution and the solid state is comparatively studied by X-ray crystallography and ~1H NMRspectroscopy. The results obtained show that the phenolic groups in the crystal 1 can successivelypenetrate into the adjacent β-cyclodextrin cavities from the secondary side to form head-to-taillinear polymeric su-pramolecule with a 2-fold screw axis. The self-assembly behavior also can bedetermined in D_2O solution, giving a self-association constant of 240 mol^(-1)·L. Using thepresent and previous structures reported for the relevant β-cyclodextrin derivatives, i.e.,mono(6-anilino-6-deoxy)-β-cyclodextrin, mono(6-phenylselenyl-6-deoxy)-β-cyclodextrin, andmono(6-phenylthio-6-deoxy)-β-cyclodextrin, we further reveal the factors governing the formationsof supramolecular assemblies.
