Linear Polypseudorotaxanes Possessing Many Metal Centers Constructed from Inclusion Complexes of α-, β-, and γ-Cyclodextrins with 4,4‘-Dipyridine

Three cyclodextrin-based complexes, 1-3, bearing external coordination sites for metal cations were prepared in satisfactory yields (over 50%) by reactions of alpha-, beta-, and gamma-cyclodextrins with 4,4'-dipyridine in aqueous solutions. Subsequently, these inclusion complexes were further assembled to form linear polypseudorotaxanes 4-6 through the coordination linkage of Ni(II) or Cu(II) ions, and their assembly behaviors were comprehensively investigated in both solutions and the solid state by means of 1H NMR, FT-IR, UV-vis spectroscopy, conductivity titration, powder X-ray diffraction patterning, thermogravimetric and differential thermal analysis, scanning electron microscopy, scanning tunneling microscopy, and transmission electron microscopy. The results showed that these polypseudorotaxanes existed as individual linear arrays at a low concentration but tended to form polymeric rodlike fibers at a relatively high concentration. Significantly, the volume of the cyclodextrin cavity used not only determined the inclusion complexation stoichiometry between cyclodextrin and 4,4'-dipyridine but also predominated the morphology of resulting polypseudorotaxanes.