The formation of a metastable supercooled alkyl-π molecular liquid was prohibited by subtle alteration of the molecular structure.

A supramolecular cross-linked cross-linker, capable of introducing rotaxane cross-links to vinyl polymers, has been developed for the rational synthesis of polyrotaxane networks. The experimental results reveal that the combination of an oligocyclodextrin (OCD) and a terminal bulky group-tethering macromonomer (TBM) forms a polymer-network structure having polymerizable moieties through supramolecular cross-linking. Radical polymerization of a variety of typical vinyl monomers in the presence of the vinylic supramolecular cross-linker (VSC) afforded the corresponding vinyl polymers cross-linked through the rotaxane cross-links (RCP) as transparent stable films in high yields under both photoinitiated and thermal polymerization conditions. A poly(N,N-dimethylacrylamide)-based hydrogel synthesized by using VSC, RCPDMAAm , displayed a unique mechanical property. The small-angle X-ray scattering (SAXS) results, indicating patterns characteristic of a polyrotaxane network, clearly suggested the presence and role of the rotaxane cross-links. The confirmation of the introduction of rotaxane-cross-links into vinyl polymers strongly reveals the significant usefulness of VSC.

A catalyst- and solvent-free synthesis of cyclodextrin-based polyrotaxanes exploiting a stable nitrile N-oxide as an end-capping agent was achieved. The C-C bond-forming end-capping reaction of an allyl-terminated pseudopolyrotaxane with the nitrile N-oxide proceeded smoothly by solid-state grinding in a mortar to afford a polyrotaxane.

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