How Does PHEMA Pass through the Cavity of γ-CDs to Create Mismatched Overfit Polypseudorotaxanes?

A syndiotactic-rich PHEMA oligomer (rr = 74%, DP = 29, PDI = 1.19) was synthesized and subsequently subjected to self-assembly with a varying amount of γ-CDs in its aqueous solution to create mismatched overfit polypseudorotaxanes (PPRs). The inclusion complexation proceeded in an obvious mismatched manner between the cavity of γ-CDs and the cross-sectional area of an incoming PHEMA chain. The 2D-NOESY NMR analysis provided direct evidence indicating that two adjacent pendant hydroxyethyl groups in PHEMA preferably adopt a curled conformation to pass through the cavity of γ-CDs, giving the PPRs characteristics of a mismatched overfit instead of a matched tight-fit crystal structure. The results suggested that the mutual adaption of pendant side chains of HEMA units with the cavity geometry of γ-CDs would play a dominant role in this unfavorable overfit inclusion complexation besides the size of γ-CDs and the stereoregularity of the PHEMA chain.