Propagation-Instigated Self-Limiting Polymerization of Multiarmed Amphiphiles into Finite Supramolecular Polymers

A fundamental goal in the noncovalent synthesis of ordered supramolecular polymers (SPs) is to achieve precise control over their size and size distribution; however, the reversible nature of noncovalent interactions often results in formation of living SPs with high dispersity in length. We report here on the self-limiting supramolecular polymerization (SPZ) of a series of multiarmed amphiphiles with propagation-attenuated reactivities that can automatically terminate the polymerization process, enabling effective control in both lengths and polydispersity. Through incorporating multiarmed oligoethylene-glycol (OEG) onto a quadratic aromatic segment, the lengths of the resultant SPs can be tuned from ∼1 μm to 130 and 50 nm with a polydispersity index of ∼1.2 for the last two SPs. We believe that the level of chain frustration of the multiarmed OEG segments, determined by both the number of arms and the degree of polymerization, poses physical and entropic constrains for supramolecular propagation to exceed a threshold length.