Terpyridine-Induced Folding of Anisotropic Polyphosphoester Platelets

The folding of macromolecules is of great importance in nature. Also in synthetic polymer chemistry, single-chain nanoparticles, i.e. folding synthetic macromolecules, are a current research topic to mimic protein folding and to generate well-defined structures. Here, we present the "folding" of anisotropic polymer platelets to further mimic natural folding processes on the (sub)micrometer scale. We report on the synthesis of terpyridine-functionalized long-chain polyphosphoesters by acyclic diene metathesis polymerization that can crystallize in dilute solution into anisotropic polymer crystal platelets. As the terpyridine units are expelled to the platelet surface, terpyridine-metal interactions could be induced by adding nickel(II) bis(acetylacetonate) (Ni(acac)₂) to the platelet dispersion in ethyl acetate. These polymer crystals were "folded" to homogeneous nanoparticles with a wrinkled structure, which were visualized by transmission electron microscopy (TEM). The size and size distribution of the obtained assemblies could be altered by varying the concentration of Ni(acac)₂. In contrast, no wrinkled structures but rather intrachain cross-linking was observed, when Ni(acac)₂ was added to the homogeneous polymer solution before crystallization. We believe that this concept of "folding" anisotropic polymer platelets will further enhance the control of morphologies on (sub)micrometer particles and might be useful for catalysis or separation.