Photostable Helical Polyfurans

Abstract

This report describes the design and synthesis of a new class of polyfurans bearing ester side chains. The macromolecules can be synthesized using catalyst-transfer polycondensation, providing precise control over molecular weight and molecular weight distribution. Such obtained furan ester polymers are significantly more photostable than their alkyl analogues owing to the electron-withdrawing nature of the attached subunit. Most interestingly, they spontaneously fold into a compact π-stacked helix, yielding a complex multilayer cylindrical nanoparticle with a hollow, rigid, conjugated core composed of the polyfuran backbone and a soft, insulating outer layer formed by the ester side chains. The length of polymer side chains dictates the outer diameter of such nanoparticles, which for the hexyl ester groups used in the present study is equal to ∼2.3 nm. The inner cavity of the conjugated core is lined with oxygen atoms, which set its effective diameter to 0.4 nm. Furthermore, installation of bulkier, branched chiral ester side chains on the repeat unit yields structures that, upon change of solvent, can reversibly transition between an ordered chiral helical folded and disordered unfolded state.