Polymer Containing Multiple Secondary Structures—A Competition between Helical Induction and C‐T Complexation

Abstract

AbstractThough “foldamers” have greatly developed, molecules that fold beyond 2° structures are less common. The design and synthesis of triblock copolymers of the “A‐B‐A” type containing two types of helix formation blocks are presented. Two blocks (A and B) are chosen, with one comprised of L‐polyproline as block “A” and the other block (B) comprised with three naphthalene diimide‐derivatives separated by two proline residues. Block (B) is carefully designed to serve as a bifunctional initiator for the ring‐opening polymerization of proline‐N‐carboxy anhydride as well as to encapsulate an electron‐rich aromatic species by charge transfer complexation (C‐T). As a result of (C‐T) complexation with dialkoxy pyrene, the native helical structure of the middle block is transformed into a 1D columnar structure without affecting the 2° structure of the polyproline block. In this way, the initial helix1‐b‐helix2‐b‐helix1 structure of the block copolymers is transformed into a helix1‐b‐columnar‐b‐helix1 structure. The C‐T complexation and related structural changes of the block copolymers are characterized using UV‐vis, fluorescence, and circular dichroism spectroscopy.