Intramolecular Folding of Coil-Helix Block Copolymers Induced by Quadrupole Interactions.

True tertiary architectures with defined local secondary structures are rare in synthetic systems. Adapting well-developed synthetic building blocks and controlling their folding through diverse interactions can be a general approach toward this goal. In this contribution, the synthesis of 3D hierarchical assemblies with distinct secondary domains formed through the intramolecular folding of a block copolymer containing a coil-like poly(styrene) (PS) block with a helical poly(isocyanide) block induced by phenyl-pentafluorophenyl quadrupole interactions is reported. The PS block is prepared via atom-transfer radical polymerization and end functionalized with a nickel complex that serves as a macroinitiator for the polymerization of chiral isocyanides bearing pentafluorophenyl pendants. The folding behavior of the coil-helix block copolymers is investigated by dynamic light scattering, NMR spectroscopy, wide-angle X-ray scattering, and differential scanning calorimetry.