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Abstract 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.
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Rapid Access to Diverse Multicomponent Hierarchical Nanostructures from Mixed‐Graft Block Copolymers
Abstract Multicomponent nanostructured materials assembled from molecular building blocks received wide attention due to their precisely integrated multifunctionalities. However, discovery of these materials with desirable composition and morphology was limited by their low synthetic scalability and narrow structural tuning window with given building blocks. Here, we report a scalable and diversity‐oriented synthetic approach to hierarchically structured nanomaterials based on a few readily accessible building blocks. Mixed‐graft block copolymers containing sequence‐defined side chains were prepared through ring‐opening metathesis copolymerization of three or four types of macromonomers. Intramolecularly defined interfaces promoted the formation of ordered hierarchical structures with lattice sizes tunable across multiple length scales. The same set of macromonomers were arranged and combined in different ways, providing access to diverse morphologies in the resultant structures.
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- Award ID(s):
- 2003875
- PAR ID:
- 10373383
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 61
- Issue:
- 41
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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