Hierarchical Self-Assembly of Halogen-Bonded Block Copolymer Complexes into Upright Cylindrical Domains

Roberto Milani, Nikolay Houbenov, Francisco Fernandez-Palacio, Gabriella Cavallo, Alessandro Luzio, Johannes Haataja, Gabriele Giancane, Marco Saccone, Arri Priimagi, Pierangelo Metrangolo*, Olli Ikkala

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

48 Citations (Scopus)
414 Downloads (Pure)


Self-assembly of block copolymers into well-defined, ordered arrangements of chemically distinct domains is a reliable strategy for preparing tailored nanostructures. Microphase separation results from the system, minimizing repulsive interactions between dissimilar blocks and maximizing attractive interactions between similar blocks. Supramolecular methods have also achieved this separation by introducing small-molecule additives binding specifically to one block by noncovalent interactions. Here, we use halogen bonding as a supramolecular tool that directs the hierarchical self-assembly of low-molecular-weight perfluorinated molecules and diblock copolymers. Microphase separation results in a lamellar-within-cylindrical arrangement and promotes upright cylindrical alignment in films upon rapid casting and without further annealing. Such cylindrical domains with internal lamellar self-assemblies can be cleaved by solvent treatment of bulk films, resulting in separated and segmented cylindrical micelles stabilized by halogen-bond-based supramolecular crosslinks. These features, alongside the reversible nature of halogen bonding, provide a robust modular approach for nanofabrication.

Original languageEnglish
Pages (from-to)417-426
Number of pages10
Issue number3
Publication statusPublished - 9 Mar 2017
MoE publication typeA1 Journal article-refereed


  • block copolymers
  • halogen bond
  • hierarchical self-assembly
  • nanofabrication
  • supramolecular complexes


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