title: Hierarchical Self-Assembly of Halogen-Bonded Block Copolymer Complexes into Upright Cylindrical Domains.
abstract: 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.
authors.affiliation: VTT Technical Research Centre of Finland Ltd., 02044 VTT Espoo, Finland.
authors.forename: Roberto
authors.initials: R
authors.lastname: Milani
authors.affiliation: Department of Applied Physics, HYBER Centre of Excellence, Aalto University, 02150 Espoo, Finland.
authors.forename: Nikolay
authors.initials: N
authors.lastname: Houbenov
authors.affiliation: Laboratory of Nanostructured Fluorinated Materials (NFMLab), Department of Chemistry, Materials, and Chemical Engineering "Giulio Natta", Politecnico di Milano, 20131 Milano, Italy.
authors.forename: Francisco
authors.initials: F
authors.lastname: Fernandez-Palacio
authors.affiliation: Laboratory of Nanostructured Fluorinated Materials (NFMLab), Department of Chemistry, Materials, and Chemical Engineering "Giulio Natta", Politecnico di Milano, 20131 Milano, Italy.
authors.forename: Gabriella
authors.initials: G
authors.lastname: Cavallo
authors.affiliation: Center for Nano Science and Technology@PoliMi, Istituto Italiano di Tecnologia, 20131 Milano, Italy.
authors.forename: Alessandro
authors.initials: A
authors.lastname: Luzio
authors.affiliation: Department of Applied Physics, HYBER Centre of Excellence, Aalto University, 02150 Espoo, Finland.
authors.forename: Johannes
authors.initials: J
authors.lastname: Haataja
authors.affiliation: Dipartimento Beni Culturali, Università del Salento, 73100 Lecce, Italy.
authors.forename: Gabriele
authors.initials: G
authors.lastname: Giancane
authors.affiliation: Department of Chemistry and Bioengineering, Tampere University of Technology, 33101 Tampere, Finland.
authors.forename: Marco
authors.initials: M
authors.lastname: Saccone
authors.affiliation: Department of Chemistry and Bioengineering, Tampere University of Technology, 33101 Tampere, Finland.
authors.forename: Arri
authors.initials: A
authors.lastname: Priimagi
authors.affiliation: VTT Technical Research Centre of Finland Ltd., 02044 VTT Espoo, Finland; Department of Applied Physics, HYBER Centre of Excellence, Aalto University, 02150 Espoo, Finland; Laboratory of Nanostructured Fluorinated Materials (NFMLab), Department of Chemistry, Materials, and Chemical Engineering "Giulio Natta", Politecnico di Milano, 20131 Milano, Italy; Center for Nano Science and Technology@PoliMi, Istituto Italiano di Tecnologia, 20131 Milano, Italy.
authors.forename: Pierangelo
authors.initials: P
authors.lastname: Metrangolo
authors.affiliation: Department of Applied Physics, HYBER Centre of Excellence, Aalto University, 02150 Espoo, Finland.
authors.forename: Olli
authors.initials: O
authors.lastname: Ikkala
keywords: SDG9: Industry, innovation, and infrastructure; block copolymers; halogen bond; hierarchical self-assembly; nanofabrication; supramolecular complexes