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 (Corresponding Author), Olli Ikkala

Research output: Contribution to journalArticleScientificpeer-review

23 Citations (Scopus)

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.
Original languageEnglish
Pages (from-to)417-426
Number of pages10
JournalChem
Volume2
Issue number3
DOIs
Publication statusPublished - 9 Mar 2017
MoE publication typeA1 Journal article-refereed

Fingerprint

Halogens
halogen
Self assembly
Block copolymers
Microphase separation
Molecules
Nanostructures
Micelles
annealing
Nanotechnology
Casting
Molecular Weight
Molecular weight
Annealing

Keywords

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

Cite this

Milani, R., Houbenov, N., Fernandez-Palacio, F., Cavallo, G., Luzio, A., Haataja, J., ... Ikkala, O. (2017). Hierarchical Self-Assembly of Halogen-Bonded Block Copolymer Complexes into Upright Cylindrical Domains. Chem, 2(3), 417-426. https://doi.org/10.1016/j.chempr.2017.02.003
Milani, Roberto ; Houbenov, Nikolay ; Fernandez-Palacio, Francisco ; Cavallo, Gabriella ; Luzio, Alessandro ; Haataja, Johannes ; Giancane, Gabriele ; Saccone, Marco ; Priimagi, Arri ; Metrangolo, Pierangelo ; Ikkala, Olli. / Hierarchical Self-Assembly of Halogen-Bonded Block Copolymer Complexes into Upright Cylindrical Domains. In: Chem. 2017 ; Vol. 2, No. 3. pp. 417-426.
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Milani, R, Houbenov, N, Fernandez-Palacio, F, Cavallo, G, Luzio, A, Haataja, J, Giancane, G, Saccone, M, Priimagi, A, Metrangolo, P & Ikkala, O 2017, 'Hierarchical Self-Assembly of Halogen-Bonded Block Copolymer Complexes into Upright Cylindrical Domains', Chem, vol. 2, no. 3, pp. 417-426. https://doi.org/10.1016/j.chempr.2017.02.003

Hierarchical Self-Assembly of Halogen-Bonded Block Copolymer Complexes into Upright Cylindrical Domains. / Milani, Roberto; Houbenov, Nikolay; Fernandez-Palacio, Francisco; Cavallo, Gabriella; Luzio, Alessandro; Haataja, Johannes; Giancane, Gabriele; Saccone, Marco; Priimagi, Arri; Metrangolo, Pierangelo (Corresponding Author); Ikkala, Olli.

In: Chem, Vol. 2, No. 3, 09.03.2017, p. 417-426.

Research output: Contribution to journalArticleScientificpeer-review

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AU - Milani, Roberto

AU - Houbenov, Nikolay

AU - Fernandez-Palacio, Francisco

AU - Cavallo, Gabriella

AU - Luzio, Alessandro

AU - Haataja, Johannes

AU - Giancane, Gabriele

AU - Saccone, Marco

AU - Priimagi, Arri

AU - Metrangolo, Pierangelo

AU - Ikkala, Olli

N1 - Project code: 100495

PY - 2017/3/9

Y1 - 2017/3/9

N2 - 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.

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DO - 10.1016/j.chempr.2017.02.003

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JO - Chem

JF - Chem

SN - 2451-9294

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