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

doi:10.1016/j.chempr.2017.02.003

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

Aalto University
Polytechnic University of Milan
Istituto Italiano di Tecnologia (IIT)
University of Salento
Tampere University of Technology (TUT)

Research output: Contribution to journal › Article › Scientific › peer-review

61 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 language	English
Pages (from-to)	417-426
Journal	Chem
Volume	2
Issue number	3
DOIs	https://doi.org/10.1016/j.chempr.2017.02.003
Publication status	Published - 9 Mar 2017
MoE publication type	A1 Journal article-refereed

Funding

This work was carried out under the Academy of Finland's Centres of Excellence program (2014–2019) and made use of the Aalto University Nanomicroscopy Center premises. The European Research Council is gratefully acknowledged for funding the Starting Grant FOLDHALO (grant agreement number 307108) to P.M. and the Advanced Grant MIMEFUN (grant agreement number 291364) to O.I. This work was also partially supported by the Academy of Finland under project nos. 260565, 276537, and 284508.

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 9 Industry, Innovation, and Infrastructure

Keywords

halogen bond
block copolymers
hierarchical self-assembly
supramolecular complexes
nanofabrication

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10.1016/j.chempr.2017.02.003Licence: CC BY-NC-ND

Cite this

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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.",

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doi = "10.1016/j.chempr.2017.02.003",

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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

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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.

AB - 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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KW - hierarchical self-assembly

KW - supramolecular complexes

KW - nanofabrication

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

Abstract

Funding

UN SDGs

Keywords

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