TY - JOUR
T1 - Hierarchical Self-Assembly of Halogen-Bonded Block Copolymer Complexes into Upright Cylindrical Domains
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 - Funding Information:
Project code: 100495
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. Matti Lehtimäki is acknowledged for his XRD support.
Publisher Copyright:
© 2017 The Authors
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.
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.
KW - halogen bond
KW - block copolymers
KW - hierarchical self-assembly
KW - supramolecular complexes
KW - nanofabrication
UR - http://www.scopus.com/inward/record.url?scp=85014778403&partnerID=8YFLogxK
U2 - 10.1016/j.chempr.2017.02.003
DO - 10.1016/j.chempr.2017.02.003
M3 - Article
VL - 2
SP - 417
EP - 426
JO - Chem
JF - Chem
SN - 2451-9294
IS - 3
ER -