Halogen bonding versus hydrogen bonding in driving self-assembly and performance of light-responsive supramolecular polymers

A. Priimagi (Corresponding Author), G. Cavallo, A. Forni, M. Gorynsztejn-Leben, M. Kaivola, Pierangelo Metrangolo (Corresponding Author), Roberto Milani, A. Shishido, T. Pilati, G. Resnati (Corresponding Author), G. Terraneo

Research output: Contribution to journalArticleScientificpeer-review

123 Citations (Scopus)

Abstract

Halogen bonding is arguably the least exploited among the many non‐covalent interactions used in dictating molecular self‐assembly. However, its directionality renders it unique compared to ubiquitous hydrogen bonding. Here, the role of this directionality in controlling the performance of light‐responsive supramolecular polymers is highlighted. In particular, it is shown that light‐induced surface patterning, a unique phenomenon occurring in azobenzene‐containing polymers, is more efficient in halogen‐bonded polymer–azobenzene complexes than in the analogous hydrogen‐bonded complexes. A systematic study is performed on a series of azo dyes containing different halogen or hydrogen bonding donor moieties, complexed to poly(4‐vinylpyridine) backbone. Through single‐atom substitution of the bond‐donor, control of both the strength and the nature of the noncovalent interaction between the azobenzene units and the polymer backbone is achieved. Importantly, such substitution does not significantly alter the electronic properties of the azobenzene units, hence providing us with unique tools in studying the structure–performance relationships in the light‐induced surface deformation process. The results represent the first demonstration of light‐responsive halogen‐bonded polymer systems and also highlight the remarkable potential of halogen bonding in fundamental studies of photoresponsive azobenzene‐containing polymers.
Original languageEnglish
Pages (from-to)2572-2579
Number of pages7
JournalAdvanced Functional Materials
Volume22
Issue number12
DOIs
Publication statusPublished - 2012
MoE publication typeA1 Journal article-refereed

Fingerprint

Halogens
halogens
Self assembly
self assembly
Hydrogen bonds
Polymers
polymers
hydrogen
Azobenzene
Substitution reactions
Azo Compounds
substitutes
Azo dyes
Electronic properties
Demonstrations
dyes
interactions
electronics

Keywords

  • Halogen bonding
  • self-assembly
  • surface relief gratings
  • optically active materials
  • supramolecular polymers

Cite this

Priimagi, A., Cavallo, G., Forni, A., Gorynsztejn-Leben, M., Kaivola, M., Metrangolo, P., ... Terraneo, G. (2012). Halogen bonding versus hydrogen bonding in driving self-assembly and performance of light-responsive supramolecular polymers. Advanced Functional Materials, 22(12), 2572-2579. https://doi.org/10.1002/adfm.201200135
Priimagi, A. ; Cavallo, G. ; Forni, A. ; Gorynsztejn-Leben, M. ; Kaivola, M. ; Metrangolo, Pierangelo ; Milani, Roberto ; Shishido, A. ; Pilati, T. ; Resnati, G. ; Terraneo, G. / Halogen bonding versus hydrogen bonding in driving self-assembly and performance of light-responsive supramolecular polymers. In: Advanced Functional Materials. 2012 ; Vol. 22, No. 12. pp. 2572-2579.
@article{80279522a59949f39b1c093735b561a4,
title = "Halogen bonding versus hydrogen bonding in driving self-assembly and performance of light-responsive supramolecular polymers",
abstract = "Halogen bonding is arguably the least exploited among the many non‐covalent interactions used in dictating molecular self‐assembly. However, its directionality renders it unique compared to ubiquitous hydrogen bonding. Here, the role of this directionality in controlling the performance of light‐responsive supramolecular polymers is highlighted. In particular, it is shown that light‐induced surface patterning, a unique phenomenon occurring in azobenzene‐containing polymers, is more efficient in halogen‐bonded polymer–azobenzene complexes than in the analogous hydrogen‐bonded complexes. A systematic study is performed on a series of azo dyes containing different halogen or hydrogen bonding donor moieties, complexed to poly(4‐vinylpyridine) backbone. Through single‐atom substitution of the bond‐donor, control of both the strength and the nature of the noncovalent interaction between the azobenzene units and the polymer backbone is achieved. Importantly, such substitution does not significantly alter the electronic properties of the azobenzene units, hence providing us with unique tools in studying the structure–performance relationships in the light‐induced surface deformation process. The results represent the first demonstration of light‐responsive halogen‐bonded polymer systems and also highlight the remarkable potential of halogen bonding in fundamental studies of photoresponsive azobenzene‐containing polymers.",
keywords = "Halogen bonding, self-assembly, surface relief gratings, optically active materials, supramolecular polymers",
author = "A. Priimagi and G. Cavallo and A. Forni and M. Gorynsztejn-Leben and M. Kaivola and Pierangelo Metrangolo and Roberto Milani and A. Shishido and T. Pilati and G. Resnati and G. Terraneo",
note = "Project code: 70913",
year = "2012",
doi = "10.1002/adfm.201200135",
language = "English",
volume = "22",
pages = "2572--2579",
journal = "Advanced Functional Materials",
issn = "1616-301X",
publisher = "Wiley",
number = "12",

}

Priimagi, A, Cavallo, G, Forni, A, Gorynsztejn-Leben, M, Kaivola, M, Metrangolo, P, Milani, R, Shishido, A, Pilati, T, Resnati, G & Terraneo, G 2012, 'Halogen bonding versus hydrogen bonding in driving self-assembly and performance of light-responsive supramolecular polymers', Advanced Functional Materials, vol. 22, no. 12, pp. 2572-2579. https://doi.org/10.1002/adfm.201200135

Halogen bonding versus hydrogen bonding in driving self-assembly and performance of light-responsive supramolecular polymers. / Priimagi, A. (Corresponding Author); Cavallo, G.; Forni, A.; Gorynsztejn-Leben, M.; Kaivola, M.; Metrangolo, Pierangelo (Corresponding Author); Milani, Roberto; Shishido, A.; Pilati, T.; Resnati, G. (Corresponding Author); Terraneo, G.

In: Advanced Functional Materials, Vol. 22, No. 12, 2012, p. 2572-2579.

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

T1 - Halogen bonding versus hydrogen bonding in driving self-assembly and performance of light-responsive supramolecular polymers

AU - Priimagi, A.

AU - Cavallo, G.

AU - Forni, A.

AU - Gorynsztejn-Leben, M.

AU - Kaivola, M.

AU - Metrangolo, Pierangelo

AU - Milani, Roberto

AU - Shishido, A.

AU - Pilati, T.

AU - Resnati, G.

AU - Terraneo, G.

N1 - Project code: 70913

PY - 2012

Y1 - 2012

N2 - Halogen bonding is arguably the least exploited among the many non‐covalent interactions used in dictating molecular self‐assembly. However, its directionality renders it unique compared to ubiquitous hydrogen bonding. Here, the role of this directionality in controlling the performance of light‐responsive supramolecular polymers is highlighted. In particular, it is shown that light‐induced surface patterning, a unique phenomenon occurring in azobenzene‐containing polymers, is more efficient in halogen‐bonded polymer–azobenzene complexes than in the analogous hydrogen‐bonded complexes. A systematic study is performed on a series of azo dyes containing different halogen or hydrogen bonding donor moieties, complexed to poly(4‐vinylpyridine) backbone. Through single‐atom substitution of the bond‐donor, control of both the strength and the nature of the noncovalent interaction between the azobenzene units and the polymer backbone is achieved. Importantly, such substitution does not significantly alter the electronic properties of the azobenzene units, hence providing us with unique tools in studying the structure–performance relationships in the light‐induced surface deformation process. The results represent the first demonstration of light‐responsive halogen‐bonded polymer systems and also highlight the remarkable potential of halogen bonding in fundamental studies of photoresponsive azobenzene‐containing polymers.

AB - Halogen bonding is arguably the least exploited among the many non‐covalent interactions used in dictating molecular self‐assembly. However, its directionality renders it unique compared to ubiquitous hydrogen bonding. Here, the role of this directionality in controlling the performance of light‐responsive supramolecular polymers is highlighted. In particular, it is shown that light‐induced surface patterning, a unique phenomenon occurring in azobenzene‐containing polymers, is more efficient in halogen‐bonded polymer–azobenzene complexes than in the analogous hydrogen‐bonded complexes. A systematic study is performed on a series of azo dyes containing different halogen or hydrogen bonding donor moieties, complexed to poly(4‐vinylpyridine) backbone. Through single‐atom substitution of the bond‐donor, control of both the strength and the nature of the noncovalent interaction between the azobenzene units and the polymer backbone is achieved. Importantly, such substitution does not significantly alter the electronic properties of the azobenzene units, hence providing us with unique tools in studying the structure–performance relationships in the light‐induced surface deformation process. The results represent the first demonstration of light‐responsive halogen‐bonded polymer systems and also highlight the remarkable potential of halogen bonding in fundamental studies of photoresponsive azobenzene‐containing polymers.

KW - Halogen bonding

KW - self-assembly

KW - surface relief gratings

KW - optically active materials

KW - supramolecular polymers

U2 - 10.1002/adfm.201200135

DO - 10.1002/adfm.201200135

M3 - Article

VL - 22

SP - 2572

EP - 2579

JO - Advanced Functional Materials

JF - Advanced Functional Materials

SN - 1616-301X

IS - 12

ER -