The halogen bond in the design of functional supramolecular materials: Recent advances

A. Priimagi (Corresponding Author), G. Cavallo, Pierangelo Metrangolo (Corresponding Author), G. Resnati (Corresponding Author)

Research output: Contribution to journalArticleScientificpeer-review

437 Citations (Scopus)

Abstract

Halogen bonding is an emerging noncovalent interaction for constructing supramolecular assemblies. Though similar to the more familiar hydrogen bonding, four primary differences between these two interactions make halogen bonding a unique tool for molecular recognition and the design of functional materials. First, halogen bonds tend to be much more directional than (single) hydrogen bonds. Second, the interaction strength scales with the polarizability of the bond-donor atom, a feature that researchers can tune through single-atom mutation. In addition, halogen bonds are hydrophobic whereas hydrogen bonds are hydrophilic. Lastly, the size of the bond-donor atom (halogen) is significantly larger than hydrogen. As a result, halogen bonding provides supramolecular chemists with design tools that cannot be easily met with other types of noncovalent interactions and opens up unprecedented possibilities in the design of smart functional materials.This Account highlights the recent advances in the design of halogen-bond-based functional materials. Each of the unique features of halogen bonding, directionality, tunable interaction strength, hydrophobicity, and large donor atom size, makes a difference. Taking advantage of the hydrophobicity, researchers have designed small-size ion transporters. The large halogen atom size provided a platform for constructing all-organic light-emitting crystals that efficiently generate triplet electrons and have a high phosphorescence quantum yield. The tunable interaction strengths provide tools for understanding light-induced macroscopic motions in photoresponsive azobenzene-containing polymers, and the directionality renders halogen bonding useful in the design on functional supramolecular liquid crystals and gel-phase materials. Although halogen bond based functional materials design is still in its infancy, we foresee a bright future for this field. We expect that materials designed based on halogen bonding could lead to applications in biomimetics, optics/photonics, functional surfaces, and photoswitchable supramolecules.
Original languageEnglish
Pages (from-to)2686-2695
Number of pages9
JournalAccounts of Chemical Research
Volume46
Issue number11
DOIs
Publication statusPublished - 2013
MoE publication typeA1 Journal article-refereed

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Halogens
Functional materials
Atoms
Hydrogen bonds
Hydrophobicity
Liquid Crystals
Molecular recognition
Phosphorescence
Intelligent materials
Biomimetics
Quantum yield
Photonics
Hydrogen
Optics
Polymers
Gels

Cite this

Priimagi, A. ; Cavallo, G. ; Metrangolo, Pierangelo ; Resnati, G. / The halogen bond in the design of functional supramolecular materials : Recent advances. In: Accounts of Chemical Research. 2013 ; Vol. 46, No. 11. pp. 2686-2695.
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The halogen bond in the design of functional supramolecular materials : Recent advances. / Priimagi, A. (Corresponding Author); Cavallo, G.; Metrangolo, Pierangelo (Corresponding Author); Resnati, G. (Corresponding Author).

In: Accounts of Chemical Research, Vol. 46, No. 11, 2013, p. 2686-2695.

Research output: Contribution to journalArticleScientificpeer-review

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