Halogen bonding in polymer science: from crystal engineering to functional supramolecular polymers and materials

Berger, Gilles; Soubhye, Jalal; Meyer, Franck

doi:10.1039/c5py00354g

Cited by 229 publications

(216 citation statements)

References 139 publications

(129 reference statements)

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“…According to the IUPAC recommendations in 2013 [30], a halogen bond is defined as follows; "A halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity". This attractive interaction between a halogen atom and an electronegative atom can facilitate a vast variety of applications in different fields including material science, synthetic chemistry, polymer science, and in bimolecular systems [28,29,31,32]. By combining halogen-bonded systems with metals [33,34], metallosupramolecular assemblies have been discovered with several important properties including redox, magnetic, non-linear optical, gas adsorption, and catalytic properties [35,36].…”

Section: Introductionmentioning

confidence: 99%

The Role of Halogen Bonding in Controlling Assembly and Organization of Cu(II)-Acac Based Coordination Complexes

et al. 2017

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Abstract:In order to explore the use of non-covalent interactions in the deliberate assembly of metal-supramolecular architectures, a series of β-diketone based ligands capable of simultaneously acting as halogen-bond donors and chelating ligands were synthesized. The three ligands, L1, L2, and L3, carry ethynyl-activated chlorine, bromine, and iodine atoms, respectively and copper(II) complexes of all three ligands were crystallized from different solvents, acetonitrile, ethyl acetate, and nitromethane in order to study specific ligand-solvent interaction. The free ligands L2 and L3, with more polarizable halogen atoms, display C-X· · · O halogen bonds in the solid state, whereas the chloro-analogue (L1) does not engage in halogen bonding. Both acetonitrile and ethyl acetate act as halogen-bond acceptors in Cu(II)-complexes of L2 and L3 whereas nitromethane is present as a 'space-filling' guest without participating in any significant intermolecular interactions in Cu(II)-complexes of L2. L3, which is decorated with an iodoethynyl moiety and consistently engages in halogen-bonds with suitable acceptors. This systematic structural analysis allows us to rank the relative importance of a variety of electron-pair donors in these metal complexes.

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Section: Introductionmentioning

confidence: 99%

The Role of Halogen Bonding in Controlling Assembly and Organization of Cu(II)-Acac Based Coordination Complexes

et al. 2017

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“…25 The benefits of halogen bonding, such as the high directionality and tunability, 26−28 have recently been recognized in the design of functional materials. 29,30 In particular, halogen-bonded, azobenzene-containing co-crystals 31−33 and (amorphous) supramolecular side-chain polymers 34,35 have shown extremely interesting photoresponsive properties, even superior to their hydrogen-bonded counterparts. Since the first demonstration in 2004, 36 several halogen-bonded LCs have been reported.…”

Section: Introductionmentioning

confidence: 99%

Efficient Light-Induced Phase Transitions in Halogen-Bonded Liquid Crystals

et al. 2016

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Here, we present a new family of light-responsive, fluorinated supramolecular liquid crystals (LCs) showing efficient and reversible light-induced LC-to-isotropic phase transitions. Our materials design is based on fluorinated azobenzenes, where the fluorination serves to strengthen the noncovalent interaction with bond-accepting stilbazole molecules, and increase the lifetime of the cis-form of the azobenzene units. The halogen-bonded LCs were characterized by means of X-ray diffraction, hot-stage polarized optical microscopy, and differential scanning calorimetry. Simultaneous analysis of light-induced changes in birefringence, absorption, and optical scattering allowed us to estimate that <4% of the mesogenic units in the cis-form suffices to trigger the full LC-to-isotropic phase transition. We also report a light-induced and reversible crystal-to-isotropic phase transition, which has not been previously observed in supramolecular complexes. In addition to fundamental understanding of light-responsive supramolecular complexes, we foresee this study to be important in the development of bistable photonic devices and supramolecular actuators.

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“…Halogen bond (XB) interactions are prevalent in many areas of chemistry, [1][2][3][4][5][6][7] demonstrating important applications in catalysis, [8][9][10][11] crystal engineering [12][13][14] and rational drug design. Halogen bond (XB) interactions are prevalent in many areas of chemistry, [1][2][3][4][5][6][7] demonstrating important applications in catalysis, [8][9][10][11] crystal engineering [12][13][14] and rational drug design.…”

Section: Introductionmentioning

confidence: 99%

On the Interplay between Charge‐Shift Bonding and Halogen Bonding

et al. 2020

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The nature of halogen-bond interactions has been analysed from the perspective of the astatine element, which is potentially the strongest halogen-bond donor. Relativistic quantum calculations on complexes formed between halide anions and a series of Y 3 CÀ X (Y=F to X, X=I, At) halogen-bond donors disclosed unexpected trends, e. g., At 3 CÀ At revealing a weaker donating ability than I 3 CÀ I despite a stronger polarizability. All the observed peculiarities have their origin in a specific component of CÀ Y bonds: the charge-shift bonding.Descriptors of the Quantum Chemical Topology show that the halogen-bond strength can be quantitatively anticipated from the magnitude of charge-shift bonding operating in Y 3 CÀ X. The charge-shift mechanism weakens the ability of the halogen atom X to engage in halogen bonds. This outcome provides rationales for outlier halogen-bond complexes, which are at variance with the consensus that the halogen-bond strength scales with the polarizability of the halogen atom.

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Halogen bonding in polymer science: from crystal engineering to functional supramolecular polymers and materials

Abstract: The applications of halogen bonding in surface functionalization, soft, luminescent and magnetic materials, interpenetrated networks, synthetic methods, and separation and inclusion techniques are reviewed.

Cited by 229 publications

References 139 publications

The Role of Halogen Bonding in Controlling Assembly and Organization of Cu(II)-Acac Based Coordination Complexes

The Role of Halogen Bonding in Controlling Assembly and Organization of Cu(II)-Acac Based Coordination Complexes

Efficient Light-Induced Phase Transitions in Halogen-Bonded Liquid Crystals

On the Interplay between Charge‐Shift Bonding and Halogen Bonding

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