Transmembrane anion transport mediated by halogen-bond donors

Jentzsch, Andreas Vargas; Emery, Daniel; Mareda, Jiri; Nayak, Susanta K.; Metrangolo, Pierangelo; Resnati, Giuseppe; Sakai, Naomi; Matile, Stefan

doi:10.1038/ncomms1902

Cited by 240 publications

(155 citation statements)

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“…Although the utilization of halogen bonding (XB) in solid-state crystal engineering has been extensively explored [3][4][5][6][7] , its application in solution-phase molecular recognition and self-assembly remains underdeveloped, despite the obvious analogy with the ubiquitous hydrogen bond 8 . It is only very recently that seminal applications of XB to the fields of molecular recognition and assembly 9,10 , anion binding [11][12][13][14][15][16] and membrane transport 17 , catalysis 18 , structural biology 19 and medicinal chemistry 20 have resulted in an explosion of interest in this non-covalent intermolecular interaction.…”

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confidence: 99%

Halogen bonding in water results in enhanced anion recognition in acyclic and rotaxane hosts

et al. 2014

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Halogen bonding (XB), the attractive interaction between an electron-deficient halogen atom and a Lewis base, has undergone a dramatic development as an intermolecular force analogous to hydrogen bonding (HB). However, its utilization in the solution phase remains underdeveloped. Furthermore, the design of receptors capable of strong and selective recognition of anions in water remains a significant challenge. Here we demonstrate the superiority of halogen bonding over hydrogen bonding for strong anion binding in water, to the extent that halide recognition by a simple acyclic mono-charged receptor is achievable. Quantification of iodide binding by rotaxane hosts reveals the strong binding by the XB-rotaxane is driven exclusively by favourable enthalpic contributions arising from the halogen-bonding interactions, whereas weaker association with the HB-rotaxanes is entropically driven. These observations demonstrate the unique nature of halogen bonding in water as a strong alternative interaction to the ubiquitous hydrogen bonding in molecular recognition and assembly.

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confidence: 99%

Halogen bonding in water results in enhanced anion recognition in acyclic and rotaxane hosts

et al. 2014

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“…17 The 2013 IUPAC XB definition states: "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". 18 The counterintuitive electrophilic behavior of the elements of the XVII group arises from the anisotropic molecular electrostatic potential distribution around halogens atoms, which shows the emergence of a region of positive electrostatic potential, called -hole, along the extension of the covalent bond the halogen atom is involved in.…”

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confidence: 99%

Natural Abundance ¹⁵N and ¹³C Solid‐State NMR Chemical Shifts: High Sensitivity Probes of the Halogen Bond Geometry

Vioglio

Catalano

Vasylyeva

et al. 2016

Chemistry A European J

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Solid-State Nuclear Magnetic Resonance (SSNMR) is a versatile characterization technique that can provide a plethora of information complementary to Single Crystal X-Ray Diffraction (SCXRD) analysis. However, the latter is still pivotal in assessing the halogen bond (XB) occurrence and having a rough estimation of its strength through the normalized distance parameter (RXB), obtained from experimental crystallographic data. Herein, we present an experimental and computational investigation of the relationship between the strength of an XB and the SSNMR chemical shifts of the nonquadrupolar nuclei either directly involved in the interaction ( 15 N) or covalently bonded to the halogen atom ( 13 C). We have prepared two series of X-bonded co-crystals based upon two different dipyridyl modules, and several halobenzenes and diiodoalkanes, as XB-donors. SCXRD structures of three novel co-crystals between 1,2-bis(4-pyridyl)ethane, and 1,4-diiodobenzene, 1,6-diiodododecafluorohexane, and 1,8-diiodohexadecafluorooctane are reported. For the first time, the change in the 15 N SSNMR chemical shifts upon XB formation is shown to experimentally correlate with the strength of the XB. The same overall trend is confirmed by density functional theory (DFT) calculations of the chemical shifts.13 C NQS experiments show a positive, linear correlation between the chemical shifts and the C-I elongation, which is an indirect probe of the strength of the XB. These correlations can be of general utility to estimate the strength of the XB occurring in diverse adducts by using affordable SSNMR analysis.In recent years, halogen bonding (XB) has been attracting increasing attention thanks to its applications in different fields, e.g., crystal engineering, materials chemistry, and biochemistry.1-3 The success of this specific noncovalent interaction derives from its unique physico-chemical properties, namely strength, selectivity, tunability, and directionality.4,5 XB spans an energy range similar to that of the more commonly used hydrogen bonding, i.e., 5-200 kJ/mol.6 By changing the XB-donor atom involved in the interaction or its covalently-bound substituents it is possible to fine-tune the final strength of the XB, an extremely useful feature for the design of new supramolecular species. 7 In addition, XB is strongly directional, 8,9 thus enabling the predictable alignment of molecular building blocks into crystalline architectures and functional materials, such as photoresponsive polymers, pharmaceutical co-crystals, porous materials, among others.10-14 XB plays also a key role in anion recognition and coordination both in solid state and in solution, 15,16 ability of relevant interest especially for biological systems. 17 The 2013 IUPAC XB definition states: "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". 18 The counterintuitive electrophilic b...

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“…Anion binding by iodoperfluoroalkanes and -arenes underlies the ability of these compounds to facilitate the transport of anions across lipid bilayers, apparently by a cooperative mechanism involving complexes of higher than 1:1 stoichiometry [35]. Compounds having multiple C-I bonds -as components of ditopic ion transporters [36] or rigid-rod scaffolds [37] -also show interesting activities in this regard.…”

Section: Monodentate Haloorganic Donorsmentioning

confidence: 99%

Anion Recognition in Solution via Halogen Bonding

Taylor

2014

Topics in Current Chemistry

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An overview of the interactions between anions and electron-deficient, covalently bound halogens is presented. It might be anticipated that species such as halides and oxoanions would be good acceptors of halogen bonds because of their relatively high charge densities and nucleophilicities. The stabilities of the trihalide anions X3 (-) provide a clear indication that this is indeed the case. The thermodynamics of formation of the trihalides, and of analogous complexes between anions and monodentate haloorganics in organic solvent, are discussed in detail. Although the incorporation of multiple interacting groups to achieve high guest affinity has been a key principle of supramolecular chemistry for decades, it is only recently that multidentate halogen bond donors capable of anion recognition have been reported. This contribution highlights the range of architectures that have been employed as the basis for multidentate halogen bond donor design. Examples of selective and high-affinity anion recognition through halogen bonding, including implementations in polar, protic media, are discussed.

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Transmembrane anion transport mediated by halogen-bond donors

Cited by 240 publications

References 41 publications

Halogen bonding in water results in enhanced anion recognition in acyclic and rotaxane hosts

Halogen bonding in water results in enhanced anion recognition in acyclic and rotaxane hosts

Natural Abundance ¹⁵N and ¹³C Solid‐State NMR Chemical Shifts: High Sensitivity Probes of the Halogen Bond Geometry

Anion Recognition in Solution via Halogen Bonding

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Transmembrane anion transport mediated by halogen-bond donors

Cited by 240 publications

References 41 publications

Halogen bonding in water results in enhanced anion recognition in acyclic and rotaxane hosts

Halogen bonding in water results in enhanced anion recognition in acyclic and rotaxane hosts

Natural Abundance 15N and 13C Solid‐State NMR Chemical Shifts: High Sensitivity Probes of the Halogen Bond Geometry

Anion Recognition in Solution via Halogen Bonding

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Natural Abundance ¹⁵N and ¹³C Solid‐State NMR Chemical Shifts: High Sensitivity Probes of the Halogen Bond Geometry