An Adaptable and Dynamically Porous Organic Salt Traps Unique Tetrahalide Dianions

Martí‐Rujas, Javier; Meazza, Lorenzo; Lim, Gin Keat; Terraneo, Giancarlo; Pilati, Tullio; Harris, Kenneth David Maclean; Metrangolo, Pierangelo; Resnati, Giuseppe

doi:10.1002/anie.201307552

Cited by 77 publications

(48 citation statements)

References 33 publications

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“…Walbaum et al showed that the tetra(diiodine)chloride ([Cl(I 2 ) 4 ] – ) dimer exhibits kinetic stability . Similarly, Martí‐Rujas et al made the tetrahalide anion [I 2 Cl 2 ] 2– , and found it to be a linear complex, Cl – ···I 2 ···Cl – , involving X‐bonds between a central I 2 molecule and two Cl – anions. This X‐bonding Cl – ···I 2 ···Cl – has also been utilized subsequently in a supermolecular assembly .…”

Section: Introductionmentioning

confidence: 99%

Hydrogen‐ and Halogen‐Bonds between Ions of like Charges: Are They Anti‐Electrostatic in Nature?

Wang

Zhang

et al. 2017

J Comput Chem

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Recent theoretical studies suggested that hydrogen bonds between ions of like charges are of a covalent nature due to the dominating n →σ* charge-transfer (CT) interaction. In this work, energy profiles of typical hydrogen (H) and halogen (X) bonding systems formed from ions of like charges are explored using the block-localized wavefunction (BLW) method, which can derive optimal geometries and wave functions with the CT interaction "turned off." The results demonstrate that the kinetic stability, albeit reduced, is maintained for most investigated systems even after the intermolecular CT interaction is quenched. Further energy decomposition analyses based on the BLW method reveal that, despite a net repulsive Coulomb repulsion, a stabilizing component exists due to the polarization effect that plays significant role in the kinetic stability of all systems. Moreover, the fingerprints of the augmented electrostatic interaction due to polarization are apparent in the variation patterns of the electron density. All in all, much like in standard H- and X-bonds, the stability of such bonds between ions of like charges is governed by the competition between the stabilizing electrostatic and charge transfer interactions and the destabilizing deformation energy and Pauli exchange repulsion. While in most cases of "anti-electrostatic" bonds the CT interaction is of a secondary importance, we also find cases where CT is decisive. As such, this work validates the existence of anti-electrostatic H- and X-bonds. © 2017 Wiley Periodicals, Inc.

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Section: Introductionmentioning

confidence: 99%

Hydrogen‐ and Halogen‐Bonds between Ions of like Charges: Are They Anti‐Electrostatic in Nature?

Wang

Zhang

et al. 2017

J Comput Chem

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“…[27][28][29] Halogen bonding refers to the noncovalent interaction involving ah alogen atom as the electrophilic species. [30] Halogen bonding has proven to be av iable tool in crystal engineering, [31][32][33][34] and is also emerging as an oncovalent interaction of choice in designing functional supramolecular materials. [35,36] Thanks to its high directionality, [37] halogen bonding is an effective tool in constructing supramolecular liquid crystals from non-mesogenic starting compounds, [38][39][40] yet no halogen-bonded ILCs have been demonstrated up to date.T he strength of the halogen bond can be tuned by choosing the halogen involved [41] and fluorination of the chemical groups at the vicinity of the bond-donor atoms increases the strength of resulting interactions.…”

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confidence: 99%

Superfluorinated Ionic Liquid Crystals Based on Supramolecular, Halogen‐Bonded Anions

et al. 2016

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Unconventional ionic liquid crystals in which the liquid crystallinity is enabled by halogen‐bonded supramolecular anions [CnF2 n+1‐I⋅⋅⋅I⋅⋅⋅I‐CnF2 n+1]− are reported. The material system is unique in many ways, demonstrating for the first time 1) ionic, halogen‐bonded liquid crystals, and 2) imidazolium‐based ionic liquid crystals in which the occurrence of liquid crystallinity is not driven by the alkyl chains of the cation.

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“…The large amount of structures produced allows many interesting contributions based on the analysis of structural databases [9][10][11][12][13]. And, indeed, most of the applications of XB are in the materials science: porous systems [14][15][16], liquid crystals [17], light-emitting materials [18,19] and magnetic materials [20,21] are only some applicative fields fruitfully explored with XB-based materials.…”

Section: Introductionmentioning

confidence: 99%

Characterization of Halogen Bonded Adducts in Solution by Advanced NMR Techniques

Ciancaleoni

2017

Magnetochemistry

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Abstract:In the last 20 years, a huge volume of experimental work into halogen bonding (XB) has been produced. Most of the systems have been characterized by solid state X-ray crystallography, whereas in solution the only routine technique is titration (by using 1 H and 19 F nuclear magnetic resonance (NMR), infrared (IR), ultraviolet-visible (UV-Vis) or Raman spectroscopies, depending on the nature of the system), with the aim of characterizing the strength of the XB interaction. Unfortunately, titration techniques have many intrinsic limitations and they should be coupled with other, more sophisticated techniques to provide an accurate and detailed description of the geometry and stoichiometry of the XB adduct in solution. This review will show how crucial information about XB adducts can be obtained by advanced NMR techniques, nuclear Overhauser effect-based spectroscopies (NOESY, ROESY, HOESY . . . ) and diffusion NMR techniques (PGSE or DOSY).

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An Adaptable and Dynamically Porous Organic Salt Traps Unique Tetrahalide Dianions

Cited by 77 publications

References 33 publications

Hydrogen‐ and Halogen‐Bonds between Ions of like Charges: Are They Anti‐Electrostatic in Nature?

Hydrogen‐ and Halogen‐Bonds between Ions of like Charges: Are They Anti‐Electrostatic in Nature?

Superfluorinated Ionic Liquid Crystals Based on Supramolecular, Halogen‐Bonded Anions

Characterization of Halogen Bonded Adducts in Solution by Advanced NMR Techniques

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