Coordination chemistry of anions through halogen-bonding interactions

Fourmigué, Marc

doi:10.1107/s2052520617004413

Cited by 8 publications

(5 citation statements)

References 17 publications

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“…Despite the growing interest in iodoacetylenes, [42][43][44][45][46][47] there have been limited SSNMR studies of halogen-bonded compounds built with this functionalg roup. [48][49][50][51] Furthermore, there have been no systematic investigations to date comparing the effects of various halogen bond acceptors in isostructural compounds on the SSNMR observables, and no information is available directly comparing the halogen bond to the hydrogen bond in terms of NMR responses.…”

Section: Introductionmentioning

confidence: 99%

Comparing the Halogen Bond to the Hydrogen Bond by Solid‐State NMR Spectroscopy: Anion Coordinated Dimers from 2‐ and 3‐Iodoethynylpyridine Salts

Szell

Cavallo

Terraneo

et al. 2018

Chemistry A European J

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Halogen bonding is an increasingly important tool in crystal engineering, and measuring its influence on the local chemical and electronic environment is necessary to fully understand this interaction. Here, we present a systematic crystallographic and solid-state NMR study of self-complementary halogen-bonded frameworks built from the halide salts (HCl, HBr, HI, HI ) of 2-iodoethynylpyridine and 3-iodoethynylpyridine. A series of single crystal X-ray structures reveals the formation of discrete charged dimers in the solid state, directed by simultaneous X ⋅⋅⋅H-N hydrogen bonds and C-I⋅⋅⋅X halogen bonds (X=Cl, Br, I). Each compound was studied using multinuclear solid-state magnetic resonance spectroscopy, observing H to investigate the hydrogen bonds and C, Cl, and Br to investigate the halogen bonds. A natural localized molecular orbital analysis was employed to help interpret the experimental results. H SSNMR spectroscopy reveals a decrease in the chemical shift of the proton participating in the hydrogen bond as the halogen increases in size, whereas the C SSNMR reveals an increased C chemical shift of the C-I carbon for C-I⋅⋅⋅X relative to C-I⋅⋅⋅N halogen bonds. Additionally, Cl and Br SSNMR, along with computational results, have allowed us to compare the C-I⋅⋅⋅X halogen bond involving each halide in terms of NMR observables. Due to the isostructural nature of these compounds, they are ideal cases for experimentally assessing the impact of different halogen bond acceptors on the solid-state NMR response.

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Section: Introductionmentioning

confidence: 99%

Comparing the Halogen Bond to the Hydrogen Bond by Solid‐State NMR Spectroscopy: Anion Coordinated Dimers from 2‐ and 3‐Iodoethynylpyridine Salts

Szell

Cavallo

Terraneo

et al. 2018

Chemistry A European J

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“…Anion recognition through XB interactions have been intensively investigated owing to the strong interaction reinforced by charge assistance . With halides in particular, a charge-inverted coordination chemistry has even been defined, with coordination numbers up to eight . In the solid state, using di-, tri- or tetratopic XB donors, such interactions lead to the formation of 1D to 3D halogen-bonded anion organic networks. , A similar coordination chemistry of halides through ChB is still in its infancy, with some recent investigations in solution by spectroscopic methods or toward anion transport across lipid bilayers, together with theoretical studies .…”

Section: Chb Anionic Networkmentioning

confidence: 99%

Selective Activation of Chalcogen Bonding: An Efficient Structuring Tool toward Crystal Engineering Strategies

Dhaka,

Jeon,

Fourmigué

2024

Acc. Chem. Res.

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Metrics & MoreArticle Recommendations * sı Supporting Information CONSPECTUS: Among the noncovalent interactions available in the toolbox of crystal engineering, chalcogen bonding (ChB) has recently entered the growing family of σ-hole interactions, following the strong developments based on the halogen bonding (XB) interaction over the last 30 years. The monovalent character of halogens provides halogen bonding directionality and strength. Combined with the extensive organic chemistry of Br and I derivatives, it has led to many applications of XB, in solution (organocatalysis, anion recognition and transport), in the solid state (cocrystals, conducting materials, fluorescent materials, topochemical reactions, ...), in soft matter (liquid crystals, gels,•••), and in biochemistry. The recognition of the presence of two σ-holes on divalent chalcogens and the ability to activate them, as in XB, with electron-withdrawing groups (EWG) has fueled more recent interest in chalcogen bonding. However, despite being identified for many years, ChB still struggles to make a mark due to (i) the underdeveloped synthetic chemistry of heavier Se and Te; (ii) the limited stability of organic chalcogenides, especially tellurides; and (iii) the poor predictability of ChB associated with the presence of two σ-holes. It therefore invites a great deal of attention of molecular chemists to design and develop selected ChB donors, for the scrutiny of fundamentals of ChB and their successful use in different applications. This Account aims to summarize our own contributions in this direction that extend from fundamental studies focused on addressing the lack of directionality/predictability in ChB to a systematic demonstration of its potential, specifically in crystal engineering, and particularly toward anionic networks on the one hand, topochemical reactions on the other hand.In this Account, we share our recent results aimed at recovering with ChB the same degree of strength and predictability found with XB, by focusing on divalent Se and Te systems with two different substituents, one of them with an EWG, to strongly unbalance both σ-holes. For that purpose, we explored this dissymmetrization concept within three chemical families, selenocyanates R−SeCN, alkynyl derivatives R−C�C−(Se/Te)Me, and o-carborane derivatives. Such compounds were systematically engaged in cocrystals with either halides or neutral bipyridines as ChB acceptors, revealing their strong potential to chelate halides as well as their ability to organize reactive molecules such as alkenes and butadiynes toward [2+2] cycloadditions and polydiacetylene formation, respectively. This selective activation concept is not limited to ChB but can be effectively used on all other σ-hole interactions (pnictogen bond, tetrel bond, etc.) where one needs to control the directionality of the interaction.■ KEY REFERENCES• Huynh, H.-T.; Jeannin, O.; Fourmigué, M. Organic selenocyanates as strong and directional chalcogen bond donors for crystal engineering. Chem. Commun. 2017, 53, 84...

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“…The strength of the halogen bond is highly correlated with the degree of iodobenzene fluorination [ 17 ]. Therefore, it is not surprising that 1,4-diiodoperfluorobenzene and its analogs are widely used in the design of halogen-bonded supramolecular systems [ 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 ], although arylacetylene iodides also play an important role [ 16 , 29 , 30 , 31 , 32 , 33 , 34 , 35 ]. In the absence of other electron density donors, the iodine atoms in these compounds are also able to play this role, which leads to the formation of I⋯I dihalogen bonds [ 36 , 37 , 38 , 39 ], and the number of such bonds, as a rule, increases with the number of iodine atoms in the molecule [ 40 ].…”

Section: Introductionmentioning

confidence: 99%

How the Position of Substitution Affects Intermolecular Bonding in Halogen Derivatives of Carboranes: Crystal Structures of 1,2,3- and 8,9,12-Triiodo- and 8,9,12-Tribromo ortho-Carboranes

2023

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The crystal structures of two isomeric triiodo derivatives of ortho-carborane containing substituents in the three most electron-withdrawing positions of the carborane cage, 1,2,3-I3-1,2-C2B10H9, and the three most electron-donating positions, 8,9,12-I3-1,2-C2B10H9, as well as the crystal structure of 8,9,12-Br3-1,2-C2B10H9, were determined by single-crystal X-ray diffraction. In the structure of 1,2,3-I3-1,2-C2B10H9, an iodine atom attached to the boron atom (position 3) donates its lone pairs simultaneously to the σ-holes of both iodine atoms attached to the carbon atoms (positions 1 and 2) with the I⋯I distance of 3.554(2) Å and the C-I⋯I and B-I⋯I angles of 169.2(2)° and 92.2(2)°, respectively. The structure is additionally stabilized by a few B-H⋯I-shortened contacts. In the structure of 8,9,12-I3-1,2-C2B10H9, the I⋯I contacts of type II are very weak (the I⋯I distance is 4.268(4) Å, the B8-I8⋯I12 and B12-I12⋯I8 angles are 130.2(3)° and 92.2(3)°) and can only be regarded as dihalogen bonds formally. In comparison with the latter, the structure of 8,9,12-Br3-1,2-C2B10H9 demonstrates both similarities and differences. No Br⋯Br contacts of type II are observed, while there are two Br⋯Br halogen bonds of type I.

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Coordination chemistry of anions through halogen-bonding interactions

Cited by 8 publications

References 17 publications

Comparing the Halogen Bond to the Hydrogen Bond by Solid‐State NMR Spectroscopy: Anion Coordinated Dimers from 2‐ and 3‐Iodoethynylpyridine Salts

Comparing the Halogen Bond to the Hydrogen Bond by Solid‐State NMR Spectroscopy: Anion Coordinated Dimers from 2‐ and 3‐Iodoethynylpyridine Salts

Selective Activation of Chalcogen Bonding: An Efficient Structuring Tool toward Crystal Engineering Strategies

How the Position of Substitution Affects Intermolecular Bonding in Halogen Derivatives of Carboranes: Crystal Structures of 1,2,3- and 8,9,12-Triiodo- and 8,9,12-Tribromo ortho-Carboranes

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