Carborane-based heteromolecular extended networks driven by directional C–Te⋯N chalcogen bonding interactions

Beau, Maxime; Jeannin, Olivier; Fourmigué, Marc; Aubert, Emmanuel; Espinosa, Enrique; Lee, Sunhee; Han, Won-Sik; Jeon, Ie-Rang

doi:10.1039/d3cc04338j

Cited by 2 publications

(1 citation statement)

References 49 publications

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“…The excellent σ-hole donor ability of bis(telluromethyl)carborane D18 demonstrated in its cocrystals with halides (Part 3.2), together with its ditopic character led us to engage it also into cocrystallizations with the neutral ditopic ChB acceptors A5 and A6 . The structure of the cocrystals D18·A5 and D18·A6 (Figure c) revealed indeed the formation of the desired ChB-bonded chains driven by very short Te···N contacts, with RR values of 0.79 and 0.78 in D18·A5 and D18·A6 respectively …”

Section: Chb Cocrystals With Neutral Lewis Basesmentioning

confidence: 89%

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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Section: Chb Cocrystals With Neutral Lewis Basesmentioning

confidence: 89%

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

Dhaka,

Jeon,

Fourmigué

2024

Acc. Chem. Res.

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Activation of Alkenes via Chalcogen Bond: Chalcogen⋅⋅⋅π Bond Catalyzed the Diels‐Alder Reaction of 2‐Vinylindoles

Zhao,

Wang,

Zeng

2024

Eur J Org Chem

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Chalcogen bond catalysis is a promising catalytic strategy, characterized by its environmental friendliness, relatively inexpensive cost, and similar reactivity to transition metal catalysis. Experimental results suggest that the S•••π and Se•••π bonds can efficiently drive the vinyl‐indole‐based Diels‐Alder reaction (Angew. Chem. Int. Ed. 2021, 60, 9395‐9400). In this work, chalcogen bond catalysis in the Diels‐Alder reaction between 2‐vinylindoles has been investigated based on density functional theory. For this reaction, the Te•••π bond catalysis is as an alternative catalytic strategy. The Diels‐Alder reaction catalyzed by chalcogen bond is stepwise and involves two steps: the carbon–carbon bond formation process and the cyclization process. The cyclization process is the rate‐determining step. From the perspective of energy decomposition analysis, the electrostatic interaction is the main factor to cause Se•••π bond catalysis, the polarization interaction is the main factor to cause Te•••π bond catalysis. Additionally, this catalytic reaction involves the endo pathway and exo pathway. The Gibbs free energy barrier values of the endo pathway are lower than those of the exo pathway, which facilitates the formation of the endo product. This study will provide a valuable perspective on the application of chalcogen bond in the activation of alkenes.

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Carborane-based heteromolecular extended networks driven by directional C–Te⋯N chalcogen bonding interactions

Abstract: We demonstrate that o-closo-(TeMe)2carborane directs, in the presence of linear ditopic neutral Lewis bases, the formation of co-crystals with 1D extended supramolecular networks. Specifically, the network formation is systematically stabilized...

Cited by 2 publications

References 49 publications

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

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

Activation of Alkenes via Chalcogen Bond: Chalcogen⋅⋅⋅π Bond Catalyzed the Diels‐Alder Reaction of 2‐Vinylindoles

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