Chalcogen bonding and variable charge transfer degree in two polymorphs of 1 : 1 conducting salts with segregated stacks

Beau, Maxime; Jeannin, Olivier; Fourmigué, Marc; Senzier, Pascale Auban; Pasquier, Claude; Alemany, Pere; Canadell, Enric; Jeon, Ie‐Rang

doi:10.1039/d3ce00260h

Cited by 1 publication

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“…Figure 3). 25,26 Finally, it should be stressed here that this dissymmetrization approach offers the advantage of being systematic and not strictly limited to ChB. It will indeed find applications with all other interactions where several σ-holes compete for a specific acceptor, as illustrated recently in pnictogen bonding, 65 or tetrel bonding.…”

Section: Summary and Perspectivesmentioning

confidence: 91%

“…These TTF derivatives have been also recently engaged in charge transfer salts with electron acceptors such as TCNQ or TCNQF 2 (TCNQ: tetracyanoquinodimethane), providing mixed-valence salts with metallic conductivity, stabilized by Se•••N≡C TCNQ ChB interactions. 26 We wanted to extend this dissymmetrization concept to neutral ChB donors and developed this approach along three main families respectively, selenocyanates R−SeCN, alkynyl derivatives R−C�C−(Se/Te)Me, and o-carborane derivatives B 10 H 10 [C−(Se/Te)Me] 2 , as gathered in Scheme 2.…”

Section: Directionality Control Through Chalcogen Dissymmetrizationmentioning

confidence: 99%

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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: Summary and Perspectivesmentioning

confidence: 91%

Section: Directionality Control Through Chalcogen Dissymmetrizationmentioning

confidence: 99%

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

Dhaka,

Jeon,

Fourmigué

2024

Acc. Chem. Res.

Self Cite

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Chalcogen bonding and variable charge transfer degree in two polymorphs of 1 : 1 conducting salts with segregated stacks

Abstract: Harnessing a bis(selenomethyl)tetrathiafulvalene (TTF) derivative as a donor, conducting charge transfer (CT) salts are realized thanks to original packing structures supported by chalcogen bonding (ChB) interactions. Specifically, co-crystallization of EDT-TTF(SeMe)2...

Cited by 1 publication

References 34 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

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