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

ConspectusAmong 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 (organo-catalysis, 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.