Abstract
The role of the closing lecture in a Faraday Discussion is to summarise the contributions made to the Discussion over the course of the meeting and in so doing capture the main themes that have arisen. This article is based upon my Closing Remarks Lecture at the 203rd Faraday Discussion meeting on Halogen Bonding in Supramolecular and Solid State Chemistry, held in Ottawa, Canada, on 10-12th July, 2017. The Discussion included papers on fundamentals and applications of halogen bonding in the solid state and solution phase. Analogous interactions involving main group elements outside group 17 were also examined. In the closing lecture and in this article these contributions have been grouped into the four themes: (a) fundamentals, (b) beyond the halogen bond, (c) characterisation, and (d) applications. The lecture and paper also include a short reflection on past work that has a bearing on the Discussion.
Highlights
The role of the closing lecture in a Faraday Discussion is to summarise the contributions made to the Discussion over the course of the meeting and in so doing capture the main themes that have arisen
Our own work later emphasised the importance of the anisotropic charge distribution and resulting electrostatic potential around terminal halogens in developing an understanding of electrophilic interactions, predominantly hydrogen bonding, with terminal halogens,[17] but led us to become involved in studying halogen bonding.[18,19,20]
It is clear that the electrostatic model is central to describing halogen bonds and their p-block analogues, but that care is needed in interpreting solid-state arrangements, as while it may be convenient to assign halogen bonds or hydrogen bonds as structure directing, these may not be the main cohesive intermolecular forces
Summary
Reviews by Bent on donor–acceptor interactions,[10] and by Alcock on secondary bonding,[11] describe these interactions in some detail and cover many of the points being discussed in the recent rediscovery and resurgence of interest in what are being termed tetrel bonds (group 14), pnictogen bonds (group 15), chalcogen bonds (group 16) and aerogen bonds (group 18). Such interactions are most commonly described in terms of electrostatic interactions between a lone pair of electrons (or other electron-rich site) on one molecule and an electropositive site referred to as the s-hole and situated opposite to a s-bond formed by the main-group element.[12,13] Bent described these interactions in the framework of electron donor–acceptor complexes, requiring an orbital interaction model. The cross-over point is related to the relative strengths of the hydrogen bonds and halogen bonds that are in competition
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