Halogen bonding, chalcogen bonding, pnictogen bonding, tetrel bonding: origins, current status and discussion

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 203rdFaraday Discussion meeting on Halogen Bonding in Supramolecular and Solid State Chemistry, held in Ottawa, Canada, on 10–12thJuly, 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.

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Multiple Bonds between Transition Metals and ?Bare? Main Group Elements: Links between Inorganic Solid State Chemistry and Organometallic Chemistry

Angewandte Chemie International Edition in English ◽

10.1002/anie.198600561 ◽

1986 ◽

Vol 25 (1) ◽

pp. 56-76 ◽

Cited By ~ 163

Author(s):

Wolfgang A. Herrmann

Keyword(s):

Solid State ◽

Transition Metals ◽

Organometallic Chemistry ◽

Main Group ◽

Solid State Chemistry ◽

Multiple Bonds ◽

Main Group Elements

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A comparative experimental and theoretical investigation of hydrogen-bond, halogen-bond and π–π interactions in the solid-state supramolecular assembly of 2- and 4-formylphenyl arylsulfonates

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s2053229618008355 ◽

2018 ◽

Vol 74 (7) ◽

pp. 816-829 ◽

Cited By ~ 2

Author(s):

Hina Andleeb ◽

Imtiaz Khan ◽

Antonio Bauzá ◽

Muhammad Nawaz Tahir ◽

Jim Simpson ◽

...

Keyword(s):

Solid State ◽

Density Functional ◽

Halogen Bond ◽

Noncovalent Interactions ◽

Supramolecular Assembly ◽

Halogen Bonding ◽

Type I ◽

Supramolecular Architectures ◽

Solid State Structures

To explore the operational role of noncovalent interactions in supramolecular architectures with designed topologies, a series of solid-state structures of 2- and 4-formylphenyl 4-substituted benzenesulfonates was investigated. The compounds are 2-formylphenyl 4-methylbenzenesulfonate, C14H12O4S, 3a, 2-formylphenyl 4-chlorobenzenesulfonate, C13H9ClO4S, 3b, 2-formylphenyl 4-bromobenzenesulfonate, C13H9BrO4S, 3c, 4-formylphenyl 4-methylbenzenesulfonate, C14H12O4S, 4a, 4-formylphenyl 4-chlorobenzenesulfonate, 4b, C13H9ClO4S, and 4-formylphenyl 4-bromobenzenesulfonate, C13H9BrO4S, 4c. The title compounds were synthesized under basic conditions from salicylaldehyde/4-hydroxybenzaldehydes and various aryl sulfonyl chlorides. Remarkably, halogen-bonding interactions are found to be important to rationalize the solid-state crystal structures. In particular, the formation of O...X (X = Cl and Br) and type I X...X halogen-bonding interactions have been analyzed by means of density functional theory (DFT) calculations and characterized using Bader's theory of `atoms in molecules' and molecular electrostatic potential (MEP) surfaces, confirming the relevance and stabilizing nature of these interactions. They have been compared to antiparallel π-stacking interactions that are formed between the arylsulfonates.

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Halogen bonding stabilizes acis-azobenzene derivative in the solid state: a crystallographic study

Acta Crystallographica Section B Structural Science Crystal Engineering and Materials ◽

10.1107/s2052520617003444 ◽

2017 ◽

Vol 73 (2) ◽

pp. 227-233 ◽

Cited By ~ 4

Author(s):

Marco Saccone ◽

Antti Siiskonen ◽

Franisco Fernandez-Palacio ◽

Arri Priimagi ◽

Giancarlo Terraneo ◽

...

Keyword(s):

Solid State ◽

Density Functional ◽

Rational Design ◽

Halogen Bond ◽

Phase Segregation ◽

Halogen Bonding ◽

Density Functional Theory Calculations ◽

Aliphatic Chain ◽

Molecular Arrangement

Crystals oftrans- andcis-isomers of a fluorinated azobenzene derivative have been prepared and characterized by single-crystal X-ray diffraction. The presence of F atoms on the aromatic core of the azobenzene increases the lifetime of the metastablecis-isomer, allowing single crystals of thecis-azobenzene to be grown. Structural analysis on thecis-azobenzene, complemented with density functional theory calculations, highlights the active role of the halogen-bond contact (N...I synthon) in promoting the stabilization of thecis-isomer. The presence of a long aliphatic chain on the azobenzene unit induces a phase segregation that stabilizes the molecular arrangement for both thetrans- andcis-isomers. Due to the rarity ofcis-azobenzene crystal structures in the literature, our paper makes a step towards understanding the role of non-covalent interactions in driving the packing of metastable azobenzene isomers. This is expected to be important in the future rational design of solid-state, photoresponsive materials based on halogen bonding.

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