Halogen Bonding in Solution: Under Pressure

Le résumé fourni par la source

The first study of the high-pressure behavior of organic halogen bond donors in solution is presented: HP-NMR titrations were performed in various solvents, primarily with a neutral tridentate halogen bond donor and an orthoamide or halides as Lewis bases. While the orthoamide showed stronger binding upon increased pressure in CDCl 3, CD 2 Cl 2, acetone- d 6, and THF- d 8, the halides unexpectedly featured decreased association constants for the first three solvents. For comparison, bromide was also titrated against dicationic halogen and chalcogen bond donors as well as a thiourea as a representative hydrogen bond donor, with the latter showing weaker binding at elevated pressure. Qualitative agreement with this data was achieved via thermodynamic modeling using PC-SAFT. These findings stress the important role of the solvent in halogen-bonded complexes involving charged species and are expected to provide the basis for a rational application of high pressure in applications of halogen bonding in solution.

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