Thermodynamics of Halogen Bonding in Solution: Substituent, Structural, and Solvent Effects

Citations Over TimeTop 1% of 2010 papers

Abstract

A detailed study of the thermodynamics of the halogen-bonding interaction in organic solution is presented. (19)F NMR titrations are used to determine association constants for the interactions of a variety of Lewis bases with fluorinated iodoalkanes and iodoarenes. Linear free energy relationships for the halogen bond donor ability of substituted iodoperfluoroarenes XC(6)F(4)I are described, demonstrating that both substituent constants (sigma) and calculated molecular electrostatic potential surfaces are useful for constructing such relationships. An electrostatic model is, however, limited in its ability to provide correlation with a more comprehensive data set in which both halogen bond donor and acceptor abilities are varied: the ability of computationally derived binding energies to accurately model such data is elucidated. Solvent effects also reveal limitations of a purely electrostatic depiction of halogen bonding and point to important differences between halogen bonding and hydrogen bonding.

Related Papers

• → Halogen bond tunability I: the effects of aromatic fluorine substitution on the strengths of halogen-bonding interactions involving chlorine, bromine, and iodine(2011)400 cited
• → Competition between hydrogen and halogen bonding in halogenated 1‐methyluracil: Water systems(2016)27 cited
• → Halogen substituted quinolylsalicylaldimines: Four halogens three structural types(2012)26 cited
• Halogen bonding : impact on materials chemistry and life sciences(2015)
• → Isostructural Halogen Exchange and Halogen Bonds: The Case of N-(4-Halogenobenzyl)-3-halogenopyridinium Halogenides(2022)17 cited