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Competitive Halide Binding by Halogen Versus Hydrogen Bonding: Bis‐triazole Pyridinium
Author(s) -
Nepal Binod,
Scheiner Steve
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201501921
Subject(s) - halide , halogen , chemistry , pyridinium , hydrogen bond , pyridine , halogen bond , triazole , atom (system on chip) , binding energy , chelation , crystallography , inorganic chemistry , medicinal chemistry , molecule , organic chemistry , alkyl , physics , computer science , nuclear physics , embedded system
The binding of F − , Cl − , Br − , and I − anions by bis‐triazole‐pyridine (BTP) was examined by quantum chemical calculations. There is one H atom on each of the two triazole rings that chelate the halide via H bonds. These H atoms were replaced by halogens Cl, Br, and I, thus substituting H bonds by halogen bonds. I substitution strongly enhances the binding; Br has a smaller effect, and Cl weakens the interaction. The strength of the interaction is sensitive to the overall charge on the BTP, rising as the binding agent becomes singly and then doubly positively charged. The strongest preference of a halide for halogenated as compared to unsubstituted BTP, as much as several orders of magnitude, is observed for I − . Both unsubstituted and I‐substituted BTP could be used to selectively extract F − from a mixture of halides.