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Electrochemical Activation of TTF‐Based Halogen Bond Donors: A Powerful, Selective and Sensitive Analytical Tool for Probing a Weak Interaction in Complex Media
Author(s) -
Oliveira Raquel,
Groni Sihem,
Vacher Antoine,
Barrière Frédéric,
Lorcy Dominique,
Fourmigué Marc,
Maisonhaute Emmanuel,
Schöllhorn Bernd,
Fave Claire
Publication year - 2018
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201801957
Subject(s) - chemistry , electrochemistry , halogen bond , halogen , cyclic voltammetry , lewis acids and bases , intermolecular force , redox , covalent bond , computational chemistry , chemical physics , molecule , combinatorial chemistry , inorganic chemistry , electrode , organic chemistry , alkyl , catalysis
Herein we demonstrate the electrochemical activation and detection of intermolecular halogen bonding (XB) in solution by generating the cation radical of iodo‐trimethyltetrathiafulvalene (I‐Me 3 TTF •+ ) in the presence of various Lewis‐basic anions. This work is leading to the endorsement and generalization of the concept of electrostimulating XB for molecular recognition by adjusting the properties of the XB donor via the electrochemical reversible generation of charged species. The formation of the interaction between I–Me 3 TTF •+ and Lewis bases has been investigated by cyclic voltammetry allowing to quantify the strength of the interaction ( K Ox =100 to 400 M −1 and Δ G =−12 to −15 kJ mol −1 ). Moreover spectroelectrochemical measurements along with TD‐DFT calculations have confirmed XB formation upon generation of the radical cation. The present work opens broad perspectives for the development of redox switchable XB donors in the field of molecular recognition in chemical and biological systems where non‐covalent interactions are usually key governing parameters.