Highly Selective Fluoride Recognition by a Small Tris-Urea Covalent Cage

Magalie Delecluse (1) , Cédric Colomban (1) , Bastien Chatelet (1) , Sabine Chevallier-Michaud (1) , Delphine Moraleda (1) , Jean-Pierre Dutasta (2) , Alexandre Martinez (1)

1 ISM2 - Institut des Sciences Moléculaires de Marseille
2 LC - Laboratoire de Chimie - UMR5182

A highly selective recognition of fluoride was achieved through the design of a small hemicryptophane cage (3) presenting a southern tris-urea hosting moiety. The resulting host−guest complex has been characterized by electrospray ionization-highresolution mass spectrometry, 1 H and 19 F NMR, and X-ray diffraction techniques. In particular, X-ray diffraction analysis of [3•F − ] reveals that the encapsulation of one fluoride, within 3, occurs through NH•••F − H-bonding with the six NH residues of the tris-urea ligand. An association constant of 1200 M −1 was extracted from 1 H NMR titration experiments, indicating that efficient fluoride binding also occurs in solution. Finally, in sharp contrast with previously reported urea-based hemicryptophane hosts, the small preorganized cavity found in 3 allows for an exclusive selectivity for fluoride over other competing halides.

Domaines: Chimie

Magalie Delecluse, Cédric Colomban, Bastien Chatelet, Sabine Chevallier-Michaud, Delphine Moraleda, et al.. Highly Selective Fluoride Recognition by a Small Tris-Urea Covalent Cage. Journal of Organic Chemistry, 2020, 85 (7), pp.4706-4711. ⟨10.1021/acs.joc.9b03429⟩. ⟨hal-02863548⟩