Chalcogen Bonding Macrocycles and [2]Rotaxanes for Anion Recognition

• DOI: 10.1021/jacs.6b12745
• Publication Date: 2017-01-31T21:14:11Z
• Authors: Jason Y. C. Lim; Igor Marques; Amber L. Thompson; Kirsten E. Christ...; Vítor Félix; Paul D. Beer
• Keywords: Chalcogen; Molecular Recognition

Electron-deficient heavy chalcogen atoms contain Lewis acidic σ-holes which are able to form attractive supramolecular interactions, known as bonding (ChB), with bases. However, their potential in solution-phase anion binding applications is only just beginning be realized simple acyclic systems. Herein, we explore the 5-(methylchalcogeno)-1,2,3-triazole (chalcogen = Se, Te) motif a novel ChB donor for binding. Other than being chemically robust enough incorporated into macrocyclic structures, thereby significantly expanding scope and complexity of host systems, also demonstrate, by 1H NMR DFT calculations, that oriented within macrocycle cavity chelate copper(I) endotopically. Exploiting this property, first examples mechanically interlocked [2]rotaxanes containing ChB-donor groups prepared via an active metal template strategy. Solution-phase molecular modeling studies provide compelling evidence dominant influence these In addition, unprecedented charge-assisted ChB-mediated was studied aqueous solvent mixtures, revealed considerable differences recognition behavior comparison chalcogen-free analogues. Moreover, calculations dynamics simulations mixtures indicate selectivity determined different hydrophilic characters anions allied hydration units presence anions. NMR-active nuclei atoms, heteronuclear 77Se 125Te were used directly study how influences local electronic environment bonded rotaxane sites organic mixtures.