Three triazolium-based [2]rotaxanes containing different sized axle and macrocycle components were synthesised in good yields (40-57%) through chloride anion templation. The anion recognition properties of the interlocked receptor systems were investigated using (1)H NMR titration experiments: all three rotaxanes display impressive selectivities for halide anions over the more basic oxoanion acetate. The rotaxanes incorporating shorter, more rigid axle components with aryl-substituted triazolium groups display substantially higher anion binding affinities than those with longer, bis-alkyl-substituted heterocycles, which is attributed to the increased intercomponent preorganisation afforded by the smaller axle component. Computational DFT and molecular dynamics simulations composed of unconstrained and umbrella sampling simulations corroborate the experimental observations.
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Halotriazolium axle functionalised [2]rotaxanes for anion recognition: investigating the effects of halogen-bond donor and preorganisation.
Chemistry
September 2014
Chemistry Research Laboratory, Department of Chemistry, University of Oxford, Mansfield Road, Oxford, OX1 3TA (UK), Fax: (+44) 1865-272690.
Article Synopsis
- The study focuses on creating new [2]rotaxanes using halogen-bonding 5-halo-1,2,3-triazolium axles, exploring how different halogen-bond donor atoms and preorganization affect anion recognition.
- Initial findings showed that bromide ions are the best templates for assembling these rotaxanes, leading to the first bromotriazolium axle-based [2]rotaxane, which preferentially binds bromide and iodide ions over a similar hydrogen-bonding version.
- Further synthesis of two halogen-bonding [2]rotaxanes with enhanced preorganization supports stronger halide binding, with one iodotriazolium derived rotaxane effectively recognizing halides
Increased halide recognition strength by enhanced intercomponent preorganisation in triazolium containing [2]rotaxanes.
Chemistry
December 2013
Chemistry Research Laboratory, Department of Chemistry, University of Oxford, Mansfield Road, Oxford, OX1 3TA (UK).
Three triazolium-based [2]rotaxanes containing different sized axle and macrocycle components were synthesised in good yields (40-57%) through chloride anion templation. The anion recognition properties of the interlocked receptor systems were investigated using (1)H NMR titration experiments: all three rotaxanes display impressive selectivities for halide anions over the more basic oxoanion acetate. The rotaxanes incorporating shorter, more rigid axle components with aryl-substituted triazolium groups display substantially higher anion binding affinities than those with longer, bis-alkyl-substituted heterocycles, which is attributed to the increased intercomponent preorganisation afforded by the smaller axle component.
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