Bis-Squaramide-Based [2]Rotaxane Hosts for Anion Recognition

The first examples of bis-squaramide axle containing [2]rotaxanes linked via rigid aryl and flexible alkyl spacers synthesised using copper(I) catalysed active metal template methodology are reported. The halide and oxoanion binding properties of the [2]rotaxanes in aqueous-organic solvent media are examined through extensive ¹H-NMR titration experiments to investigate the impact of integrating multiple squaramide motifs on the anion binding capabilities of the interlocked receptors. These studies reveal that the bis-squaramide rotaxane host systems exhibit enhanced halide anion binding capabilities relative to a mono-squaramide axle functionalised rotaxane, demonstrating a rare anti-Hofmeister bias halide anion selectivity trend in aqueous-organic mixtures and highlighting the efficacy of the potent solvent shielded hydrophobic interlocked binding pocket created upon mechanical bond formation. Notably, employing a rigid aryl linker between the two squaramide motifs in the axle component enables the rotaxane host to exhibit strong and selective binding of tetrahedral oxoanions. Conversely, a flexible alkyl spacer facilitates trigonal oxoanion selective recognition by the bis-squaramide [2]rotaxane.