Synthesis and characterization of a persistent paramagnetic rotaxane based on α-cyclodextrin and α,ω-alkyl disulfides

A new synthetic strategy for the preparation of persistent paramagnetic cyclodextrin-based rotaxanes is described. The method consists in the formation of inclusion complexes between α-cyclodextrin (α-CD) and α,ω-dithiols containing an octamethylene chain covalently trapped by bulky stoppers composed of 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) radical fragments. Interaction of α-CD (the bead) and 1,8-octanedithiol (the thread) occurs in aqueous alkaline media and encapsulation is obtained by nucleophilic substitution at both termini of the linear component with a bulky paramagnetic iodide [2,2,6,6-tetramethyl-4-(2-iodoacetamide)piperidine-N-oxyl]. Structure determination of the new [2]rotaxane by 1H NMR is reported and the spectroscopic data are discussed.