Synthesis and investigation of host-[2]rotaxanes that bind metal cations.

Materials that bind metal cations are highly sought after for new devices. In this report, we show that rotaxanes can transfer metal cations with picrate, perchlorate, or chloride counterions from an aqueous solution into chloroform. The rotaxanes contain a dibenzyl-24-crown-8 ether as the wheel with either a benzyl-18-crown-6 ether (CEBG-R1−3) or a 3,5-dimethylbenzyl moiety (ArBG-R) as one blocking group. Alkali and alkaline picrate salts were efficiently extracted from an aqueous solution, presented in the millimolar range, into chloroform. Large association constants were derived for the complexes in chloroform, especially for the divalent cation Mg2+. Switching the counterion to chloride greatly diminished the amount of salt extracted. To explore the transfer mechanism of the rotaxanes, a comparison was made in the amount of NaClO4, KClO4, NaCl, and KCl extracted by CEBG-R1, ArBG-R, benzyl-18-crown-6 ether (B18C6), and two model compounds, which were used to represent the crown-ether blocking group an...