Oligoether-strapped calix[4]pyrrole: an ion-pair receptor displaying cation-dependent chloride anion transport


Park, In-Won, Yoo, Jaeduk, Kim, Bohyang, Adhikari, Suman, Kim, Sung Kuk, Yeon, Yerim, Haynes, Cally J. E., Sutton, Jennifer L., Tong, Christine C., Lynch, Vincent M., Sessler, Jonathan L., Gale, Philip A. and Lee, Chang-Hee (2012) Oligoether-strapped calix[4]pyrrole: an ion-pair receptor displaying cation-dependent chloride anion transport. Chemistry: A European Journal (doi:10.1002/chem.201103239).

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Description/Abstract

A ditopic ion-pair receptor (1), which has tunable cation- and anion-binding sites, has been synthesized and characterized. Spectroscopic analyses provide support for the conclusion that receptor 1 binds fluoride and chloride anions strongly and forms stable 1:1 complexes ([1⋅F]− and [1⋅Cl]−) with appropriately chosen salts of these anions in acetonitrile. When the anion complexes of 1 were treated with alkali metal ions (Li+, Na+, K+, Cs+, as their perchlorate salts), ion-dependent interactions were observed that were found to depend on both the choice of added cation and the initially complexed anion. In the case of [1⋅F]−, no appreciable interaction with the K+ ion was seen. On the other hand, when this complex was treated with Li+ or Na+ ions, decomplexation of the bound fluoride anion was observed. In contrast to what was seen with Li+, Na+, K+, treating [1⋅F]− with Cs+ ions gave rise to a stable, host-separated ion-pair complex, [F⋅1⋅Cs], which contains the Cs+ ion bound in the cup-like portion of the calix[4]pyrrole. Different complexation behavior was seen in the case of the chloride complex, [1⋅Cl]−. Here, no appreciable interaction was observed with Na+ or K+. In contrast, treating with Li+ produces a tight ion-pair complex, [1⋅Li⋅Cl], in which the cation is bound to the crown moiety. In analogy to what was seen for [1⋅F]−, treatment of [1⋅Cl]− with Cs+ ions gives rise to a host-separated ion-pair complex, [Cl⋅1⋅Cs], in which the cation is bound to the cup of the calix[4]pyrrole. As inferred from liposomal model membrane transport studies, system 1 can act as an effective carrier for several chloride anion salts of Group 1 cations, operating through both symport (chloride+cation co-transport) and antiport (nitrate-for-chloride exchange) mechanisms. This transport behavior stands in contrast to what is seen for simple octamethylcalix[4]pyrrole, which acts as an effective carrier for cesium chloride but does not operates through a nitrate-for-chloride anion exchange mechanism

Item Type: Article
ISSNs: 1521-3765
Subjects: Q Science > QD Chemistry
Divisions: Faculty of Natural and Environmental Sciences > Chemistry > Molecular Assembly, Function & Structure
ePrint ID: 210961
Date Deposited: 16 Feb 2012 15:12
Last Modified: 27 Mar 2014 19:50
URI: http://eprints.soton.ac.uk/id/eprint/210961

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