Ion pair-induced conformational motion in calix[4]arene-strapped calix[4]pyrroles
- Authors
- Kim, Sung Kuk; Lynch, Vincent M.; Hay, Benjamin P.; Kim, Jong Seung; Sessler, Jonathan L.
- Issue Date
- 2015
- Publisher
- ROYAL SOC CHEMISTRY
- Citation
- CHEMICAL SCIENCE, v.6, no.2, pp.1404 - 1413
- Indexed
- SCIE
SCOPUS
- Journal Title
- CHEMICAL SCIENCE
- Volume
- 6
- Number
- 2
- Start Page
- 1404
- End Page
- 1413
- URI
- https://scholar.korea.ac.kr/handle/2021.sw.korea/96133
- DOI
- 10.1039/c4sc03272a
- ISSN
- 2041-6520
- Abstract
- In order to understand the still-poorly understood interplay between calix[4]arene conformations and cation and anion recognition in multicomponent systems, the ion pair receptors 1 and 2 were synthesized. In solution and in the solid state, the calix[4]arene subunit of receptor 1 adopts a cone conformation, while that of 2 interconverts between the cone and the partial cone conformation. These geometric features differ from previous systems where the calix[4]arene moiety was locked in the 1,3-alternate conformation. A combination of H-1 NMR spectroscopic analyses and single crystal X-ray diffraction studies reveal that receptor 1 binds the fluoride and the chloride anion via significantly different binding modes, displaying, for instance, 1 : 1 and 2 : 3 binding stoichiometries with CsF and CsCl, respectively. In the case of 2, the conformation of the calix[4]arene constituent of 2 is highly dependent on the size and quantity of anions present. For example, upon treatment of 2 with the fluoride anion (as both the TBA(+) and Cs+ salts), the calix[4]arene unit coexists as cone and partial cone conformers that are inter-convertible. In the presence of excess CsF, the aromatic rings of the calix[4]arene subunit becomes locked in the pinched cone conformation with the result that an ion pair-mediated coordination polymer is formed. In the presence of excess CsCl, the calix[4]arene unit of 2 adopts only the partial cone conformation stabilized by aryl CH-anion hydrogen bonding interactions. The present systems constitute a rare set of related receptors wherein the effects of conformational changes are so tightly coupled with ion recognition.
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