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Ion pair-induced conformational motion in calix[4]arene-strapped calix[4]pyrroles

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/c4sc03272a· OSTI ID:1624915
 [1];  [2];  [3];  [4];  [2]
  1. Department of Chemistry; The University of Texas at Austin; Austin; USA; DOE/OSTI
  2. Department of Chemistry; The University of Texas at Austin; Austin; USA
  3. Supramolecular Design Institute; Oak Ridge; USA
  4. Department of Chemistry; Korea University; Seoul 136-701; Korea
+ Show Author Affiliations

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 1H 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.

Research Organization:
Univ. of Texas, Austin, TX (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
FG02-01ER15186
OSTI ID:
1624915
Journal Information:
Chemical Science, Journal Name: Chemical Science Journal Issue: 2 Vol. 6; ISSN 2041-6520; ISSN CSHCBM
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (10)

Molecular Engineering of Free-Base Porphyrins as Ligands-The N−H⋅⋅⋅X Binding Motif in Tetrapyrroles journal November 2018
The Nature of Ion-Pair Recognition by Tetra-phosphonate Calix[4]pyrroles journal February 2018
Molekulares Engineering freier Porphyrinbasen als Liganden - das N-H⋅⋅⋅X-Bindungsmotiv in Tetrapyrrolen journal November 2018
Post-synthetic modification of a macrocyclic receptor via regioselective imidazolium ring-opening journal January 2016
Strapped calix[4]pyrroles: from syntheses to applications journal January 2020
New dimensions in calix[4]pyrrole: the land of opportunity in supramolecular chemistry journal January 2019
Bis(naphthol)-based fluorescent chemoprobe for cesium cation and its immobilisation on silica nanoparticle as a high selective adsorbent journal January 2017
Super Extended Calix[4]Pyrroles as Candidate for Binding Mercury journal November 2018
Bis(naphthol)-based fluorescent chemoprobe for cesium cation and its immobilisation on silica nanoparticle as a high selective adsorbent text January 2017
Bis(naphthol)-based fluorescent chemoprobe for cesium cation and its immobilisation on silica nanoparticle as a high selective adsorbent text January 2017

Figures / Tables (16)

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