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

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 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 anmore » 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.« less

Authors:
 [1];  [1];  [2];  [3];  [1]
  1. Department of Chemistry; The University of Texas at Austin; Austin; USA
  2. Supramolecular Design Institute; Oak Ridge; USA
  3. Department of Chemistry; Korea University; Seoul 136-701; Korea
Publication Date:
Research Org.:
Univ. of Texas, Austin, TX (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1624915
Grant/Contract Number:  
FG02-01ER15186
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 6; Journal Issue: 2; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
Chemistry

Citation Formats

Kim, Sung Kuk, Lynch, Vincent M., Hay, Benjamin P., Kim, Jong Seung, and Sessler, Jonathan L. Ion pair-induced conformational motion in calix[4]arene-strapped calix[4]pyrroles. United States: N. p., 2015. Web. https://doi.org/10.1039/c4sc03272a.
Kim, Sung Kuk, Lynch, Vincent M., Hay, Benjamin P., Kim, Jong Seung, & Sessler, Jonathan L. Ion pair-induced conformational motion in calix[4]arene-strapped calix[4]pyrroles. United States. https://doi.org/10.1039/c4sc03272a
Kim, Sung Kuk, Lynch, Vincent M., Hay, Benjamin P., Kim, Jong Seung, and Sessler, Jonathan L. Thu . "Ion pair-induced conformational motion in calix[4]arene-strapped calix[4]pyrroles". United States. https://doi.org/10.1039/c4sc03272a. https://www.osti.gov/servlets/purl/1624915.
@article{osti_1624915,
title = {Ion pair-induced conformational motion in calix[4]arene-strapped calix[4]pyrroles},
author = {Kim, Sung Kuk and Lynch, Vincent M. and Hay, Benjamin P. and Kim, Jong Seung and Sessler, Jonathan L.},
abstractNote = {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.},
doi = {10.1039/c4sc03272a},
journal = {Chemical Science},
number = 2,
volume = 6,
place = {United States},
year = {2015},
month = {1}
}

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Free Publicly Available Full Text
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Cited by: 18 works
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Figures / Tables:

Fig. 1 Fig. 1: Front and side views of the single crystal X-ray diffraction structure of 1$ethyl acetate. Most hydrogen atoms have been omitted for clarity.

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    Works referencing / citing this record:

    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
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    Molecular Engineering of Free-Base Porphyrins as Ligands-The N−H⋅⋅⋅X Binding Motif in Tetrapyrroles
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