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Title: 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];  [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
+ 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, Vol. 6, Issue 2; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 25 works
Citation information provided by
Web of Science

References (20)

Novel Cavity Design Using Calix[ n ]arene Skeletons:  Toward Molecular Recognition and Metal Binding journal August 1997
Kinetically stable complexes of alkali cations with rigidified calix[4]arenes: synthesis, x-ray structures, and complexation of calixcrowns and calixspherands journal September 1989
Complexation of alkali metal cations by conformationally rigid, stereoisomeric calix[4]arene crown ethers: a quantitative evaluation of preorganization journal September 1990
Synthesis, Complexation, and Membrane Transport Studies of 1,3-Alternate Calix[4]arene-crown-6 Conformers: A New Class of Cesium Selective Ionophores journal March 1995
1,3-Dialkoxycalix[4]arenecrowns-6 in 1,3-Alternate Conformation: Cesium-Selective Ligands that Exploit Cation-Arene Interactions journal August 1994
1,3-Alternate Calix[4]arenecrown-5 Conformers: New Synthetic Ionophores with Better K+/Na+ Selectivity than Valinomycin journal April 1996
Selectivity of Calix[4]arene-crown-6 for Cesium Ion in Ise: Effect of the Conformation journal December 1995
Relative stabilities of teramethoxycalix[4]arenes: combined NMR spectroscopy and molecular mechanics studies journal January 1992
“Cone” - “Partial-cone” Isomerism in Tetramethoxycalix[4]arenes. Influence of Solvent Polarity and Metal Ions journal January 1993
Crown-6-calix[4]arene-Capped Calix[4]pyrrole: An Ion-Pair Receptor for Solvent-Separated CsF Ions journal October 2008
A Calix[4]arene Strapped Calix[4]pyrrole: An Ion-Pair Receptor Displaying Three Different Cesium Cation Recognition Modes journal April 2010
Controlling Cesium Cation Recognition via Cation Metathesis within an Ion Pair Receptor journal January 2012
KF and CsF Recognition and Extraction by a Calix[4]crown-5 Strapped Calix[4]pyrrole Multitopic Receptor journal December 2012
Capture and metathesis-based release of potassium salts by a multitopic ion receptor journal January 2013
Calix[4]pyrrole-Based Ion Pair Receptors journal June 2014
Calix[4]pyrrole dimers bearing rigid spacers: towards the synthesis of cooperative anion binding agents journal August 2000
Naphthocrown-Strapped Calix[4]pyrroles: Formation of Self-Assembled Structures by Ion-Pair Recognition journal July 2014
Influence of Substituents on the Strength of Aryl C−H···Anion Hydrogen Bonds journal October 2005
Anion–arene adducts: C–H hydrogen bonding, anion–π interaction, and carbon bonding motifs journal January 2008
A Pyrrolyl-Based Triazolophane: A Macrocyclic Receptor With CH and NH Donor Groups That Exhibits a Preference for Pyrophosphate Anions journal October 2010

Cited By (10)

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
Molecular Engineering of Free-Base Porphyrins as Ligands-The N−H⋅⋅⋅X Binding Motif in Tetrapyrroles 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
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 journal January 2017
Bis(naphthol)-based fluorescent chemoprobe for cesium cation and its immobilisation on silica nanoparticle as a high selective adsorbent text January 2017

Linked Research (9)

Figures / Tables (16)

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