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. 2013 Sep 23;52(39):10275-80.
doi: 10.1002/anie.201303881. Epub 2013 Aug 12.

Selective nitrate binding in competitive hydrogen bonding solvents: do anion-π interactions facilitate nitrate selectivity?

Michelle M Watt  1 , Lev N Zakharov, Michael M Haley, Darren W Johnson
Affiliations

Selective nitrate binding in competitive hydrogen bonding solvents: do anion-π interactions facilitate nitrate selectivity?

Michelle M Watt et al. Angew Chem Int Ed Engl. .

Abstract

New tripodal urea receptors demonstrate preferential binding of anions over competitive hydrogen bonding solvents. 1H NMR titrations in 10% DMSO-d6/CDCl3 show a higher affinity for nitrate over the halides for the fluorinated receptor, which is lost when the fluorines are removed. An “anion–π” interaction between the nitrate and the π-system of the ethynyl-substituted arene is proposed as the source of this selectivity.

Keywords: anion recognition; anion-π interactions; host-guest systems; receptors; supramolecular chemistry.

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Figures

Figure 1
Figure 1
Crystal packing of 1 (top) showing a dimer capped by a total of eight acetone molecules and (bottom) showing these dimers are mostly discrete, interacting with each other through only π-stacking (solvent omitted for clarity).
Figure 1
Figure 1
Crystal packing of 1 (top) showing a dimer capped by a total of eight acetone molecules and (bottom) showing these dimers are mostly discrete, interacting with each other through only π-stacking (solvent omitted for clarity).
Figure 2
Figure 2
Crystal packing of 1 with (a,c,e,g) TBACl and (b,d,f,h) TBANO3, highlighting the overall 1:1 interactions between host and anionic guest in the (a,b) monomer, (c,d) stacked column, and with the conjugated π-system (e,f). Cation (blue) and solvent (orange) interactions are shown in g and h.
Figure 3
Figure 3
Example stacked 1H NMR spectra for the titration of nitrate into a 1 mM solution of receptor 1 in 10% DMSO-d6/CDCl3
Figure 4
Figure 4
Stacked 1H NMR spectra for the titration of (a) Cl− and (b) NO3− into a 1 mM solution of receptor 2 in 10% DMSO-d6/CDCl3.
Scheme 1
Scheme 1
Synthesis of tripodal receptors 1 and 2.
See this image and copyright information in PMC

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