Hydrogen
Bonding Interaction between Active Methylene
Hydrogen Atoms and an Anion as a Binding Motif for Anion Recognition:
Experimental Studies and Theoretical Rationalization
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Abstract
Two
new reagents, having similar spatial arrangements for hydrogen
atoms of the active methylene functionalities, were synthesized and
interactions of such reagents with different anionic analytes were
studied using electronic spectroscopy as well as by using <sup>1</sup>H and <sup>31</sup>P NMR spectroscopic methods. Experimental studies
revealed that these two reagents showed preference for binding to
F<sup>–</sup> and OAc<sup>–</sup>. Detailed theoretical
studies along with the above-mentioned spectroscopic studies were
carried out to understand the contribution of the positively charged
phosphonium ion, along with methylene functionality, in achieving
the observed preference of these two receptors for binding to F<sup>–</sup> and OAc<sup>–</sup>. Observed differences in
the binding affinities of these two reagents toward fluoride and acetate
ions also reflected the role of acidity of such methylene hydrogen
atoms in controlling the efficiencies of the hydrogen bonding in anion–H<sub>methylene</sub> interactions. Hydrogen bonding interactions at lower
concentrations of these two anionic analytes and deprotonation equilibrium
at higher concentration were observed with associated electronic spectral
changes as well as visually detectable change in solution color, an
observation that is generally common for other strong hydrogen bond
donor functionalities like urea and thiourea. DFT calculations performed
with the M06/6-31+G**//M05-2X/6-31G* level of theory showed that F<sup>–</sup> binds more strongly than OAc<sup>–</sup> with
the reagent molecules. The deprotonation of methylene hydrogen atom
of receptors with F<sup>–</sup> ion was observed computationally.
The metal complex as reagent showed even stronger binding energies
with these analytes, which corroborated the experimental results