TY - JOUR
T1 - Halide anion recognition by calix[4]pyrrole
T2 - A quantum chemical study
AU - Pichierri, Fabio
N1 - Funding Information:
The author gratefully acknowledges RIKEN (The Institute of Physical and Chemical Research, Japan) for the computer resources made available to him and for financial support.
Copyright:
Copyright 2018 Elsevier B.V., All rights reserved.
PY - 2002/4/5
Y1 - 2002/4/5
N2 - The spherical recognition of halide anions by the calix[4]pyrrole molecule has been investigated with the aid of Hartree-Fock, hybrid DPT (B3LYP), and semi-empirical (PM3) quantum chemical methods. The free calix[4]pyrrole molecule adopts the 1,3-alternate conformation, as confirmed by an earlier X-ray crystal structure analysis, whereas a transition to a cone-like conformation occurs upon capture of a single halide anion. The calculated binding energies of the calix[4]pyrrole: halide anion complexes decrease monotonically along the group 17 anions, i.e. from fluoride to iodide, in agreement with the experimentally determined binding constants. Furthermore, a linear correlation of the calculated binding energy against both the standard reduction potential and the Pauling electronegativity has been found. Finally, a possible mechanism of halide anion capture by the calix[4]pyrrole receptor has been proposed on the basis of both theoretical calculations and crystallographic data.
AB - The spherical recognition of halide anions by the calix[4]pyrrole molecule has been investigated with the aid of Hartree-Fock, hybrid DPT (B3LYP), and semi-empirical (PM3) quantum chemical methods. The free calix[4]pyrrole molecule adopts the 1,3-alternate conformation, as confirmed by an earlier X-ray crystal structure analysis, whereas a transition to a cone-like conformation occurs upon capture of a single halide anion. The calculated binding energies of the calix[4]pyrrole: halide anion complexes decrease monotonically along the group 17 anions, i.e. from fluoride to iodide, in agreement with the experimentally determined binding constants. Furthermore, a linear correlation of the calculated binding energy against both the standard reduction potential and the Pauling electronegativity has been found. Finally, a possible mechanism of halide anion capture by the calix[4]pyrrole receptor has been proposed on the basis of both theoretical calculations and crystallographic data.
KW - Calix[4]pyrrole
KW - DFT
KW - HF-MO
KW - Halide anion recognition
KW - PM3 calculations
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U2 - 10.1016/S0166-1280(01)00749-7
DO - 10.1016/S0166-1280(01)00749-7
M3 - Article
AN - SCOPUS:0037023162
VL - 581
SP - 117
EP - 127
JO - Computational and Theoretical Chemistry
JF - Computational and Theoretical Chemistry
SN - 2210-271X
IS - 1-3
ER -