Effect of fluorine substitution in calix[4]pyrrole: A DFT study

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Using density functional theory we investigate the ground-state geometries and electronic structures of calix[4]pyrrole (C4P) and its fluorine analogue (F-C4P). The HOMO-LUMO energy gap of C4P is 5.9 eV and remains nearly the same upon H-by-F replacement (5.7 eV). Fluorine substitution increases both the vertical and adiabatic ionization potentials of C4P by ∼0.8 eV while the electron affinity of either macrocycle is negative thus indicating that the corresponding radical anion in the gas-phase is thermodynamically unstable. It is shown that the topology of the LUMOs of both C4P and F-C4P have important implications for the spherical recognition of halide anions. The simulated IR, NMR, and electronic spectra display important fingerprints for the characterization of these macrocycles.

Original languageEnglish
Pages (from-to)36-42
Number of pages7
JournalJournal of Molecular Structure: THEOCHEM
Issue number1-3
Publication statusPublished - 2008 Dec 15


  • Calix[4]pyrrole
  • DFT
  • Electronic structure
  • Theoretical spectra

ASJC Scopus subject areas

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry


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