Ab initio equilibrium geometry and vibrational spectroscopic study of 25,26,27,28-tetrahydroxycalix[4]arene

F. Billes, Ildikó Mohammed-Ziegler

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

The aim of this work was to present a comprehensive vibrational spectroscopic study of 25,26,27,28-tetrahydroxycalix[4]arene. For this purpose, quantum chemical calculations were carried out at the ab initio HF/4-31G* level, as a consequence of the great size of the molecule. In the frame of these calculations, the symmetry of the molecule was investigated. Trying C4V, C2V, and Cs symmetries as input, the geometry optimization, however, pointed to the C2 configuration. In the latter case, all the calculated vibrational frequencies were greater than zero, and therefore the equilibrium geometry could be identified. Medium and far infrared as well as Raman spectra of the compound were measured. On the basis of the calculated force constants and geometric parameters, normal coordinate analysis was applied for the interpretation of the experimental vibrational spectra. Problems arose with the choice of the internal coordinates of the molecule, which are important from the point of view of the internal macrocycle ("lower rim") of the molecule. On the basis of the theory of redundant coordinates, a program was written for choosing the coordinates of this 16-membered cycle. Full interpretation of the vibrational fundamentals of the compound is presented. Several force constant matrix elements have surprisingly high values. As a result of the normal coordinate analysis, the relative rigidity of the lower rim was concluded. Ab initio calculations and assignment of the vibrational spectra of 25,26,27,28-tetrahydroxycalix[4]arene based on the calculations are presented.

Original languageEnglish
Pages (from-to)451-459
Number of pages9
JournalSupramolecular Chemistry
Volume14
Issue number5
DOIs
Publication statusPublished - Oct 2002

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Vibrational spectra
Molecules
Geometry
Rigidity
Raman scattering
Infrared radiation
25,26,27,28-tetrahydroxycalix(4)arene

Keywords

  • Ab initio
  • Calix[4]arene
  • Geometry
  • Normal coordinate analysis
  • Vibrational spectra

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Ab initio equilibrium geometry and vibrational spectroscopic study of 25,26,27,28-tetrahydroxycalix[4]arene. / Billes, F.; Mohammed-Ziegler, Ildikó.

In: Supramolecular Chemistry, Vol. 14, No. 5, 10.2002, p. 451-459.

Research output: Contribution to journalArticle

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