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

The aim of this work was to present a comprehensive vibrational spectroscopic study of 25,26,27,28-tetrahy-droxycalix[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 C-4v, C-2v, and C-s symmetries as input, the geometry optimization, however, pointed to the C-2 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.