The hydrogen bonding and conformations of p-tert-butylcalix[4]arene as studied by IR spectroscopy and by DFT calculations.

IR and far IR spectra of p-tert-butylcalix[4]arene were recorded at various temperatures between 16 and 180 degrees C and spectra of solutions and crystalline solids were obtained. Ab initio density functional calculations gave vibrational frequencies and infrared intensities for four conformers: cone, partial cone, 1,2- and 1,3-alternate. Complete assignments were made for experimental IR spectra of the cone conformer. The bands characteristic for each conformation were defined. It was revealed that O--H stretching low-frequency shift Deltanu in the cone conformation exceeds Deltanu shifts for other conformers. The effect was stipulated by a cooperative interaction of cyclic hydrogen bonds. The obtained spectra-structure correlation can be used for characteristic of calixarenes conformation.