mPW1PW91 study for conformational isomers of methylene bridge-monosubstituted tetramethoxycalix[4]arenes

Structures of ten conformational isomers of methylene bridge-monosubstituted tetramethoxycalix[4]arenes, 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetramethoxy-2-ethylcalix[4]arene (1), and methyl 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetramethoxycalix[4]arene-2-carboxylate (2) were optimized by quantum mechanical mPW1PW91/6-31G(d,p) (hybrid Hartree–Fock density functional) calculations. The total electronic and Gibbs free energies of the various conformations (cone, partial cone, 1,2-alternate, and 1,3-alternate) of 1 and 2 were analyzed. The cone (equatorial) and partial cone (equatorial) conformers were disclosed to be the most stable among all the isomers of 1 and 2. The calculated structures agreed well with the experimental results. The IR spectra were calculated at the mPW1PW91/6-31G(d,p) level for the most stable conformer of each methylene bridge-monosubstituted tetramethoxycalix[4]arene.