DFT study of the conformation, hydrogen bonds, IR, Raman, and NMR spectra of 1,3-disubstituted p-tert-butylthiacalix[4]arenes

Context The molecular design of spatially preorganized molecules is one of the critical issues in organic chemistry. Molecular recognition and multipoint binding define them. They organize nanoscale assemblies and devices and stably form host-guest inclusion complexes. Not only is this kind of research important in theory but it also has applications. They are used to create the basic elements of sensory devices: elements of cellular electronics, functional nanofilms and coatings, molecular switches, etc. Thiacalix[4]arenes are a useful molecular platform for constructing a wide range of preorganized receptor structures. This research aims to examine the structure and spectra of distally substituted para-tert-butylthiacalix[4]arene aliphatic (C1) and aromatic (C2) esters. The comparison of the spectra of C1, C2, and C3 makes it possible to reveal the structures and H-bonds of these compounds. The structures and H-bonds of these compounds can be seen by analyzing the spectra of C1, C2, and C3. Calculations were made for the spectra of various C1 and C2 molecule conformations. The most stable conformation for C1 and C2 molecules is a distorted cone 2 (DC2) with the same ester group orientation. The pinched cone (PC) conformation is the most unstable. Thiacalixarene molecules' cavities shrink from 3.61 to 3.57 angstrom when aromatic ester groups take the place of aliphatic ester groups. Two OH groups are linked to an oxygen atom in the DC1 and DC2 conformations of the C1 and C2 molecules. H-bonds in C1 and C2 molecules affect the supramolecular characteristics of these molecules. A drop in ionization energy and increases in electron affinity, chemical potential, softness, electrophilicity index, and dipole moment occur when aliphatic esters are replaced with aromatic ones. Methods Disubstituted aliphatic and aromatic esters' IR, Raman, and NMR spectra have been investigated. The DFT/B3LYP/6-311G(d,p) method and the GAUSSIAN 09W software were used to determine the vibrational spectra of molecules and optimize their geometry. A gauge-independent (GIAO) approach was used to determine chemical shifts in the NMR spectra with respect to tetramethylsilane.