Vibrational spectra, co-operative intramolecular hydrogen bonding and conformations of calix[4]arene and thiacalix[4]arene molecules and their para-tert-butyl derivatives.
The IR and Raman spectra and conformations of calix[4]arene, thiacalix[4]arene and their p-tert-butyl derivatives have been analysed within the framework of scaled quantum mechanics (SQM). It is shown that the introduction of four p-tert-Bu groups into the calixarene molecules influences the relative energies of their conformers and the enthalpy of the cooperative intramolecular H-bonding (DeltaH(intra)) almost negligibly. DeltaH(intra), evaluated from Iogansen's rule, amounts to approximately 26-28 kcal mol(-1) for the calixarenes and approximately 20-21 kcal mol(-1) for the thiacalixarenes, which essentially exceeds the enthalpies of non-cooperative H-bonds formed by related phenols. As a result of this strong bonding, bands of stretching, bending and torsion vibrations of an eight-membered cyclic system (OH...)4 arise, e.g., two delta(OH)4 bands are observed in the IR spectra of the most highly symmetric C4 cone conformations of calix[4]arene and thiacalix[4]arene. The "duplication" of the number of OH infrared bands is a good new indicator of cooperativity of intramolecular H-bonding of the calixarenes.
Katsyuba
Sergey
S
A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Centre of the Russian Academy of Sciences, Arbuzov str. 8, 420088 Kazan, Russia. katsyuba@iopc.knc.ru
Kovalenko
Valeri
V
Chernova
Alla
A
Vandyukova
Elena
E
Zverev
Vladislav
V
Shagidullin
Roald
R
Antipin
Igor
I
Solovieva
Svetlana
S
Stoikov
Ivan
I
Konovalov
Alexander
A