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Conformational diversity and dynamics of distally disubstituted calix and thiacalix[4]arenes in solution
Author(s) -
Latypov Shamil K.,
Kharlamov Sergey V.,
Muravev Anton A.,
Balandina Alsu A.,
Solovieva Svetlana E.,
Antipin Igor S.,
Konovalov Alexander I.
Publication year - 2013
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3101
Subject(s) - chemistry , oxygen atom , quantum chemical , group (periodic table) , atom (system on chip) , symmetry (geometry) , crystallography , molecular dynamics , stereochemistry , computational chemistry , molecule , geometry , organic chemistry , mathematics , computer science , embedded system
According to the quantum chemical calculations and Dynamic NMR experiments in the distally disubstituted classical and thiacalix[4]arenes (CCA and TCA) in addition to the C 2v symmetrical pinched cone (PC) conformation, the distorted cone (DC) form with an approximate C s overall symmetry (with two OH groups bonded to one oxygen atom) also corresponds to the energy minimum. Moreover, in DC form, two different mutual orientations of O–R groups at a lower rim lead to two stable conformations: the first ‐ with both these groups directed outward, the second ‐ with both these groups pointing toward the same direction. In CCA, the PC is essentially favoured over the DC, while in TCA, energies of these forms are similar or the latter may be even preferable. Copyright © 2013 John Wiley & Sons, Ltd.