Structure and conformational equilibrium of thiacalix[4]arene by density functional theory

Ab initio and density functional studies of cooperative hydrogen bonding in calix[4]-and calix[6]arenes

“…As far as we know, there is only one publication that reports on calculations of calixarene (tetramethoxycalix [4]arene) (again without full geometry optimization) by the second order Möller Plesset method [8]. Also, note the following: the results of RHF/6-31G(d) and RHF/6-31G calculations of the structural and energy parameters of hydrogen bonding in compound I are quite comparable with one another and with experimental data (see also [6,9]); the experimental values of the energy parameters of hydrogen bonding in calixarenes are yet unknown; RHF/6-31G(d), RHF/6-31G(d,p), 2/6-31G(d), and 2/6-31G(d,p) studies of compound III still present great difficulty. As can be seen from the data of Tables 1, 2, and 3, calculations on calix [4]arenes using 3-21G, 3-21G(d,p), 6-31G, and 6-31G(d) bases, as well as calculations on calix [6]arenes using STO-2G, 3-21G, and 6-31G bases, give reliable structural data because the results of these calculations are in reasonable agreement with experimental data (see also [13]).…”

“…In recent years, experimental and theoretical publications on calix [4]-and calix [6]arenes [1][2][3][4][5][6][7][8][9][10][11] have increased in number. These compounds along with crown ethers are useful in modeling molecular recognition processes and in studies of molecular and ion transfer across cell membranes [10].…”

“…These compounds along with crown ethers are useful in modeling molecular recognition processes and in studies of molecular and ion transfer across cell membranes [10]. A few works are devoted to studies of calix [4]arenes and thiacalix [4]arenes by ab initio [7-9, 12, 13] and density functional [6][7][8][9]14] methods, and only one work deals with investigation of calix [6]arenes by these methods [13]. None of these works dealing with calixarenes has reported on hydrogen bond energy calculations, although this energy is the key factor of conformational stability and conformational lability of calixarenes with free hydroxyl groups [12] and their reactivity [11].…”

Molecular design of a “molecular syringe” mimic for metal cations using a 1,3‐alternate calix[4]arene cavity

“…[17][18][19][20][21][22][23] Recently a considerably progress is observed in quantum modeling of supermolecules. DFT studies on hydroxylated calix [4]arene, 24,25 thiacalix [4]arene, 26 and tetramethoxycalix [4]arene 27 have been published. What's more, the 1,3-alternate-25, 27-bis(1-octyloxy)-calix [4]arene-crown-6-H 3 O 1 complex species, 28 the amide linked lower rim 1,3-dibenzimidazole derivative of calix [4]arene, 29 and the equilibrium structure of 25,27-dihydroxycalix[4]-arene -crown-6 complex with cesium ion were all carried out by the DFT method.…”

mPW1PW91 Calculated Relative Stabilities and Structures for the Conformers of 1,3-dimethoxy-p-tert-butylthiacalix[4]crown-5-ether

“…5 Thiacalix [4]arenes in the presence of sulfur atoms instead of methylene groups exhibit novel structural and functional features including easy oxidation of sulfur bridges and extra binding sites, which make these compounds very interesting with potential applications such as inclusion of a variety of guest molecules, recognition of metal ions, chiral recognition, novel anion receptors, and novel dendriticshelled molecular receptors. [6][7][8][9][10][11][12][13][14][15] Therefore, one of the obvious classes of ionophores suitable for selective complexation of alkali metal 522 김광호 ․ 최종인…”