Computational study of the structural, energetic, and acid-base properties of calix[4]arenes

Grootenhuis, Peter D. J.; Kollman, Peter A.; Groenen, Leo C.; Reinhoudt, David N.; Hummel, G.J. van; Ugozzoli, Franco; Andreetti, G. D.

doi:10.1021/ja00167a010

Cited by 280 publications

(208 citation statements)

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“…The deviation of these data from the value obtained by RHF/6-31G(d) (26.7 kcal/mole) is -6.2 kcal/mole, 7.2 kcal/mole, 0.2 kcal/mole, 4.9 kcal/mole, -1.3 kcal/mole, -2.3 kcal/mole, -2.0 kcal/mole, -1.4 kcal/mole, 4.1 kcal/mole, and -1.9 kcal/mole, respectively, or 23.2%, 27.0%, 0.8%, 18.4%, 4.9%, 8.6%, 7.5%, 5.2%, 15.4%, and 7.1%, respectively. One can conclude that the above-mentioned semiempirical methods (AM1 [1], PM3) and the RHF/6-31G(d)/RHF/STO-2G technique, as well as RHF/STO-2G, RHF/3-21G, and RHF/6-31G, provide information about the magnitude of changes in the H bond energy in the compounds under study, which is in reasonable agreement with the data of RHF/6-31G(d) calculations (Table 5) [1,12]. The ab initio methods of calculation, where geometry optimization is fulfilled in one approximation and the energy of a structure is calculated in another (in particular, at second order Möller Plesset level of theory), obviously slightly exaggerate the strength of H bonds in calix [4]arene; as a result, changes in H bond energy obtained by these methods approximate the value obtained by RHF/STO-2G.…”

Section: Discussion Of Resultsmentioning

confidence: 90%

“…The energies of cooperative hydrogen bonds in calix [4]arene and calix [6]arene were calculated by the procedure suggested by P. Grootenhuis [1] and applied previously [12]. At first we determined the energy of the neutral compound relative to the energy of the monoanion obtained by proton elimination from the optimized neutral structure of the cone conformer of calix [4]arene or compressed cone conformer of calix [6]arene and subsequently optimized with the same level of accuracy as for the neutral conformer (Grad RMS = 10 -6 Hartree/Bohr):…”

Section: Calculation Proceduresmentioning

confidence: 99%

“…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].…”

mentioning

confidence: 99%

“…The H bond of this type may also be characterized in terms of the cooperative effect of H bonds, increasing with the length of the chain. These quantities were evaluated by the technique suggested by P. Grootenhuis [1] based on the results of geometry optimization by several ab initio methods.…”

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confidence: 99%

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

et al. 2006

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The cone conformation of 4 symmetry is shown by the Hartree-Fock method (3-21G basis) to be the predominant conformer of calix [4]arene; the compressed cone of 2 symmetry is the major conformer of calix [6] [7-9, 12, 13] and density functional [6-9, 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].The stability of the hydrogen bond in calixarene was correlated with the reaction route involving this compound when dialkoxydihydroxycalix[4]arene was synthesized from monoalkoxytrihydroxycalix[4]arene [11] (Fig. 1). Similar alkylation and acylation reactions with intermediate phenoxide anions stabilized by the maximum number of stable hydrogen bonds were also reported for calixarenes having larger rings [11]. In his review [11] D. Rudkevich demonstrated in detail that intramolecular hydrogen bonds are as important as intermolecular hydrogen bonds for molecular void formation. Therefore further investigation of intramolecular hydrogen bonding in "guest-host" complexes (in particular, investigation of the energy parameters of hydrogen bonds) is of great importance in view of the influence of intramolecular hydrogen bonds on the route and rate of transformations involving cleavage and formation of covalent bonds and on the complexation ability of cavitands.I. I. Mechnikov Odessa National University; andrej_novikov@mail.ru, andrej_novikov@ukr.net.

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Section: Discussion Of Resultsmentioning

confidence: 90%

Section: Calculation Proceduresmentioning

confidence: 99%

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

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“…Other measurements in non aqueous solvents were carried by Shinkai and co-workers 12 for p-tert-butylcalix[n]arenes who found, for n = 4, an apparent pKa of 4.11. It seems that with the change of solvent for acetonitrile, the calixarene remains in the same range of acidity, when compared with ammonium ions, confirming a more acidic behavior of calixarenes in relation to the corresponding phenols, 13 despite the change in solvent properties.…”

Section: Resultsmentioning

confidence: 82%

Interaction of Calix[4]arene and Aliphatic Amines: A Combined NMR, Spectrophotometric and Conductimetric Investigation

Nachtigall¹,

Lazzarotto²,

Nome³

2002

J. Braz. Chem. Soc.

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As constantes relacionadas ao equilíbrio entre calix [4]areno e aminas alifáticas em acetonitrila foram medidas por métodos condutivimétrico e espectrométrico e as estruturas dos sais estudadas por espectroscopia de RMN. Em concentrações próximas a 10 -4 mol L -1 predominam os íons livres, enquanto que a 10 -2 mol L -1 aumenta a proporção de pares iônicos. Os valores das constantes para as reações ácido-base permitem avaliar o valor de pKa do calix[4]areno em acetonitrila, igual a 16,6 unidades de pKa. A análise do conjunto de dados está de acordo com a proposta de complexos com o íon amônio em posição exo-calix.The constants related to the equilibria between calix[4]arene and aliphatic amines in acetonitrile were measured by conductimetric and spectrophotometric methods, and the structures of the salts studied by NMR spectroscopy. In concentrations about 10 -4 mol L -1 , free ions are at higher proportion, whereas at 10 -2 mol L -1 there is an increase of ion-pairs proportion. The values of the constants found for acid-base reactions allow an evaluation of the value of pKa for calix [4]arene in acetonitrile as 16.6 pKa units. The analysis of data agrees with a proposal of exo-calix ammonium ion.

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Höhere Homologe der Calixpyrrole:meso-substituierte Calix[6]pyrrole

1998

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Eine 1,3,5‐alternate‐Konformation der Pyrrolringe weist das in einer Zweistufensynthese erstmals hergestellte Calix[6]pyrrol 1 im Kristall auf (siehe Bild). Obwohl es in Form des Adduktes 1⋅3 CH3COCH3⋅H2O⋅CHCl3 kristallisierte, befinden sich keine Solvensmoleküle im Hohlraum (Querschnittfläche ca. 60 Å2) dieses an den meso‐Positionen abwechselnd dimethyl‐ und diphenylsubstituierten Makrocyclus.

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Computational study of the structural, energetic, and acid-base properties of calix[4]arenes

Cited by 280 publications

References 2 publications

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

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

Interaction of Calix[4]arene and Aliphatic Amines: A Combined NMR, Spectrophotometric and Conductimetric Investigation

Höhere Homologe der Calixpyrrole:meso-substituierte Calix[6]pyrrole

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