Lower rim calix(4)arene ketone derivatives and their interaction with alkali metal cations. Structural and thermodynamic (solution and complexation) characterisation of the tetraphenyl ketone derivative and its sodium complex

Namor, Angela F. Danil de; Kowalska, Dorota; Castellano, Eduardo E.; Piro, Oscar E.; Velarde, Félix J. Sueros; Salas, José Villanueva

doi:10.1039/b104355m

Cited by 26 publications

(40 citation statements)

References 32 publications

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“…The smallest variations are recorded for the protons of the alkyl residues (t-Bu, Ad and Ph) attached to the ketone function and tert-butyl groups. Similar observations have been made for dihomooxa diethylamide [20] and closely related calix [4]arene derivatives [12,13,32,33]. A closer examination of the spectral changes upon complexation indicates considerable differences between the alkali and alkaline earth cation series.…”

Section: Proton Nmr Studiessupporting

confidence: 63%

Complexation and Transport of Alkali and Alkaline Earth Metal Cations byp-tert-Butyldihomooxacalix[4]arene Tetraketone Derivatives

Marcos

Félix

Ascenso³

et al. 2006

Supramolecular Chemistry

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The binding properties of three p-tert-butyldihomooxacalix[4]arene tetraketone derivatives (tert-butyl 2b, adamantyl 2c and phenyl 2d) in the cone conformation and one derivative (methyl 2a) in a partial cone conformation, towards alkali and alkaline earth metal cations have been established by extraction studies of metal picrates from water into dichloromethane, stability constant measurements in methanol and acetonitrile, and by 1 H NMR spectrometry. Transport experiments of metal picrates through a dichloromethane membrane were also performed. The results are compared to those obtained with closely-related calix[n]arene derivatives (n 5 4 and 5) and discussed in terms of the substituents, size and conformational effects. Methylketone 2a is a poor binder for all the cations studied, due to its partial cone conformation. Ketones 2b, 2c and 2d show high extraction and complexation levels for the alkali cations, with similar profiles and preference for K 1 and Na 1 (plateau selectivity). Towards alkaline earth cations, these ketones show a strong peak selectivity for Ba 21 in extraction, but a plateau selectivity for Ca 21 , Sr 21 and Ba 21 in complexation. The nature of the substituent attached to the ketone function has some influence on their binding properties, with phenylketone 2d being a slightly weaker binder than ketones 2b and 2c. 1 H NMR titrations confirm the formation of 1:1 complexes between the ketones and the cations studied, also indicating that they should be located inside the cavity defined by the phenoxy and carbonyl oxygen atoms. Ketones 2b, 2c and 2d show transport rates that do not follow, in general, the same trends observed in extraction and complexation.

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Section: Proton Nmr Studiessupporting

confidence: 63%

Complexation and Transport of Alkali and Alkaline Earth Metal Cations byp-tert-Butyldihomooxacalix[4]arene Tetraketone Derivatives

Marcos

Félix

Ascenso³

et al. 2006

Supramolecular Chemistry

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“…Her work in this area, prior to 2000, has been extensively reviewed [57]. She has published a number of detailed studies, since 2000, on a range of calix [4]arene derivatives including complexation studies of calix [4]arene ketone derivatives with sodium ions [58,59], complexation of calix [4]arene ester, ketone and acetamide derivatives with lanthanides [60], complexation of calix [4]arene pyridine derivatives with lead and mercury cations [61], complexation of calix [4]arene amines and amides with lanthanides [62], complexation of a partially substituted calix [4]arene aminophosphate derivative with a range of cations [63], complexation of calix [4]arene ester and ketone derivatives with lead and cadmium ions [64], complexation of calix [4]arene with mixed pendant arms (di-functionalised with ethylethanoate and ethylthioethoxy groups) with a range of cations [65,66]. Many of these studies offered a comprehensive investigation into the role of solvation of host and guest species in a given medium, and indeed medium effects feature as one of the main areas of focus of investigation in all of these studies.…”

Section: Complexationmentioning

confidence: 99%

Coordination chemistry of calix[4]arene derivatives with lower rim functionalisation and their applications

Creaven

Donlon

McGinley

2009

Coordination Chemistry Reviews

209

150

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“…N,N-dimethylformamide and dimethyl sulfoxide) were rarely investigated. [21][22][23] Therefore, we made an effort to study the alkali metal complexation by calixarenes in such media, paying special attention to solvent effects on the thermodynamics of the studied reactions.…”

Section: Introductionmentioning

confidence: 99%

Complexation of Alkali Metal Cations by a Tertiary Amide Calix[4]Arene Derivative in Strongly Cation Solvating Solvents

et al. 2017

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The complexation of alkali-metal cations with calix [4]arene tertiary amide derivative (L) was studied in N-methylformamide (NMF), N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO) by means of microcalorimetric and UV spectrophotometric titrations. The Gibbs energies, enthalpies, and entropies for transfer of reactants and products from N-methylformamide to other solvents were determined. Favorable enthalpic contribution to overall stability was found to be the most important for all complexation reactions, especially in the case of NaL + formation, resulting in an affinity peak of L for this cation. The complexation entropy changes were always unfavorable. The ligand dissolution was endothermic in all solvents, accompanied by positive solution entropy. The highest complex stability constants were determined in NMF, whereas in DMSO the affinity of L towards alkali metal cations was the lowest. An interesting interplay between the transfer enthalpies and entropies of the reactants and complexes was revealed and discussed in detail.

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Lower rim calix(4)arene ketone derivatives and their interaction with alkali metal cations. Structural and thermodynamic (solution and complexation) characterisation of the tetraphenyl ketone derivative and its sodium complex

Cited by 26 publications

References 32 publications

Complexation and Transport of Alkali and Alkaline Earth Metal Cations byp-tert-Butyldihomooxacalix[4]arene Tetraketone Derivatives

Complexation and Transport of Alkali and Alkaline Earth Metal Cations byp-tert-Butyldihomooxacalix[4]arene Tetraketone Derivatives

Coordination chemistry of calix[4]arene derivatives with lower rim functionalisation and their applications

Complexation of Alkali Metal Cations by a Tertiary Amide Calix[4]Arene Derivative in Strongly Cation Solvating Solvents

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