Solution thermodynamics of pyridinocalix(4)arenes and monovalent cations

Namor, Angela F. Danil de

doi:10.1016/s0010-8545(99)00071-5

Cited by 17 publications

(5 citation statements)

References 40 publications

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“…Some of the reviews that emphasize the synthesis and properties of various calixarene conjugates include oxacalixarenes, homocalixarenes, and functionalization of calix[4]arenes with different donor atoms . The other reviews are based on the coordination chemistry of larger calix[ n ]arenes including their ion sensing aspects by spectral techniques, catalytic properties of metallocalixarenes, self-assembled water-soluble p -sulfonatocalix[4,5]arenes, and thermodynamics of pyridinocalix[4]arenes with monovalent cations . Ion sensing properties of fluorescent calix[4]arene derivatives with main emphasis on the photophysical aspects ,, and the detection of toxic ions are reviewed recently.…”

Section: Introductionmentioning

confidence: 99%

Ion and Molecular Recognition by Lower Rim 1,3-Di-conjugates of Calix[4]arene as Receptors

2011

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Introduction 4658 2. Functionalization at the 1,3-Positions of Calix[4]arene 4659 3. Cation Receptors 4660 3.1. Zn 2þ Recognition 4660 3.1.1. Receptors Possessing Imino-phenolic Core 4660 3.1.2. Imino-phenolic Core Linked through Triazole Moiety 4661 3.1.3. Receptors Possessing Cores Other than the Imino-phenolic Ones 4661 3.2. Cu 2þ Recognition 4663 3.2.1. Cyclic Conjugates 4663 3.2.2. Noncyclic Conjugates 4664 3.3. Monomer/Excimer Emissions in the Presence of Fe 3þ 4666 3.4. Hg 2þ Recognition 4666 3.4.1. Cyclic Conjugates 4666 3.4.2. Noncyclic Conjugates 4667 3.5. Pb 2þ Recognition 4670 3.6. Ag þ Recognition 4671 3.7. Al 3þ Recognition 4673 3.8. Recognition of Alkali Metal Ions 4673 3.9. Recognition of Alkaline Earth Metal Ions 4676 3.10. Lanthanide Ion Recognition 4678 4. Anion Receptors 4680 4.1. Inorganic Anions 4680 4.1.1. Fluoride Recognition 4680 4.1.2. Chloride Recognition 4681 4.1.3. Iodide Recognition 4682 4.1.4. Chromate Recognition 4682 4.1.5. HSO 4 À and HSO 3 À Recognition 4683 4.1.6. Phosphate Recognition 4684 4.1.6.1. Recognition of Phosphate by Uncomplexed Calix[4]arene Conjugates 4684 4.1.6.2. Recognition of Phosphate by a Metal Complex of Calix[4]arene Conjugate 4686 4.2. Organic Anions 4687 4.2.1. Acetate Recognition 4687 4.2.2. Recognition by Dicarboxylates 4688 4.3. Chiral Recognition by Calix[4]arene Conjugates 4689 5. Amino Acids and Other Molecular Recognition 4693 5.1. Recognition of Amino Acids by Uncomplexed Calix[4]arene Conjugates 4693 5.2. Recognition of Amino Acid by Metal Complexes of the Calix[4]arene Conjugates 4694 5.3. Recognition of Other Molecular Species 4695 6. Conclusions and Future Perspectives 4697 Author Information 4698 Biographies 4698 Acknowledgment 4698 List of Abbreviations 4698 References 4699

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Section: Introductionmentioning

confidence: 99%

Ion and Molecular Recognition by Lower Rim 1,3-Di-conjugates of Calix[4]arene as Receptors

2011

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“…Pyridinocalix [4]arenes have three structural isomers. The ability of these derivatives to interact with metal cations (hard or soft) appears to be largely dependent on the position of the nitrogen atoms of the pyridyl ring with respect to the ethereal oxygens, [5][6][7][8] although limited investigations have been carried out. The availability of one of these derivatives, namely, 5,-11,17,23-tetra-tert-butyl-25,26,27,28-tetra[2-(4-pyridyl)methoxy]calix(4)arene referred to throughout the text as the 4-pyridinocalix-[4]arene (1a), led to the following work goals.…”

Section: Introductionmentioning

confidence: 99%

A Calix(4)arene Pyridine Derivative and Its Monomeric Component: Structural and Thermodynamic Aspects of Their Complexation with Metal Cations

et al. 2005

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The interaction of a calix(4)arene derivative, namely 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetra[2-(4-pyridyl)methoxy]calix(4)arene, 1a, and its monomeric component, p-tert-butylphenoxy-4-pyridine, 1b, with metal cations has been investigated in acetonitrile and methanol. (1)H NMR measurements carried out in CD(3)CN show the primary role played by the pyridyl nitrogens in their complexation with metal cations. Conductance measurements demonstrated that for all cations (except mercury) the composition of the metal ion complexes of 1a is 1:1 (ligand:metal cation). However, 1a hosts two mercury cations per unit of ligand. For the monomer 1b, complexes of 2:1 (ligand:metal cation) stoichiometries are formed with the exception of Pb(2+) (1:1 composition). The thermodynamics of complexation of these systems are reported in acetonitrile. Data in methanol are limited to stability constant values for mercury(II) and these ligands. This paper demonstrates for the first time that thermodynamic data for the complexation of the monomeric component of the ligand and metal cations contribute significantly to the interpretation of systems involving cation-calixarene interactions in solution.

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“…We have recently reported the complexation of pyridinocalix(4)arene derivatives with univalent cations and the X-ray structures of the sodium and the silver complexes of the 2-pyridinocalix(4)arene derivative (perchlorate as the counterion) − Both structures have shown the presence of a molecule of acetonitrile in the hydrophobic cavity of the macrocycle.…”

Section: Introductionmentioning

confidence: 99%

New Lower Rim Calix(4)arene Derivatives with Mixed Pendent Arms and Their Complexation Properties for Alkali-Metal Cations. Structural, Electrochemical, and Thermodynamic Characterization

et al. 2002

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The synthesis and characterization ( 1 H NMR) of two new lower rim calix(4)arene derivatives containing mixed pendent arms, namely, 5,11,17,23-tetrakis(1,1-dimethylethyl)-25,27-bis[2-(methylthio)ethoxy]-26,28bis[(pyrid-2-ylmethyl)oxy]calix(4)arene (1) and 5,11,17,23-tetrakis(1,1-dimethylethyl)-25,27-bis[2-(methylthio)ethoxy]-26,28-bis[(pyrid-3-ylmethyl)oxy]calix(4)arene (2), are reported. Transfer thermodynamic parameters of these ligands to various solvents show that these macrocycles undergo selective solvation in nonaqueous media. As far as the alkali-metal cations are concerned, 1 H NMR measurements reflect that 1 in CD 3 CN discriminates against the largest cations (K + , Rb + , and Cs + ) but interacts with Li + and Na + . These interactions appears to be more pronounced with the pendent arms containing the pyridyl ring (through the ethereal oxygens and nitrogen donor atoms) than with those containing the (methylthio)ethoxy arms (only ethereal oxygens are involved). No interaction takes place between its isomer 2 and alkali-metal cations in CD 3 CN. The complexation of the lithium and the sodium complexes was established through conductometric titrations. In all cases investigated 1:1 (ligand: metal cation) complexes are formed in acetonitrile and in benzonitrile. On the basis of the semiquantitative information provided by conductance measurements regarding the strength of complexation of 1 and the sodium cation, the sodium monoacetonitrile complex of 1 was isolated and its structure determined by X-ray diffraction methods. Thus, the cation was found in the hydrophilic cavity while the hydrophobic cavity hosts a molecule of acetonitrile. The crystallographic results confirm the key role played in the chelating process by the ethereal oxygens and the pyridyl nitrogens at the 2-position in the terminal pyridyl groups, as found in solution. The thermodynamics of complexation of 1 and alkali-metal cations (Li + and Na + ) in two dipolar aprotic solvents is interpreted in terms of the solution thermodynamics of the reactants and the product. It is the availability of these data that allows interpreting the different enthalpic and entropic contributions resulting from cation, solvent, and ligand effects. Final conclusions are given.

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Solution thermodynamics of pyridinocalix(4)arenes and monovalent cations

Cited by 17 publications

References 40 publications

Ion and Molecular Recognition by Lower Rim 1,3-Di-conjugates of Calix[4]arene as Receptors

Ion and Molecular Recognition by Lower Rim 1,3-Di-conjugates of Calix[4]arene as Receptors

A Calix(4)arene Pyridine Derivative and Its Monomeric Component: Structural and Thermodynamic Aspects of Their Complexation with Metal Cations

New Lower Rim Calix(4)arene Derivatives with Mixed Pendent Arms and Their Complexation Properties for Alkali-Metal Cations. Structural, Electrochemical, and Thermodynamic Characterization

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