Ligational Properties of Two New Phenolic Aza Cages towards Proton and Alkali Metal Ions − a Theoretical and an Experimental Approach
Identifieur interne : 001073 ( Istex/Curation ); précédent : 001072; suivant : 001074Ligational Properties of Two New Phenolic Aza Cages towards Proton and Alkali Metal Ions − a Theoretical and an Experimental Approach
Auteurs : Paolo Dapporto [Italie] ; Mauro Formica ; Vieri Fusi ; Luca Giorgi ; Mauro Micheloni [Italie] ; Roberto Pontellini ; Paola Paoli [Italie] ; Patrizia Rossi [Italie]Source :
- European Journal of Inorganic Chemistry [ 1434-1948 ] ; 2001-07.
English descriptors
- Teeft :
- Acidic, Acidic proton, Alkali metal, Alkali metal ions, Anion, Aqueous solution, Aromatic proton, Atoms distances, Average conformation, Bencini, Bianchi, Bond lengths, Bridgehead nitrogen atoms, Calcd, Cation, Cd3od, Cdcl3, Chcl3, Chem, Ciampolini, Complexation, Complexation process, Conformation, Crude product, Crystal structures, Dapporto, Diethyl ether, Ethanol, Ether, Experimental conditions, Free lithium, Full paper, Fusi, Inorg, Ligand, Ligational, Ligational properties, Lithium, Macrocyclic, Macrocyclic cavity, Metal complexes, Metal ions, Methanol, Methyl, Methyl groups, Micheloni, Mmol, Molecular cavity, Nal2, Nardi, Neutral alumina, Neutral species, Nitrogen atoms, Nitrogen oxygen atoms, Organic solutions, Organic solvents, Oxygen atom, Paoli, Para position, Perkin trans, Phenol, Phenol group, Phenolate, Phenolate form, Phenolate ring, Phenolic, Phenolic group, Phenolic oxygen atom, Proton, Protonation, Protonation constants, Reaction mixture, Room temperature, Same procedure, Simulation, Slow exchange, Snapshot, Solid state, Supramolecular chem, Synthetic procedure, Time scale, Trans, Valtancoli.
Abstract
Molecular Dynamics (MD) simulations were performed on several species (anion, zwitterion, and neutral metal complexes) of two phenolic aza cages (L1 and L2) in aqueous solution. The anionic species of the smaller L1 ligand appears to be able to selectively encapsulate Li+, while the other alkaline metal ions tested (Na+ and K+) are too large to be encapsulated. The larger cage L2 does not show any selectivity; the anion binds all the alkaline metal ions. The two aza cages L1 and L2 were synthesized. Both basicity and alkali metal complex formation were studied in aqueous solution at 25 °C in 0.15 mol dm−3 Me4NCl, using potentiometric, UV/Vis‐ and NMR‐spectroscopic techniques. Both cages behave as triprotic bases in the pH range investigated; logK1 = 12.15(6), logK2 = 7.39(5), logK3 = 1.4(1) for L1 and logK1 = 11.76(5), logK2 = 8.24(5), logK3 = 2.9(2) for L2. The last proton cannot be removed because both compounds are strongly basic under the experimental conditions studied. Proton localization was studied by UV/Vis and NMR spectroscopy, both in water and nonaqueous solutions. The crystal structures of [HL1](ClO4) and [NaL2](ClO4) were determined by X‐ray analysis. The crystals of [HL1](ClO4) are triclinic, space group P(1¯); cell parameters are a = 10.3628(8), b = 11.938(1), c = 12.201(4) Å, α = 117.53(1), β = 101.25(1), γ = 102.774°. The crystals of [NaL2](ClO4) are monoclinic, space group P21/n; cell parameters are a = 10.6154(7), b = 17.0418(9), c = 14.9452(9) Å, β = 95.634(6)°.
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DOI: 10.1002/1099-0682(200107)2001:7<1763::AID-EJIC1763>3.0.CO;2-F
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Mauro Formica<affiliation><mods:affiliation>Institute of Chemical Sciences, University of Urbino, Piazza Rinascimento No. 6, 61029 Urbino, Italy, Fax: (internat.) + 39‐0722/350032</mods:affiliation><wicri:noCountry code="subField">39‐0722/350032</wicri:noCountry></affiliation><affiliation><mods:affiliation>Institute of Chemical Sciences, University of Urbino, Piazza Rinascimento No. 6, 61029 Urbino, Italy, Fax: (internat.) + 39‐0722/350032</mods:affiliation><wicri:noCountry code="subField">39‐0722/350032</wicri:noCountry></affiliation><affiliation><mods:affiliation>Institute of Chemical Sciences, University of Urbino, Piazza Rinascimento No. 6, 61029 Urbino, Italy, Fax: (internat.) + 39‐0722/350032</mods:affiliation><wicri:noCountry code="subField">39‐0722/350032</wicri:noCountry></affiliation><affiliation><mods:affiliation>Institute of Chemical Sciences, University of Urbino, Piazza Rinascimento No. 6, 61029 Urbino, Italy, Fax: (internat.) + 39‐0722/350032</mods:affiliation><wicri:noCountry code="subField">39‐0722/350032</wicri:noCountry></affiliation>Le document en format XML
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Marta No. 3, 50139 Florence, Italy</mods:affiliation><country xml:lang="fr">Italie</country><wicri:regionArea>“Sergio Stecco” Department of Energy Engineering, University of Florence, Via S. Marta No. 3, 50139 Florence</wicri:regionArea></affiliation></author><author><name sortKey="Formica, Mauro" sort="Formica, Mauro" uniqKey="Formica M" first="Mauro" last="Formica">Mauro Formica</name><affiliation><mods:affiliation>Institute of Chemical Sciences, University of Urbino, Piazza Rinascimento No. 6, 61029 Urbino, Italy, Fax: (internat.) + 39‐0722/350032</mods:affiliation><wicri:noCountry code="subField">39‐0722/350032</wicri:noCountry></affiliation></author><author><name sortKey="Fusi, Vieri" sort="Fusi, Vieri" uniqKey="Fusi V" first="Vieri" last="Fusi">Vieri Fusi</name><affiliation><mods:affiliation>Institute of Chemical Sciences, University of Urbino, Piazza Rinascimento No. 6, 61029 Urbino, Italy, Fax: (internat.) + 39‐0722/350032</mods:affiliation><wicri:noCountry code="subField">39‐0722/350032</wicri:noCountry></affiliation></author><author><name sortKey="Giorgi, Luca" sort="Giorgi, Luca" uniqKey="Giorgi L" first="Luca" last="Giorgi">Luca Giorgi</name><affiliation><mods:affiliation>Institute of Chemical Sciences, University of Urbino, Piazza Rinascimento No. 6, 61029 Urbino, Italy, Fax: (internat.) + 39‐0722/350032</mods:affiliation><wicri:noCountry code="subField">39‐0722/350032</wicri:noCountry></affiliation></author><author><name sortKey="Micheloni, Mauro" sort="Micheloni, Mauro" uniqKey="Micheloni M" first="Mauro" last="Micheloni">Mauro Micheloni</name><affiliation><mods:affiliation>Institute of Chemical Sciences, University of Urbino, Piazza Rinascimento No. 6, 61029 Urbino, Italy, Fax: (internat.) + 39‐0722/350032</mods:affiliation></affiliation><affiliation wicri:level="1"><mods:affiliation>E-mail: mauro@chim.uniurb.it</mods:affiliation><country wicri:rule="url">Italie</country></affiliation></author><author><name sortKey="Pontellini, Roberto" sort="Pontellini, Roberto" uniqKey="Pontellini R" first="Roberto" last="Pontellini">Roberto Pontellini</name><affiliation><mods:affiliation>Institute of Chemical Sciences, University of Urbino, Piazza Rinascimento No. 6, 61029 Urbino, Italy, Fax: (internat.) + 39‐0722/350032</mods:affiliation><wicri:noCountry code="subField">39‐0722/350032</wicri:noCountry></affiliation></author><author><name sortKey="Paoli, Paola" sort="Paoli, Paola" uniqKey="Paoli P" first="Paola" last="Paoli">Paola Paoli</name><affiliation wicri:level="1"><mods:affiliation>“Sergio Stecco” Department of Energy Engineering, University of Florence, Via S. Marta No. 3, 50139 Florence, Italy</mods:affiliation><country xml:lang="fr">Italie</country><wicri:regionArea>“Sergio Stecco” Department of Energy Engineering, University of Florence, Via S. Marta No. 3, 50139 Florence</wicri:regionArea></affiliation></author><author><name sortKey="Rossi, Patrizia" sort="Rossi, Patrizia" uniqKey="Rossi P" first="Patrizia" last="Rossi">Patrizia Rossi</name><affiliation wicri:level="1"><mods:affiliation>“Sergio Stecco” Department of Energy Engineering, University of Florence, Via S. Marta No. 3, 50139 Florence, Italy</mods:affiliation><country xml:lang="fr">Italie</country><wicri:regionArea>“Sergio Stecco” Department of Energy Engineering, University of Florence, Via S. Marta No. 3, 50139 Florence</wicri:regionArea></affiliation></author></analytic><monogr></monogr><series><title level="j" type="main">European Journal of Inorganic Chemistry</title><title level="j" type="alt">EUROPEAN JOURNAL OF INORGANIC CHEMISTRY</title><idno type="ISSN">1434-1948</idno><idno type="eISSN">1099-0682</idno><imprint><biblScope unit="vol">2001</biblScope><biblScope unit="issue">7</biblScope><biblScope unit="page" from="1763">1763</biblScope><biblScope unit="page" to="1774">1774</biblScope><biblScope unit="page-count">12</biblScope><publisher>WILEY‐VCH Verlag GmbH</publisher><pubPlace>Weinheim</pubPlace><date type="published" when="2001-07">2001-07</date></imprint><idno type="ISSN">1434-1948</idno></series></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">1434-1948</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="Teeft" xml:lang="en"><term>Acidic</term><term>Acidic proton</term><term>Alkali metal</term><term>Alkali metal ions</term><term>Anion</term><term>Aqueous solution</term><term>Aromatic proton</term><term>Atoms distances</term><term>Average conformation</term><term>Bencini</term><term>Bianchi</term><term>Bond lengths</term><term>Bridgehead nitrogen atoms</term><term>Calcd</term><term>Cation</term><term>Cd3od</term><term>Cdcl3</term><term>Chcl3</term><term>Chem</term><term>Ciampolini</term><term>Complexation</term><term>Complexation process</term><term>Conformation</term><term>Crude product</term><term>Crystal structures</term><term>Dapporto</term><term>Diethyl ether</term><term>Ethanol</term><term>Ether</term><term>Experimental conditions</term><term>Free lithium</term><term>Full paper</term><term>Fusi</term><term>Inorg</term><term>Ligand</term><term>Ligational</term><term>Ligational properties</term><term>Lithium</term><term>Macrocyclic</term><term>Macrocyclic cavity</term><term>Metal complexes</term><term>Metal ions</term><term>Methanol</term><term>Methyl</term><term>Methyl groups</term><term>Micheloni</term><term>Mmol</term><term>Molecular cavity</term><term>Nal2</term><term>Nardi</term><term>Neutral alumina</term><term>Neutral species</term><term>Nitrogen atoms</term><term>Nitrogen oxygen atoms</term><term>Organic solutions</term><term>Organic solvents</term><term>Oxygen atom</term><term>Paoli</term><term>Para position</term><term>Perkin trans</term><term>Phenol</term><term>Phenol group</term><term>Phenolate</term><term>Phenolate form</term><term>Phenolate ring</term><term>Phenolic</term><term>Phenolic group</term><term>Phenolic oxygen atom</term><term>Proton</term><term>Protonation</term><term>Protonation constants</term><term>Reaction mixture</term><term>Room temperature</term><term>Same procedure</term><term>Simulation</term><term>Slow exchange</term><term>Snapshot</term><term>Solid state</term><term>Supramolecular chem</term><term>Synthetic procedure</term><term>Time scale</term><term>Trans</term><term>Valtancoli</term></keywords></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">Molecular Dynamics (MD) simulations were performed on several species (anion, zwitterion, and neutral metal complexes) of two phenolic aza cages (L1 and L2) in aqueous solution. The anionic species of the smaller L1 ligand appears to be able to selectively encapsulate Li+, while the other alkaline metal ions tested (Na+ and K+) are too large to be encapsulated. The larger cage L2 does not show any selectivity; the anion binds all the alkaline metal ions. The two aza cages L1 and L2 were synthesized. Both basicity and alkali metal complex formation were studied in aqueous solution at 25 °C in 0.15 mol dm−3 Me4NCl, using potentiometric, UV/Vis‐ and NMR‐spectroscopic techniques. Both cages behave as triprotic bases in the pH range investigated; logK1 = 12.15(6), logK2 = 7.39(5), logK3 = 1.4(1) for L1 and logK1 = 11.76(5), logK2 = 8.24(5), logK3 = 2.9(2) for L2. The last proton cannot be removed because both compounds are strongly basic under the experimental conditions studied. Proton localization was studied by UV/Vis and NMR spectroscopy, both in water and nonaqueous solutions. The crystal structures of [HL1](ClO4) and [NaL2](ClO4) were determined by X‐ray analysis. The crystals of [HL1](ClO4) are triclinic, space group P(1¯); cell parameters are a = 10.3628(8), b = 11.938(1), c = 12.201(4) Å, α = 117.53(1), β = 101.25(1), γ = 102.774°. The crystals of [NaL2](ClO4) are monoclinic, space group P21/n; cell parameters are a = 10.6154(7), b = 17.0418(9), c = 14.9452(9) Å, β = 95.634(6)°.</div></front></TEI></record>Pour manipuler ce document sous Unix (Dilib)
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