Allosteric Tuning of the Intra‐Cavity Binding Properties of a Calix[6]arene through External Binding to a ZnII Center Coordinated to Amino Side Chains
Identifieur interne : 000C83 ( Istex/Corpus ); précédent : 000C82; suivant : 000C84Allosteric Tuning of the Intra‐Cavity Binding Properties of a Calix[6]arene through External Binding to a ZnII Center Coordinated to Amino Side Chains
Auteurs : Ulrich Darbost ; Olivier Sénèque ; Yun Li ; Gildas Bertho ; Jérôme Marrot ; Marie-Noëlle Rager ; Olivia Reinaud ; Ivan JabinSource :
- Chemistry – A European Journal [ 0947-6539 ] ; 2007-02-23.
English descriptors
Abstract
Molecular recognition by calix[6]arene‐based receptors bearing three primary alkylamino side chain arms (1) is described. Complexation of ZnII ion provides the dinuclear μ‐hydroxo complex ${{\bf 2}{{{\rm OH}\hfill \atop {\rm G}\hfill}}}$, XRD characterization of which, together with solution studies, provided evidence of its hosting of neutral polar organic guests G. Treatment of this complex with a carboxylic acid or a sulfonamide (XH) results in the formation of mononuclear species ${{\bf 3}{{{\rm X}\hfill \atop {\rm G}\hfill}}}$, one of which (X = Cl) has been characterized by XRD. A dicationic complex ${{\bf 3}{{{\rm RNH}{_{2}}\hfill \atop {\rm G}\hfill}}}$ is obtained upon treatment of ${{\bf 2}{{{\rm OH}\hfill \atop {\rm G}\hfill}}}$ with a mixture of an alkylamine and a strong acid. Each of these ZnII complexes features a tetrahedral metal ion bound to the three amino arms of ligand 1 and to an exogenous ligand (either HO−, X−, or RNH2) sitting outside of the cavity. As a result, the metal ion structures the calixarene core, constraining it in a cone conformation suitable for guest hosting. The receptor properties of these compounds have been explored in detail and are compared with those of the trisammonium receptor ${{\bf 1}{{3\,{\rm H}{^{+}}\hfill \atop {\rm G}\hfill}}}$, based on the same calixarene core, as well as those of the trisimidazole‐based dicationic Zn funnel complexes. This study reveals very different host properties, in spite of the common hydrophobic, π‐basic, and hydrogen‐bonding acceptor properties of the calixarene cores. A harder external ligand produces a less polarized receptor that is consequently particularly sensitive to the hydrogen‐bonding ability of its guest. The less electron‐rich the apical ligand, and a fortiori the trisammonium host, the more sensitive the receptor to the dipole moment of the guest. All this stands in contrast with the funnel Zn complexes, in which the coordination link plays a dominant role. It is also shown that the asymmetry of an exo‐coordinated enantiopure amino ligand is sensed by the guest. This supramolecular system nicely illustrates how the receptor properties of a hydrophobic cavity can be allosterically tuned by the environment.
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DOI: 10.1002/chem.200601040
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ISTEX:F49D95EB94D7748EF4C0EA0BD4DF59A593E68704Le document en format XML
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xml:lang="en">Allosteric Tuning of the Intra‐Cavity Binding Properties of a Calix[6]arene through External Binding to a ZnII Center Coordinated to Amino Side Chains</title><author><name sortKey="Darbost, Ulrich" sort="Darbost, Ulrich" uniqKey="Darbost U" first="Ulrich" last="Darbost">Ulrich Darbost</name><affiliation><mods:affiliation>Unité de Recherche en Chimie Organique et Macromoléculaire (URCOM), Université du Havre, 25 rue Philippe Lebon, BP 540, 76058 Le Havre cedex, France, Fax: (+33) 232‐744‐391</mods:affiliation></affiliation></author><author><name sortKey="Seneque, Olivier" sort="Seneque, Olivier" uniqKey="Seneque O" first="Olivier" last="Sénèque">Olivier Sénèque</name><affiliation><mods:affiliation>Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, UMR CNRS 8601, Université René Descartes, 45 rue des Saints Pères, 75270 Paris cedex 06, France, Fax: (+33) 142‐868‐387</mods:affiliation></affiliation></author><author><name sortKey="Li, Yun" sort="Li, Yun" uniqKey="Li Y" first="Yun" last="Li">Yun Li</name><affiliation><mods:affiliation>Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, UMR CNRS 8601, Université René Descartes, 45 rue des Saints Pères, 75270 Paris cedex 06, France, Fax: (+33) 142‐868‐387</mods:affiliation></affiliation></author><author><name sortKey="Bertho, Gildas" sort="Bertho, Gildas" uniqKey="Bertho G" first="Gildas" last="Bertho">Gildas Bertho</name><affiliation><mods:affiliation>Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, UMR CNRS 8601, Université René Descartes, 45 rue des Saints Pères, 75270 Paris cedex 06, France, Fax: (+33) 142‐868‐387</mods:affiliation></affiliation></author><author><name sortKey="Marrot, Jerome" sort="Marrot, Jerome" uniqKey="Marrot J" first="Jérôme" last="Marrot">Jérôme Marrot</name><affiliation><mods:affiliation>Institut Lavoisier, UMR CNRS 8180, Université de Versailles St‐Quentin en Yvelines, 45 av. des Etats‐Unis, 78035 Versailles cedex, France</mods:affiliation></affiliation></author><author><name sortKey="Rager, Marie Oelle" sort="Rager, Marie Oelle" uniqKey="Rager M" first="Marie-Noëlle" last="Rager">Marie-Noëlle Rager</name><affiliation><mods:affiliation>Service de RMN, Ecole Nationale Supérieure de Chimie de Paris (ENSCP), 11 rue Pierre et Marie Curie, 75231 Paris Cedex 05, France</mods:affiliation></affiliation></author><author><name sortKey="Reinaud, Olivia" sort="Reinaud, Olivia" uniqKey="Reinaud O" first="Olivia" last="Reinaud">Olivia Reinaud</name><affiliation><mods:affiliation>Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, UMR CNRS 8601, Université René Descartes, 45 rue des Saints Pères, 75270 Paris cedex 06, France, Fax: (+33) 142‐868‐387</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: Olivia.Reinaud@univ‐paris5.fr</mods:affiliation></affiliation></author><author><name sortKey="Jabin, Ivan" sort="Jabin, Ivan" uniqKey="Jabin I" first="Ivan" last="Jabin">Ivan Jabin</name><affiliation><mods:affiliation>Unité de Recherche en Chimie Organique et Macromoléculaire (URCOM), Université du Havre, 25 rue Philippe Lebon, BP 540, 76058 Le Havre cedex, France, Fax: (+33) 232‐744‐391</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: ivan.jabin@univ‐lehavre.fr</mods:affiliation></affiliation></author></analytic><monogr></monogr><series><title level="j">Chemistry – A European Journal</title><title level="j" type="abbrev">Chemistry – A European Journal</title><idno type="ISSN">0947-6539</idno><idno type="eISSN">1521-3765</idno><imprint><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><date type="published" when="2007-02-23">2007-02-23</date><biblScope unit="volume">13</biblScope><biblScope unit="issue">7</biblScope><biblScope unit="page" from="2078">2078</biblScope><biblScope unit="page" to="2088">2088</biblScope></imprint><idno type="ISSN">0947-6539</idno></series><idno type="istex">F49D95EB94D7748EF4C0EA0BD4DF59A593E68704</idno><idno type="DOI">10.1002/chem.200601040</idno><idno type="ArticleID">CHEM200601040</idno></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0947-6539</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>allosterism</term><term>calixarenes</term><term>host–guest systems</term><term>supramolecular chemistry</term><term>zinc</term></keywords></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract">Molecular recognition by calix[6]arene‐based receptors bearing three primary alkylamino side chain arms (1) is described. Complexation of ZnII ion provides the dinuclear μ‐hydroxo complex ${{\bf 2}{{{\rm OH}\hfill \atop {\rm G}\hfill}}}$, XRD characterization of which, together with solution studies, provided evidence of its hosting of neutral polar organic guests G. Treatment of this complex with a carboxylic acid or a sulfonamide (XH) results in the formation of mononuclear species ${{\bf 3}{{{\rm X}\hfill \atop {\rm G}\hfill}}}$, one of which (X = Cl) has been characterized by XRD. A dicationic complex ${{\bf 3}{{{\rm RNH}{_{2}}\hfill \atop {\rm G}\hfill}}}$ is obtained upon treatment of ${{\bf 2}{{{\rm OH}\hfill \atop {\rm G}\hfill}}}$ with a mixture of an alkylamine and a strong acid. Each of these ZnII complexes features a tetrahedral metal ion bound to the three amino arms of ligand 1 and to an exogenous ligand (either HO−, X−, or RNH2) sitting outside of the cavity. As a result, the metal ion structures the calixarene core, constraining it in a cone conformation suitable for guest hosting. The receptor properties of these compounds have been explored in detail and are compared with those of the trisammonium receptor ${{\bf 1}{{3\,{\rm H}{^{+}}\hfill \atop {\rm G}\hfill}}}$, based on the same calixarene core, as well as those of the trisimidazole‐based dicationic Zn funnel complexes. This study reveals very different host properties, in spite of the common hydrophobic, π‐basic, and hydrogen‐bonding acceptor properties of the calixarene cores. A harder external ligand produces a less polarized receptor that is consequently particularly sensitive to the hydrogen‐bonding ability of its guest. The less electron‐rich the apical ligand, and a fortiori the trisammonium host, the more sensitive the receptor to the dipole moment of the guest. All this stands in contrast with the funnel Zn complexes, in which the coordination link plays a dominant role. It is also shown that the asymmetry of an exo‐coordinated enantiopure amino ligand is sensed by the guest. This supramolecular system nicely illustrates how the receptor properties of a hydrophobic cavity can be allosterically tuned by the environment.</div></front></TEI><istex><corpusName>wiley</corpusName><author><json:item><name>Ulrich Darbost Dr.</name><affiliations><json:string>Unité de Recherche en Chimie Organique et Macromoléculaire (URCOM), Université du Havre, 25 rue Philippe Lebon, BP 540, 76058 Le Havre cedex, France, Fax: (+33) 232‐744‐391</json:string></affiliations></json:item><json:item><name>Olivier Sénèque Dr.</name><affiliations><json:string>Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, UMR CNRS 8601, Université René Descartes, 45 rue des Saints Pères, 75270 Paris cedex 06, France, Fax: (+33) 142‐868‐387</json:string></affiliations></json:item><json:item><name>Yun Li Dr.</name><affiliations><json:string>Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, UMR CNRS 8601, Université René Descartes, 45 rue des Saints Pères, 75270 Paris cedex 06, France, Fax: (+33) 142‐868‐387</json:string></affiliations></json:item><json:item><name>Gildas Bertho Dr.</name><affiliations><json:string>Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, UMR CNRS 8601, Université René Descartes, 45 rue des Saints Pères, 75270 Paris cedex 06, France, Fax: (+33) 142‐868‐387</json:string></affiliations></json:item><json:item><name>Jérôme Marrot</name><affiliations><json:string>Institut Lavoisier, UMR CNRS 8180, Université de Versailles St‐Quentin en Yvelines, 45 av. des Etats‐Unis, 78035 Versailles cedex, France</json:string></affiliations></json:item><json:item><name>Marie‐Noëlle Rager</name><affiliations><json:string>Service de RMN, Ecole Nationale Supérieure de Chimie de Paris (ENSCP), 11 rue Pierre et Marie Curie, 75231 Paris Cedex 05, France</json:string></affiliations></json:item><json:item><name>Olivia Reinaud Prof.</name><affiliations><json:string>Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, UMR CNRS 8601, Université René Descartes, 45 rue des Saints Pères, 75270 Paris cedex 06, France, Fax: (+33) 142‐868‐387</json:string><json:string>E-mail: Olivia.Reinaud@univ‐paris5.fr</json:string></affiliations></json:item><json:item><name>Ivan Jabin Dr.</name><affiliations><json:string>Unité de Recherche en Chimie Organique et Macromoléculaire (URCOM), Université du Havre, 25 rue Philippe Lebon, BP 540, 76058 Le Havre cedex, France, Fax: (+33) 232‐744‐391</json:string><json:string>E-mail: ivan.jabin@univ‐lehavre.fr</json:string></affiliations></json:item></author><subject><json:item><lang><json:string>eng</json:string></lang><value>allosterism</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>calixarenes</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>host–guest systems</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>supramolecular chemistry</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>zinc</value></json:item></subject><articleId><json:string>CHEM200601040</json:string></articleId><language><json:string>eng</json:string></language><originalGenre><json:string>article</json:string></originalGenre><qualityIndicators><score>8</score><pdfVersion>1.3</pdfVersion><pdfPageSize>595 x 842 pts (A4)</pdfPageSize><refBibsNative>true</refBibsNative><keywordCount>5</keywordCount><abstractCharCount>2237</abstractCharCount><pdfWordCount>7075</pdfWordCount><pdfCharCount>41479</pdfCharCount><pdfPageCount>11</pdfPageCount><abstractWordCount>336</abstractWordCount></qualityIndicators><title>Allosteric Tuning of the Intra‐Cavity Binding Properties of a Calix[6]arene through External Binding to a ZnII Center Coordinated to Amino Side 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ZnII Center Coordinated to Amino Side Chains</title></titleStmt><publicationStmt><authority>ISTEX</authority><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><availability><p>Copyright © 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</p></availability><date>2007</date></publicationStmt><notesStmt><note>Région Haute‐Normandie</note></notesStmt><sourceDesc><biblStruct type="inbook"><analytic><title level="a" type="main" xml:lang="en">Allosteric Tuning of the Intra‐Cavity Binding Properties of a Calix[6]arene through External Binding to a ZnII Center Coordinated to Amino Side Chains</title><author xml:id="author-1"><persName><forename type="first">Ulrich</forename><surname>Darbost</surname></persName><roleName type="degree">Dr.</roleName><affiliation>Unité de Recherche en Chimie Organique et Macromoléculaire (URCOM), Université du Havre, 25 rue Philippe Lebon, BP 540, 76058 Le Havre cedex, France, Fax: (+33) 232‐744‐391</affiliation></author><author xml:id="author-2"><persName><forename type="first">Olivier</forename><surname>Sénèque</surname></persName><roleName type="degree">Dr.</roleName><affiliation>Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, UMR CNRS 8601, Université René Descartes, 45 rue des Saints Pères, 75270 Paris cedex 06, France, Fax: (+33) 142‐868‐387</affiliation></author><author xml:id="author-3"><persName><forename type="first">Yun</forename><surname>Li</surname></persName><roleName type="degree">Dr.</roleName><affiliation>Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, UMR CNRS 8601, Université René Descartes, 45 rue des Saints Pères, 75270 Paris cedex 06, France, Fax: (+33) 142‐868‐387</affiliation></author><author xml:id="author-4"><persName><forename type="first">Gildas</forename><surname>Bertho</surname></persName><roleName type="degree">Dr.</roleName><affiliation>Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, UMR CNRS 8601, Université René Descartes, 45 rue des Saints Pères, 75270 Paris cedex 06, France, Fax: (+33) 142‐868‐387</affiliation></author><author xml:id="author-5"><persName><forename type="first">Jérôme</forename><surname>Marrot</surname></persName><affiliation>Institut Lavoisier, UMR CNRS 8180, Université de Versailles St‐Quentin en Yvelines, 45 av. des Etats‐Unis, 78035 Versailles cedex, France</affiliation></author><author xml:id="author-6"><persName><forename type="first">Marie‐Noëlle</forename><surname>Rager</surname></persName><affiliation>Service de RMN, Ecole Nationale Supérieure de Chimie de Paris (ENSCP), 11 rue Pierre et Marie Curie, 75231 Paris Cedex 05, France</affiliation></author><author xml:id="author-7"><persName><forename type="first">Olivia</forename><surname>Reinaud</surname></persName><roleName type="degree">Prof.</roleName><email>Olivia.Reinaud@univ‐paris5.fr</email><affiliation>Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, UMR CNRS 8601, Université René Descartes, 45 rue des Saints Pères, 75270 Paris cedex 06, France, Fax: (+33) 142‐868‐387</affiliation></author><author xml:id="author-8"><persName><forename type="first">Ivan</forename><surname>Jabin</surname></persName><roleName type="degree">Dr.</roleName><email>ivan.jabin@univ‐lehavre.fr</email><affiliation>Unité de Recherche en Chimie Organique et Macromoléculaire (URCOM), Université du Havre, 25 rue Philippe Lebon, BP 540, 76058 Le Havre cedex, France, Fax: (+33) 232‐744‐391</affiliation></author></analytic><monogr><title level="j">Chemistry – A European Journal</title><title level="j" type="abbrev">Chemistry – A European Journal</title><idno type="pISSN">0947-6539</idno><idno type="eISSN">1521-3765</idno><idno type="DOI">10.1002/(ISSN)1521-3765</idno><imprint><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><date type="published" when="2007-02-23"></date><biblScope unit="volume">13</biblScope><biblScope unit="issue">7</biblScope><biblScope unit="page" from="2078">2078</biblScope><biblScope unit="page" to="2088">2088</biblScope></imprint></monogr><idno type="istex">F49D95EB94D7748EF4C0EA0BD4DF59A593E68704</idno><idno type="DOI">10.1002/chem.200601040</idno><idno type="ArticleID">CHEM200601040</idno></biblStruct></sourceDesc></fileDesc><profileDesc><creation><date>2007</date></creation><langUsage><language ident="en">en</language></langUsage><abstract><p>Molecular recognition by calix[6]arene‐based receptors bearing three primary alkylamino side chain arms (1) is described. Complexation of ZnII ion provides the dinuclear μ‐hydroxo complex ${{\bf 2}{{{\rm OH}\hfill \atop {\rm G}\hfill}}}$, XRD characterization of which, together with solution studies, provided evidence of its hosting of neutral polar organic guests G. Treatment of this complex with a carboxylic acid or a sulfonamide (XH) results in the formation of mononuclear species ${{\bf 3}{{{\rm X}\hfill \atop {\rm G}\hfill}}}$, one of which (X = Cl) has been characterized by XRD. A dicationic complex ${{\bf 3}{{{\rm RNH}{_{2}}\hfill \atop {\rm G}\hfill}}}$ is obtained upon treatment of ${{\bf 2}{{{\rm OH}\hfill \atop {\rm G}\hfill}}}$ with a mixture of an alkylamine and a strong acid. Each of these ZnII complexes features a tetrahedral metal ion bound to the three amino arms of ligand 1 and to an exogenous ligand (either HO−, X−, or RNH2) sitting outside of the cavity. As a result, the metal ion structures the calixarene core, constraining it in a cone conformation suitable for guest hosting. The receptor properties of these compounds have been explored in detail and are compared with those of the trisammonium receptor ${{\bf 1}{{3\,{\rm H}{^{+}}\hfill \atop {\rm G}\hfill}}}$, based on the same calixarene core, as well as those of the trisimidazole‐based dicationic Zn funnel complexes. This study reveals very different host properties, in spite of the common hydrophobic, π‐basic, and hydrogen‐bonding acceptor properties of the calixarene cores. A harder external ligand produces a less polarized receptor that is consequently particularly sensitive to the hydrogen‐bonding ability of its guest. The less electron‐rich the apical ligand, and a fortiori the trisammonium host, the more sensitive the receptor to the dipole moment of the guest. All this stands in contrast with the funnel Zn complexes, in which the coordination link plays a dominant role. It is also shown that the asymmetry of an exo‐coordinated enantiopure amino ligand is sensed by the guest. This supramolecular system nicely illustrates how the receptor properties of a hydrophobic cavity can be allosterically tuned by the environment.</p></abstract><abstract><p>External tuning of the host properties of calix[6]arene Zn complexes: ZnII coordination by a calix[6]arene bearing three primary amino arms has been explored and found to result in tetrahedral complexes with the labile site oriented toward the outside of the cavity. The resulting calixarene cone acts as a polarized receptor, the host properties of which can be allosterically tuned through the external binding of either anionic or neutral ligands to the capping ZnII ion (see scheme).</p></abstract><textClass xml:lang="en"><keywords scheme="keyword"><list><head>keywords</head><item><term>allosterism</term></item><item><term>calixarenes</term></item><item><term>host–guest systems</term></item><item><term>supramolecular chemistry</term></item><item><term>zinc</term></item></list></keywords></textClass><textClass><keywords scheme="Journal Subject"><list><head>article-category</head><item><term>Full Paper</term></item></list></keywords></textClass></profileDesc><revisionDesc><change when="2006-07-19">Received</change><change when="2007-02-23">Published</change></revisionDesc></teiHeader></istex:fulltextTEI><json:item><original>false</original><mimetype>text/plain</mimetype><extension>txt</extension><uri>https://api.istex.fr/document/F49D95EB94D7748EF4C0EA0BD4DF59A593E68704/fulltext/txt</uri></json:item></fulltext><metadata><istex:metadataXml wicri:clean="Wiley, elements deleted: body"><istex:xmlDeclaration>version="1.0" encoding="UTF-8" standalone="yes"</istex:xmlDeclaration><istex:document><component version="2.0" type="serialArticle" xml:lang="en"><header><publicationMeta level="product"><publisherInfo><publisherName>WILEY‐VCH Verlag</publisherName><publisherLoc>Weinheim</publisherLoc></publisherInfo><doi registered="yes">10.1002/(ISSN)1521-3765</doi><issn type="print">0947-6539</issn><issn type="electronic">1521-3765</issn><idGroup><id type="product" value="CHEM"></id></idGroup><titleGroup><title type="main" xml:lang="en">Chemistry – A European Journal</title><title type="short">Chemistry – A European Journal</title></titleGroup></publicationMeta><publicationMeta level="part" position="70"><doi origin="wiley" registered="yes">10.1002/chem.v13:7</doi><numberingGroup><numbering type="journalVolume" number="13">13</numbering><numbering type="journalIssue">7</numbering></numberingGroup><coverDate startDate="2007-02-23">February 23, 2007</coverDate></publicationMeta><publicationMeta level="unit" type="article" position="20" status="forIssue"><doi origin="wiley" registered="yes">10.1002/chem.200601040</doi><idGroup><id type="unit" value="CHEM200601040"></id></idGroup><countGroup><count type="pageTotal" number="11"></count></countGroup><titleGroup><title type="articleCategory">Full Paper</title><title type="tocHeading1">Full Papers</title></titleGroup><copyright ownership="publisher">Copyright © 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</copyright><eventGroup><event type="manuscriptReceived" date="2006-07-19"></event><event type="firstOnline" date="2006-12-04"></event><event type="publishedOnlineFinalForm" date="2007-02-08"></event><event type="xmlConverted" agent="Converter:JWSART34_TO_WML3G version:2.3.6 mode:FullText source:FullText result:FullText mathml2tex" date="2010-05-18"></event><event type="xmlConverted" agent="Converter:WILEY_ML3G_TO_WILEY_ML3GV2 version:3.8.8" date="2014-01-09"></event><event type="xmlConverted" agent="Converter:WML3G_To_WML3G version:4.1.7 mode:FullText,remove_FC" date="2014-10-15"></event></eventGroup><numberingGroup><numbering type="pageFirst">2078</numbering><numbering type="pageLast">2088</numbering></numberingGroup><objectNameGroup><objectName elementName="figure">Scheme</objectName></objectNameGroup><linkGroup><link type="toTypesetVersion" href="file:CHEM.CHEM200601040.pdf"></link></linkGroup></publicationMeta><contentMeta><countGroup><count type="figureTotal" number="10"></count><count type="tableTotal" number="2"></count><count type="referenceTotal" number="51"></count></countGroup><titleGroup><title type="main" xml:lang="en">Allosteric Tuning of the Intra‐Cavity Binding Properties of a Calix[6]arene through External Binding to a Zn<sup>II</sup> Center Coordinated to Amino Side Chains</title></titleGroup><creators><creator xml:id="au1" creatorRole="author" affiliationRef="#aa"><personName><givenNames>Ulrich</givenNames><familyName>Darbost</familyName><degrees>Dr.</degrees></personName></creator><creator xml:id="au2" creatorRole="author" affiliationRef="#ab"><personName><givenNames>Olivier</givenNames><familyName>Sénèque</familyName><degrees>Dr.</degrees></personName></creator><creator xml:id="au3" creatorRole="author" affiliationRef="#ab"><personName><givenNames>Yun</givenNames><familyName>Li</familyName><degrees>Dr.</degrees></personName></creator><creator xml:id="au4" creatorRole="author" affiliationRef="#ab"><personName><givenNames>Gildas</givenNames><familyName>Bertho</familyName><degrees>Dr.</degrees></personName></creator><creator xml:id="au5" creatorRole="author" affiliationRef="#ac"><personName><givenNames>Jérôme</givenNames><familyName>Marrot</familyName></personName></creator><creator xml:id="au6" creatorRole="author" affiliationRef="#ad"><personName><givenNames>Marie‐Noëlle</givenNames><familyName>Rager</familyName></personName></creator><creator xml:id="au7" creatorRole="author" affiliationRef="#ab"><personName><givenNames>Olivia</givenNames><familyName>Reinaud</familyName><degrees>Prof.</degrees></personName><contactDetails><email normalForm="Olivia.Reinaud@univ-paris5.fr">Olivia.Reinaud@univ‐paris5.fr</email></contactDetails></creator><creator xml:id="au8" creatorRole="author" affiliationRef="#aa"><personName><givenNames>Ivan</givenNames><familyName>Jabin</familyName><degrees>Dr.</degrees></personName><contactDetails><email normalForm="ivan.jabin@univ-lehavre.fr">ivan.jabin@univ‐lehavre.fr</email></contactDetails></creator></creators><affiliationGroup><affiliation xml:id="aa" countryCode="FR" type="organization"><unparsedAffiliation>Unité de Recherche en Chimie Organique et Macromoléculaire (URCOM), Université du Havre, 25 rue Philippe Lebon, BP 540, 76058 Le Havre cedex, France, Fax: (+33) 232‐744‐391</unparsedAffiliation></affiliation><affiliation xml:id="ab" countryCode="FR" type="organization"><unparsedAffiliation>Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, UMR CNRS 8601, Université René Descartes, 45 rue des Saints Pères, 75270 Paris cedex 06, France, Fax: (+33) 142‐868‐387</unparsedAffiliation></affiliation><affiliation xml:id="ac" countryCode="FR" type="organization"><unparsedAffiliation>Institut Lavoisier, UMR CNRS 8180, Université de Versailles St‐Quentin en Yvelines, 45 av. des Etats‐Unis, 78035 Versailles cedex, France</unparsedAffiliation></affiliation><affiliation xml:id="ad" countryCode="FR" type="organization"><unparsedAffiliation>Service de RMN, Ecole Nationale Supérieure de Chimie de Paris (ENSCP), 11 rue Pierre et Marie Curie, 75231 Paris Cedex 05, France</unparsedAffiliation></affiliation></affiliationGroup><keywordGroup xml:lang="en" type="author"><keyword xml:id="kwd1">allosterism</keyword><keyword xml:id="kwd2">calixarenes</keyword><keyword xml:id="kwd3">host–guest systems</keyword><keyword xml:id="kwd4">supramolecular chemistry</keyword><keyword xml:id="kwd5">zinc</keyword></keywordGroup><fundingInfo><fundingAgency>Région Haute‐Normandie</fundingAgency></fundingInfo><supportingInformation><p>Supporting information for this article is available on the WWW under <url href="http://www.wiley-vch.de/contents/jc_2111/2007/f601040_s.pdf">http://www.wiley‐vch.de/contents/jc_2111/2007/f601040_s.pdf</url> or from the author.</p></supportingInformation><abstractGroup><abstract type="main" xml:lang="en"><title type="main">Abstract</title><p>Molecular recognition by calix[6]arene‐based receptors bearing three primary alkylamino side chain arms (<b>1</b>) is described. Complexation of Zn<sup>II</sup> ion provides the dinuclear μ‐hydroxo complex <span type="tex">${{\bf 2}{{{\rm OH}\hfill \atop {\rm G}\hfill}}}$<inlineGraphic alt="equation image" location="equation/tex2gif-ueqn-1.gif" href=""></inlineGraphic></span>, XRD characterization of which, together with solution studies, provided evidence of its hosting of neutral polar organic guests G. Treatment of this complex with a carboxylic acid or a sulfonamide (XH) results in the formation of mononuclear species <span type="tex">${{\bf 3}{{{\rm X}\hfill \atop {\rm G}\hfill}}}$<inlineGraphic alt="equation image" location="equation/tex2gif-ueqn-2.gif" href=""></inlineGraphic></span>, one of which (X = Cl) has been characterized by XRD. A dicationic complex <span type="tex">${{\bf 3}{{{\rm RNH}{_{2}}\hfill \atop {\rm G}\hfill}}}$<inlineGraphic alt="equation image" location="equation/tex2gif-ueqn-3.gif" href=""></inlineGraphic></span> is obtained upon treatment of <span type="tex">${{\bf 2}{{{\rm OH}\hfill \atop {\rm G}\hfill}}}$<inlineGraphic alt="equation image" location="equation/tex2gif-ueqn-4.gif" href=""></inlineGraphic></span> with a mixture of an alkylamine and a strong acid. Each of these Zn<sup>II</sup> complexes features a tetrahedral metal ion bound to the three amino arms of ligand <b>1</b> and to an exogenous ligand (either HO<sup>−</sup>, X<sup>−</sup>, or RNH<sub>2</sub>) sitting outside of the cavity. As a result, the metal ion structures the calixarene core, constraining it in a cone conformation suitable for guest hosting. The receptor properties of these compounds have been explored in detail and are compared with those of the trisammonium receptor <span type="tex">${{\bf 1}{{3\,{\rm H}{^{+}}\hfill \atop {\rm G}\hfill}}}$<inlineGraphic alt="equation image" location="equation/tex2gif-ueqn-5.gif" href=""></inlineGraphic></span>, based on the same calixarene core, as well as those of the trisimidazole‐based dicationic Zn funnel complexes. This study reveals very different host properties, in spite of the common hydrophobic, π‐basic, and hydrogen‐bonding acceptor properties of the calixarene cores. A harder external ligand produces a less polarized receptor that is consequently particularly sensitive to the hydrogen‐bonding ability of its guest. The less electron‐rich the apical ligand, and a fortiori the trisammonium host, the more sensitive the receptor to the dipole moment of the guest. All this stands in contrast with the funnel Zn complexes, in which the coordination link plays a dominant role. It is also shown that the asymmetry of an <i>exo</i>‐coordinated enantiopure amino ligand is sensed by the guest. This supramolecular system nicely illustrates how the receptor properties of a hydrophobic cavity can be allosterically tuned by the environment.</p></abstract><abstract type="graphical" xml:lang="en"><p><b>External tuning</b> of the host properties of calix[6]arene Zn complexes: Zn<sup>II</sup> coordination by a calix[6]arene bearing three primary amino arms has been explored and found to result in tetrahedral complexes with the labile site oriented toward the outside of the cavity. The resulting calixarene cone acts as a polarized receptor, the host properties of which can be allosterically tuned through the external binding of either anionic or neutral ligands to the capping Zn<sup>II</sup> ion (see scheme).<blockFixed type="graphic"><mediaResourceGroup><mediaResource alt="image" eRights="yes" copyright="WILEY-VCH" href="urn:x-wiley:09476539:media:CHEM200601040:content"></mediaResource><mediaResource alt="thumbnail image" rendition="webLoRes" mimeType="image/gif" href=""></mediaResource><mediaResource alt="original image" rendition="webOriginal" mimeType="image/gif" href=""></mediaResource><mediaResource alt="magnified image" rendition="webHiRes" mimeType="image/gif" href=""></mediaResource></mediaResourceGroup></blockFixed></p></abstract></abstractGroup></contentMeta></header></component></istex:document></istex:metadataXml><mods version="3.6"><titleInfo lang="en"><title>Allosteric Tuning of the Intra‐Cavity Binding Properties of a Calix[6]arene through External Binding to a ZnII Center Coordinated to Amino Side Chains</title></titleInfo><titleInfo type="alternative" contentType="CDATA" lang="en"><title>Allosteric Tuning of the Intra‐Cavity Binding Properties of a Calix[6]arene through External Binding to a ZnII Center Coordinated to Amino Side Chains</title></titleInfo><name type="personal"><namePart type="given">Ulrich</namePart><namePart type="family">Darbost</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>Unité de Recherche en Chimie Organique et Macromoléculaire (URCOM), Université du Havre, 25 rue Philippe Lebon, BP 540, 76058 Le Havre cedex, France, Fax: (+33) 232‐744‐391</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Olivier</namePart><namePart type="family">Sénèque</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, UMR CNRS 8601, Université René Descartes, 45 rue des Saints Pères, 75270 Paris cedex 06, France, Fax: (+33) 142‐868‐387</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Yun</namePart><namePart type="family">Li</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, UMR CNRS 8601, Université René Descartes, 45 rue des Saints Pères, 75270 Paris cedex 06, France, Fax: (+33) 142‐868‐387</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Gildas</namePart><namePart type="family">Bertho</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, UMR CNRS 8601, Université René Descartes, 45 rue des Saints Pères, 75270 Paris cedex 06, France, Fax: (+33) 142‐868‐387</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Jérôme</namePart><namePart type="family">Marrot</namePart><affiliation>Institut Lavoisier, UMR CNRS 8180, Université de Versailles St‐Quentin en Yvelines, 45 av. des Etats‐Unis, 78035 Versailles cedex, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Marie‐Noëlle</namePart><namePart type="family">Rager</namePart><affiliation>Service de RMN, Ecole Nationale Supérieure de Chimie de Paris (ENSCP), 11 rue Pierre et Marie Curie, 75231 Paris Cedex 05, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Olivia</namePart><namePart type="family">Reinaud</namePart><namePart type="termsOfAddress">Prof.</namePart><affiliation>Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, UMR CNRS 8601, Université René Descartes, 45 rue des Saints Pères, 75270 Paris cedex 06, France, Fax: (+33) 142‐868‐387</affiliation><affiliation>E-mail: Olivia.Reinaud@univ‐paris5.fr</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Ivan</namePart><namePart type="family">Jabin</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>Unité de Recherche en Chimie Organique et Macromoléculaire (URCOM), Université du Havre, 25 rue Philippe Lebon, BP 540, 76058 Le Havre cedex, France, Fax: (+33) 232‐744‐391</affiliation><affiliation>E-mail: ivan.jabin@univ‐lehavre.fr</affiliation><role><roleTerm type="text">author</roleTerm></role></name><typeOfResource>text</typeOfResource><genre type="article" displayLabel="article"></genre><originInfo><publisher>WILEY‐VCH Verlag</publisher><place><placeTerm type="text">Weinheim</placeTerm></place><dateIssued encoding="w3cdtf">2007-02-23</dateIssued><dateCaptured encoding="w3cdtf">2006-07-19</dateCaptured><copyrightDate encoding="w3cdtf">2007</copyrightDate></originInfo><language><languageTerm type="code" authority="rfc3066">en</languageTerm><languageTerm type="code" authority="iso639-2b">eng</languageTerm></language><physicalDescription><internetMediaType>text/html</internetMediaType><extent unit="figures">10</extent><extent unit="tables">2</extent><extent unit="references">51</extent></physicalDescription><abstract>Molecular recognition by calix[6]arene‐based receptors bearing three primary alkylamino side chain arms (1) is described. Complexation of ZnII ion provides the dinuclear μ‐hydroxo complex ${{\bf 2}{{{\rm OH}\hfill \atop {\rm G}\hfill}}}$, XRD characterization of which, together with solution studies, provided evidence of its hosting of neutral polar organic guests G. Treatment of this complex with a carboxylic acid or a sulfonamide (XH) results in the formation of mononuclear species ${{\bf 3}{{{\rm X}\hfill \atop {\rm G}\hfill}}}$, one of which (X = Cl) has been characterized by XRD. A dicationic complex ${{\bf 3}{{{\rm RNH}{_{2}}\hfill \atop {\rm G}\hfill}}}$ is obtained upon treatment of ${{\bf 2}{{{\rm OH}\hfill \atop {\rm G}\hfill}}}$ with a mixture of an alkylamine and a strong acid. Each of these ZnII complexes features a tetrahedral metal ion bound to the three amino arms of ligand 1 and to an exogenous ligand (either HO−, X−, or RNH2) sitting outside of the cavity. As a result, the metal ion structures the calixarene core, constraining it in a cone conformation suitable for guest hosting. The receptor properties of these compounds have been explored in detail and are compared with those of the trisammonium receptor ${{\bf 1}{{3\,{\rm H}{^{+}}\hfill \atop {\rm G}\hfill}}}$, based on the same calixarene core, as well as those of the trisimidazole‐based dicationic Zn funnel complexes. This study reveals very different host properties, in spite of the common hydrophobic, π‐basic, and hydrogen‐bonding acceptor properties of the calixarene cores. A harder external ligand produces a less polarized receptor that is consequently particularly sensitive to the hydrogen‐bonding ability of its guest. The less electron‐rich the apical ligand, and a fortiori the trisammonium host, the more sensitive the receptor to the dipole moment of the guest. All this stands in contrast with the funnel Zn complexes, in which the coordination link plays a dominant role. It is also shown that the asymmetry of an exo‐coordinated enantiopure amino ligand is sensed by the guest. This supramolecular system nicely illustrates how the receptor properties of a hydrophobic cavity can be allosterically tuned by the environment.</abstract><abstract>External tuning of the host properties of calix[6]arene Zn complexes: ZnII coordination by a calix[6]arene bearing three primary amino arms has been explored and found to result in tetrahedral complexes with the labile site oriented toward the outside of the cavity. The resulting calixarene cone acts as a polarized receptor, the host properties of which can be allosterically tuned through the external binding of either anionic or neutral ligands to the capping ZnII ion (see scheme).</abstract><note type="funding">Région Haute‐Normandie</note><subject lang="en"><genre>keywords</genre><topic>allosterism</topic><topic>calixarenes</topic><topic>host–guest systems</topic><topic>supramolecular chemistry</topic><topic>zinc</topic></subject><relatedItem type="host"><titleInfo><title>Chemistry – A European Journal</title></titleInfo><titleInfo type="abbreviated"><title>Chemistry – A European Journal</title></titleInfo><genre type="journal">journal</genre><note type="content"> Supporting information for this article is available on the WWW under http://www.wiley‐vch.de/contents/jc_2111/2007/f601040_s.pdf or from the author.</note><subject><genre>article-category</genre><topic>Full Paper</topic></subject><identifier type="ISSN">0947-6539</identifier><identifier type="eISSN">1521-3765</identifier><identifier type="DOI">10.1002/(ISSN)1521-3765</identifier><identifier type="PublisherID">CHEM</identifier><part><date>2007</date><detail type="volume"><caption>vol.</caption><number>13</number></detail><detail type="issue"><caption>no.</caption><number>7</number></detail><extent unit="pages"><start>2078</start><end>2088</end><total>11</total></extent></part></relatedItem><identifier type="istex">F49D95EB94D7748EF4C0EA0BD4DF59A593E68704</identifier><identifier type="DOI">10.1002/chem.200601040</identifier><identifier type="ArticleID">CHEM200601040</identifier><accessCondition type="use and reproduction" contentType="copyright">Copyright © 2007 WILEY‐VCH Verlag GmbH & Co. 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