Synthesis, Crystal Structures, and Properties of Molecular Squares Displaying Hydrogen and π-π Bonded Networks
Identifieur interne : 008061 ( Main/Exploration ); précédent : 008060; suivant : 008062Synthesis, Crystal Structures, and Properties of Molecular Squares Displaying Hydrogen and π-π Bonded Networks
Auteurs : Hitoshi Kumagai [Japon] ; Motoko Akita-Tanaka [Japon] ; Satoshi Kawata [Japon] ; Katsuya Inoue [Japon] ; Cameron J. Kepert [Australie] ; Mohamedally Kurmoo [France]Source :
- Crystal growth & design [ 1528-7483 ] ; 2009.
Descripteurs français
- Pascal (Inist)
- Structure cristalline, Synthèse hydrothermale, Croissance cristalline, Propriété thermique, Propriété magnétique, Ligand, Métal transition, Polyèdre coordination, Coordinat bidenté, Liaison hydrogène, Amine, Carboxylate, Pyridine, Structure supramoléculaire, Cuivre, Nickel, Dioxyde de carbone, Matériau paramagnétique, Interaction faible, Interaction échange, Cu2S, 6166, 8110, 6540D, 6166H.
- Wicri :
English descriptors
- KwdEn :
- Amines, Bidentate ligand, Carbon dioxide, Carboxylates, Coordination polyhedron, Copper, Crystal growth, Crystal structure, Exchange interactions, Hydrogen bonds, Hydrothermal synthesis, Ligands, Magnetic properties, Nickel, Paramagnetic materials, Pyridine, Supramolecular structure, Thermal properties, Transition elements, Weak interactions.
Abstract
We report the hydrothermal syntheses, single-crystal structure determinations, and the thermal and magnetic properties of five binuclear complexes obtained from either a mixture of P and M 2,2'-biphenyldicarboxylate, (2,2'-bpdc)2-, or a mixture of cis- and trans-1,4-cyclohexanedicarboxylate, (1,4-chdc)2-, as bridging ligands, di-2-pyridylamine (dpa) as a capping terminal ligand, and a divalent transition metal (Cu, Co, and Ni). All five compounds, [Co2(2,2'-bpdc)2(dpa)2] (1), [Cu2(2,2'-bpdc)2(dpa)2].4H2O (2a), [Cu2(2,2'-bpdc)2(dpa)2] . 2(2,2'-bpdcH2) . H2O (2b), [Co2(cis-chdc)2(dpa)2] (3), and [Ni2(cis-chdc)2(dpa)2] (4), consist of neutral molecular squares of two metal centers bridged by two elbowed dicarboxylate, and each metal is capped by the chelating di-2-pyridylamine, In 1, the Co(II) adopts a tetrahedral coordination from two oxygen atoms of monodentate 2,2'-bpdc2- and two nitrogen atoms from dpa. In 2a and 2b, the Cu(II) adopts distorted octahedral geometry from two bidentate 2,2'-bpdc2- and one bidentate dpa. 1, 2a, and 2b contain both P and M forms of 2,2'-bpdc2-. 3 and 4 contain octahedral metal coordination with only the chair form of cis-chdc2- as bridging ligands in bidentate mode and bidentate peripheral dpa. In each of these complexes, hydrogen bonds between the amine nitrogen and a carboxylate oxygen atom and π-π overlap between the pyridine rings of the dpa define the supramolecular interactions which contribute to the crystals' stability. The magnetic properties are those of paramagnets with weak exchange interactions, as a consequence of the distant exchange pathway between nearest neighbor moment carriers.
Affiliations:
- Australie, France, Japon
- Alsace (région administrative), Grand Est, Nouvelle-Galles du Sud
- Strasbourg, Sydney
- Université de Strasbourg, Université de Sydney
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Kepert</name><affiliation wicri:level="4"><inist:fA14 i1="03"><s1>School of Chemistry, University of Sydney</s1><s2>NSW 2006</s2><s3>AUS</s3><sZ>5 aut.</sZ></inist:fA14><country>Australie</country><placeName><settlement type="city">Sydney</settlement><region type="état">Nouvelle-Galles du Sud</region></placeName><orgName type="university">Université de Sydney</orgName></affiliation></author><author><name sortKey="Kurmoo, Mohamedally" sort="Kurmoo, Mohamedally" uniqKey="Kurmoo M" first="Mohamedally" last="Kurmoo">Mohamedally Kurmoo</name><affiliation wicri:level="4"><inist:fA14 i1="04"><s1>Laboratoire de Chimie de Coordination Organique, UMR7740-CNRS, Université de Strasbourg, Institut Le Bel, 4 rue Blaise Pascal</s1><s2>67000 Strasbourg</s2><s3>FRA</s3><sZ>6 aut.</sZ></inist:fA14><country>France</country><placeName><region type="region" nuts="2">Grand Est</region><region type="old region" nuts="2">Alsace (région administrative)</region><settlement type="city">Strasbourg</settlement><settlement type="city">Strasbourg</settlement></placeName><orgName type="university">Université de Strasbourg</orgName></affiliation></author></analytic><series><title level="j" type="main">Crystal growth & design</title><title level="j" type="abbreviated">Cryst. growth des.</title><idno type="ISSN">1528-7483</idno><imprint><date when="2009">2009</date></imprint></series></biblStruct></sourceDesc><seriesStmt><title level="j" type="main">Crystal growth & design</title><title level="j" type="abbreviated">Cryst. growth des.</title><idno type="ISSN">1528-7483</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Amines</term><term>Bidentate ligand</term><term>Carbon dioxide</term><term>Carboxylates</term><term>Coordination polyhedron</term><term>Copper</term><term>Crystal growth</term><term>Crystal structure</term><term>Exchange interactions</term><term>Hydrogen bonds</term><term>Hydrothermal synthesis</term><term>Ligands</term><term>Magnetic properties</term><term>Nickel</term><term>Paramagnetic materials</term><term>Pyridine</term><term>Supramolecular structure</term><term>Thermal properties</term><term>Transition elements</term><term>Weak interactions</term></keywords><keywords scheme="Pascal" xml:lang="fr"><term>Structure cristalline</term><term>Synthèse hydrothermale</term><term>Croissance cristalline</term><term>Propriété thermique</term><term>Propriété magnétique</term><term>Ligand</term><term>Métal transition</term><term>Polyèdre coordination</term><term>Coordinat bidenté</term><term>Liaison hydrogène</term><term>Amine</term><term>Carboxylate</term><term>Pyridine</term><term>Structure supramoléculaire</term><term>Cuivre</term><term>Nickel</term><term>Dioxyde de carbone</term><term>Matériau paramagnétique</term><term>Interaction faible</term><term>Interaction échange</term><term>Cu2S</term><term>6166</term><term>8110</term><term>6540D</term><term>6166H</term></keywords><keywords scheme="Wicri" type="topic" xml:lang="fr"><term>Cuivre</term><term>Nickel</term></keywords></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">We report the hydrothermal syntheses, single-crystal structure determinations, and the thermal and magnetic properties of five binuclear complexes obtained from either a mixture of P and M 2,2'-biphenyldicarboxylate, (2,2'-bpdc)<sup>2-</sup>, or a mixture of cis- and trans-1,4-cyclohexanedicarboxylate, (1,4-chdc)<sup>2-</sup>, as bridging ligands, di-2-pyridylamine (dpa) as a capping terminal ligand, and a divalent transition metal (Cu, Co, and Ni). All five compounds, [Co<sub>2</sub>(2,2'-bpdc)<sub>2</sub>(dpa)<sub>2</sub>] (1), [Cu<sub>2</sub>(2,2'-bpdc)<sub>2</sub>(dpa)<sub>2</sub>].4H<sub>2</sub>O (2a), [Cu<sub>2</sub>(2,2'-bpdc)<sub>2</sub>(dpa)<sub>2</sub>] . 2(2,2'-bpdcH<sub>2</sub>) . H<sub>2</sub>O (2b), [Co<sub>2</sub>(cis-chdc)<sub>2</sub>(dpa)<sub>2</sub>] (3), and [Ni<sub>2</sub>(cis-chdc)<sub>2</sub>(dpa)<sub>2</sub>] (4), consist of neutral molecular squares of two metal centers bridged by two elbowed dicarboxylate, and each metal is capped by the chelating di-2-pyridylamine, In 1, the Co(II) adopts a tetrahedral coordination from two oxygen atoms of monodentate 2,2'-bpdc<sup>2-</sup> and two nitrogen atoms from dpa. In 2a and 2b, the Cu(II) adopts distorted octahedral geometry from two bidentate 2,2'-bpdc<sup>2-</sup> and one bidentate dpa. 1, 2a, and 2b contain both P and M forms of 2,2'-bpdc<sup>2-</sup>. 3 and 4 contain octahedral metal coordination with only the chair form of cis-chdc<sup>2-</sup> as bridging ligands in bidentate mode and bidentate peripheral dpa. In each of these complexes, hydrogen bonds between the amine nitrogen and a carboxylate oxygen atom and π-π overlap between the pyridine rings of the dpa define the supramolecular interactions which contribute to the crystals' stability. The magnetic properties are those of paramagnets with weak exchange interactions, as a consequence of the distant exchange pathway between nearest neighbor moment carriers.</div></front></TEI><affiliations><list><country><li>Australie</li><li>France</li><li>Japon</li></country><region><li>Alsace (région administrative)</li><li>Grand Est</li><li>Nouvelle-Galles du Sud</li></region><settlement><li>Strasbourg</li><li>Sydney</li></settlement><orgName><li>Université de Strasbourg</li><li>Université de Sydney</li></orgName></list><tree><country name="Japon"><noRegion><name sortKey="Kumagai, Hitoshi" sort="Kumagai, Hitoshi" uniqKey="Kumagai H" first="Hitoshi" last="Kumagai">Hitoshi Kumagai</name></noRegion><name sortKey="Akita Tanaka, Motoko" sort="Akita Tanaka, Motoko" uniqKey="Akita Tanaka M" first="Motoko" last="Akita-Tanaka">Motoko Akita-Tanaka</name><name sortKey="Inoue, Katsuya" sort="Inoue, Katsuya" uniqKey="Inoue K" first="Katsuya" last="Inoue">Katsuya Inoue</name><name sortKey="Kawata, Satoshi" sort="Kawata, Satoshi" uniqKey="Kawata S" first="Satoshi" last="Kawata">Satoshi Kawata</name></country><country name="Australie"><region name="Nouvelle-Galles du Sud"><name sortKey="Kepert, Cameron J" sort="Kepert, Cameron J" uniqKey="Kepert C" first="Cameron J." last="Kepert">Cameron J. Kepert</name></region></country><country name="France"><region name="Grand Est"><name sortKey="Kurmoo, Mohamedally" sort="Kurmoo, Mohamedally" uniqKey="Kurmoo M" first="Mohamedally" last="Kurmoo">Mohamedally Kurmoo</name></region></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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