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New μ4-Oxido-Bridged Copper Benzoate Quasi-Tetrahedron and Bis-μ3-Hydroxido-Bridged Copper Azide and Copper Thiocyanate Stepped Cubanes: Core Conversion, Structural Diversity, and Magnetic Properties

hal.structure.identifierDepartment of Chemistry, Indian Institute of Technology
dc.contributor.authorSARKAR, Mrinal
hal.structure.identifierCentre de recherches Paul Pascal [CRPP]
hal.structure.identifierUniversité Sciences et Technologies - Bordeaux 1 [UB]
dc.contributor.authorCLÉRAC, Rodolphe
hal.structure.identifierUniversité Sciences et Technologies - Bordeaux 1 [UB]
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorMATHONIÈRE, Corine
hal.structure.identifierCentre de recherches Paul Pascal [CRPP]
hal.structure.identifierUniversité Sciences et Technologies - Bordeaux 1 [UB]
dc.contributor.authorG. R. HEARNS, Nigel
hal.structure.identifierDipartimento di Chimica e Centro di Strutturistica Diffrattometica
dc.contributor.authorBERTOLASI, Valerio
hal.structure.identifierDepartment of Chemistry, Indian Institute of Technology
dc.contributor.authorRAY, Debashis
dc.date.issued2010
dc.identifier.issn0020-1669
dc.description.abstractEn[Cu2(μ4-O)Cu2] and [Cu2(μ3-OH)2Cu2] geometrical arrangements are found in a new family of tetranuclear complexes: [Cu4(μ4-O)(μ-bip)2(μ-O2CPh)4] 3 0.5CH2Cl2 (1 3 0.5CH2Cl2), [Cu4(μ3-OH)2(μ-bip)2(N3)4] (2), and [Cu4- (μ3-OH)2(μ-bip)2(NCS)4(DMF)2] (3 3 2DMF) [Hbip = 2,6-bis(benzyliminomethyl)-4-methylphenol; DMF = dimethylformamide]. These complexes have been characterized by X-ray crystallography, and their magnetic properties have been studied. Complex 1 reacts with azide and thiocyanate anions, leading to 2 and 3 with a change of the [Cu4(μ4-O)] core into [Cu4(μ3-OH)2] units. These compounds are new examples of [Cu4] complexes where CuII ions are connected by two types of water-derived ligands: oxide and hydroxide. Formation of these [Cu4] complexes can be controlled by changing the bridging ligands, which allows an effective tuning of the self-assembly. The study of the magnetic properties reveals that these complexes exhibit strong intramolecular antiferromagnetic interactions to yield a ST = 0 ground state. For the three complexes, the temperature dependence of the magnetic susceptibility was fitted using a model with two isolated S = 1/2 dimers based on the H = -2J{SCu,1 3 SCu,2} spin Hamiltonian with J/kB =-289 K for 1; J/kB =-464 and -405 K for 2 and 3, respectively (where J is the exchange constant through the oxido-phenoxido or hydroxido-phenoxido bridges, respectively).
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.subjectchimie des materiaux
dc.title.enNew μ4-Oxido-Bridged Copper Benzoate Quasi-Tetrahedron and Bis-μ3-Hydroxido-Bridged Copper Azide and Copper Thiocyanate Stepped Cubanes: Core Conversion, Structural Diversity, and Magnetic Properties
dc.typeArticle de revue
dc.identifier.doi10.1021/ic100356y
dc.subject.halChimie/Matériaux
dc.subject.halChimie/Chimie inorganique
bordeaux.journalInorganic Chemistry
bordeaux.pagepp. 6575-6585
bordeaux.volume49
bordeaux.issue14
bordeaux.peerReviewedoui
hal.identifierhal-00504995
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-00504995v1
bordeaux.COinSctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Inorganic%20Chemistry&rft.date=2010&rft.volume=49&rft.issue=14&rft.spage=pp.%206575-6585&rft.epage=pp.%206575-6585&rft.eissn=0020-1669&rft.issn=0020-1669&rft.au=SARKAR,%20Mrinal&CL%C3%89RAC,%20Rodolphe&MATHONI%C3%88RE,%20Corine&G.%20R.%20HEARNS,%20Nigel&BERTOLASI,%20Valerio&rft.genre=article


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