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Enantiomeric resolution and X-ray optical activity of a tricobalt extended metal atom chain

hal.structure.identifierCentre de Recherche Paul Pascal [CRPP]
dc.contributor.authorSRINIVASAN, Anandi
hal.structure.identifierCentre de Recherche Paul Pascal [CRPP]
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorCORTIJO, Miguel
hal.structure.identifierCentre de Recherche Paul Pascal [CRPP]
dc.contributor.authorBULICANU, Vladimir
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorNAÏM, Ahmad
hal.structure.identifierCentre de Recherche Paul Pascal [CRPP]
dc.contributor.authorCLÉRAC, Rodolphe
hal.structure.identifierInstitut de minéralogie, de physique des matériaux et de cosmochimie [IMPMC]
dc.contributor.authorSAINCTAVIT, Philippe
hal.structure.identifierEuropean Synchrotron Radiation Facility [ESRF]
dc.contributor.authorROGALEV, Andrei
hal.structure.identifierEuropean Synchrotron Radiation Facility [ESRF]
dc.contributor.authorWILHELM, Fabrice
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorROSA, Patrick
hal.structure.identifierCentre de Recherche Paul Pascal [CRPP]
dc.contributor.authorHILLARD, Elizabeth
dc.date.issued2018
dc.identifier.issn2041-6520
dc.description.abstractEnA simple procedure based on anion exchange was employed for the enantiomeric resolution of the extended metal atom chain (EMAC) [Co-3(dpa)(4)(MeCN)(2)](2+). Use of the chiral salt (NBu4)(2)[As-2(tartrate)(2)], (Lambda-1 or Delta-1), resulted in the selective crystallization of the EMAC enantiomers as [Delta-Co-3(dpa)(4)(MeCN)(2)](NBu4)(2)[Lambda-As-2(tartarte)(2)](2), (Delta-2) and [Lambda-Co-3(dpa)(4)(MeCN)(2)](NBu4)(2)[Delta-As-2(tartrate)(2)](2) (Lambda-2), respectively, in the P42(1)2 space group, whereas a racemic mixture of 1 yielded [Co-3(dpa)(4)(MeCN)(2)] [As-2(tartrate)(2)]center dot 2MeCN (rac-3), which crystallized in the C2/c space group. The local electronic and magnetic structure of the EMAC enantiomers was studied, exploiting a variety of dichroisms in single crystals. A strong linear dichroism at the Co K-edge was observed in the orthoaxial configuration, whereas it vanished in the axial orientation, thus spectroscopically confirming the D-4 crystal symmetry. Compounds Delta-2 and Lambda-2 are shown to be enantiopure materials as evidenced by mirror-image natural circular dichroism spectra in the UV/vis in solution and in the X-ray range at the Co K-edge in single crystals. The surprising absence of detectable X-ray magnetic circular dichroism or X-ray magnetochiral dichroism signals at the Co K-edge, even at low temperature (3 K) and a high magnetic field (17 T), is ascribed to a strongly delocalized spin density on the tricobalt core.
dc.language.isoen
dc.publisherThe Royal Society of Chemistry
dc.subject.enNATURAL CIRCULAR-DICHROISM
dc.subject.enBOND-STRETCH ISOMERISM
dc.subject.enDI(2-PYRIDYL)AMIDE DPA
dc.subject.enCHIRAL RECOGNITION
dc.subject.enCRYSTAL-STRUCTURE
dc.subject.enCOMPLEXES
dc.subject.enASSOCIATION
dc.subject.enMECHANISM
dc.subject.enLIGANDS
dc.subject.enANION
dc.title.enEnantiomeric resolution and X-ray optical activity of a tricobalt extended metal atom chain
dc.typeArticle de revue
dc.identifier.doi10.1039/c7sc04131d
dc.subject.halChimie
bordeaux.journalChemical Science
bordeaux.page1136-1143
bordeaux.volume9
bordeaux.issue5
bordeaux.peerReviewedoui
hal.identifierhal-01714521
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-01714521v1
bordeaux.COinSctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Chemical%20Science&rft.date=2018&rft.volume=9&rft.issue=5&rft.spage=1136-1143&rft.epage=1136-1143&rft.eissn=2041-6520&rft.issn=2041-6520&rft.au=SRINIVASAN,%20Anandi&CORTIJO,%20Miguel&BULICANU,%20Vladimir&NA%C3%8FM,%20Ahmad&CL%C3%89RAC,%20Rodolphe&rft.genre=article


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