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Impact of Positional Isomers on the Selective Isolation of cis-trans Isomers in Cobaltdioxolene Chemistry and Solvation Effects on the Valence Tautomerism in the Solid State

hal.structure.identifierPanskura Banamali College
dc.contributor.authorJANA, Narayan
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorQI, Xing-Hui
hal.structure.identifierDepartment of Chemistry [CICECO]
dc.contributor.authorBRANDÃO, Paula
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
hal.structure.identifierCentre de Recherche Paul Pascal [CRPP]
dc.contributor.authorMATHONIÈRE, Corine
hal.structure.identifierPanskura Banamali College
dc.contributor.authorPANJA, Anangamohan
dc.date.issued2022
dc.identifier.issn1528-7483
dc.description.abstractEnThree new mononuclear cobalt compounds, trans-[Co(3,5-dbcat)(3,5-dbsq)(4-Etpy) 2 ]•CH 3 CN (1), cis-[Co(3,5-dbcat)(3,5-dbsq)(3-NH 2 py) 2 ]•DMF (2) and trans-[Co(3,5dbcat)(3,5-dbsq)(4-NH 2 py) 2 ]•2DMF (3) (3,5-dbcat 2and 3,5-dbsq •− stand for 3,5-di-tertbutyl-catacholate and 3,5-di-tert-butyl-semiquinonate, respectively), derived from a redoxactive o-dioxolene ligand in presence of 4-ethylpyridine (4-Etpy), 3-aminopyridine (3-NH 2 py), and 4-aminopyridine (4-NH 2 py), respectively, have been synthesized and investigated with a view to examine possible influence of pyridine derivatives and solvation on the valence tautomeric (VT) process. Single crystal X-ray diffraction data for all compounds at room temperature suggest Co(III)(3,5-dbcat)(3,5-dbsq) charge distribution in these complexes. Further insight into the crystal structures discloses the diverse noncovalent interactions offered by the isomers of aminopyridine in 2 and 3, leading to the first example 2 of selective isolation of cis and trans isomers in cobalt-dioxolene chemistry induced by the positional isomers of the ancillary ligands. Variable temperature magnetic susceptibility data for all compounds between 2 and 300 K are consistent with the structural studies. At elevated temperatures, complex 1 exhibits a VT interconversion from low spin Co(III)-(3,5-dbcat)(3,5dbsq) to high spin Co(II)-(3,5-dbsq)(3,5-dbsq), triggered by the loss of lattice solvent molecules, while a partial interconversion is observed for complex 3 even heating up to 430 K. The present report overall highlights the impact of positional isomers on the selective isolation of cis-trans isomers in cobalt-dioxolene chemistry and solvation effects on the valence tautomerism in the solid state.
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.subject.enBond angles
dc.subject.enIR and UV-visible spectroscopy
dc.subject.enCyclic voltammogram
dc.subject.enEPR Spectral data
dc.subject.enMagnetic measurements
dc.subject.enOptical reflectivity studies
dc.subject.enBond angles
dc.title.enImpact of Positional Isomers on the Selective Isolation of cis-trans Isomers in Cobaltdioxolene Chemistry and Solvation Effects on the Valence Tautomerism in the Solid State
dc.typeArticle de revue
dc.subject.halChimie/Chimie de coordination
dc.subject.halChimie/Matériaux
bordeaux.journalCrystal Growth & Design
bordeaux.page993-1004
bordeaux.volume22
bordeaux.issue2
bordeaux.peerReviewedoui
hal.identifierhal-03562063
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-03562063v1
bordeaux.COinSctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Crystal%20Growth%20&%20Design&rft.date=2022&rft.volume=22&rft.issue=2&rft.spage=993-1004&rft.epage=993-1004&rft.eissn=1528-7483&rft.issn=1528-7483&rft.au=JANA,%20Narayan&QI,%20Xing-Hui&BRAND%C3%83O,%20Paula&MATHONI%C3%88RE,%20Corine&PANJA,%20Anangamohan&rft.genre=article


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