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Dinuclear spin-crossover complexes based on tetradentate and bridging cyanocarbanion ligands

hal.structure.identifierChimie, Electrochimie Moléculaires et Chimie Analytique [CEMCA]
dc.contributor.authorMILIN, Eric
hal.structure.identifierChimie, Electrochimie Moléculaires et Chimie Analytique [CEMCA]
hal.structure.identifierLaboratoire de Physico-Chimie des Matériaux et Catalyse [Université Abderrahmane Mira - Bejaia] [LPCMC]
dc.contributor.authorBELAÏD, Sabrina
hal.structure.identifierChimie, Electrochimie Moléculaires et Chimie Analytique [CEMCA]
dc.contributor.authorPATINEC, Véronique
hal.structure.identifierChimie, Electrochimie Moléculaires et Chimie Analytique [CEMCA]
dc.contributor.authorTRIKI, Smail
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorCHASTANET, Guillaume
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorMARCHIVIE, Mathieu
dc.date.issued2016-09-06
dc.identifier.issn0020-1669
dc.description.abstractEnSpin-crossover (SCO) Fe(II) dinuclear complexes of formula [Fe2(tmpa)2(μ2-tcpd)2]·0.8(CH3OH) (1·MeOH) and [Fe2(andmpa)2(μ2-tcpd)2]·2CH3OH (2·MeOH) (tmpa = tris(2-pyridylmethyl)amine, andmpa = bis(2-pyridylmethyl)aminomethyl)aniline, (tcpd)(2-) = 2-dicyanomethylene-1,1,3,3-tetracyanopropanediide) have been synthesized and characterized by infrared spectroscopy, X-ray diffraction, and magnetic measurements. The crystal structure determinations of the two complexes (1·MeOH and 2·MeOH) and the desolvated complex 1 (from 1·MeOH) revealed a neutral centrosymmetrical dinuclear structure in which the (tcpd)(2-) cyanocarbanion acts as a double μ2-bridging ligand between two [FeL](2+) (L = tmpa (1), andmpa (2)) units involving two free coordination sites in the cis configuration. Examination of the shortest intermolecular contacts in 1·MeOH and 1 reveals no significant hydrogen bonding between the dinuclear units, while in 2·MeOH these units are held together by significant hydrogen bonds between one of the uncoordinated nitrile groups and the anilate function, giving rise to 1D supramolecular structure. The three dinuclear complexes 1, 2·MeOH, and 2 exhibit SCO behaviors which have been evidenced by the thermal evolutions of the χmT product and by the average values of the six Fe-N distances for 1 and 2·MeOH, that reveal a gradual conversion with transition temperatures (T1/2) at ca. 352 K (1), 196 K (2), and 180 K (2·MeOH). For the solvated 1·MeOH, the sharp SCO transition observed around 365 K was induced by the desolvatation process above 330 K during the magnetic measurements.
dc.description.sponsorshipBistabilité magnétique dans de nouveaux systèmes moléculaires à base de ligands anioniques pontants - ANR-12-BS07-0030
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.title.enDinuclear spin-crossover complexes based on tetradentate and bridging cyanocarbanion ligands
dc.typeArticle de revue
dc.identifier.doi10.1021/acs.inorgchem.6b01542
dc.subject.halChimie/Matériaux
bordeaux.journalInorganic Chemistry
bordeaux.page9038-9046
bordeaux.volume55
bordeaux.issue17
bordeaux.peerReviewedoui
hal.identifierhal-01367768
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-01367768v1
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