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Crystal engineering of conglomerates: dilution of racemate-forming Fe(II) and Ni(II) congeners into conglomerate-forming [Zn(bpy)3](PF6)2

hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorSERDAN, Ugo
hal.structure.identifierChimie et Biologie des Membranes et des Nanoobjets [CBMN]
dc.contributor.authorROBIN, Lucas
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorMARCHIVIE, Mathieu
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorGONIDEC, Mathieu
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorROSA, Patrick
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorDUVERGER-NÉDELLEC, Elen
hal.structure.identifierChimie et Biologie des Membranes et des Nanoobjets [CBMN]
dc.contributor.authorPOUGET, Emilie
hal.structure.identifierInstitut de minéralogie, de physique des matériaux et de cosmochimie [IMPMC]
dc.contributor.authorSAINCTAVIT, Ph.
hal.structure.identifierInstitut de minéralogie, de physique des matériaux et de cosmochimie [IMPMC]
dc.contributor.authorARRIO, Marie-Anne
hal.structure.identifierMinéralogie et magnétisme de basses dimensionnalités [IMPMC] [IMPMC_MIMABADI]
dc.contributor.authorJUHIN, Amélie
hal.structure.identifierEuropean Synchrotron Radiation Facility [Grenoble] [ESRF]
dc.contributor.authorROGALEV, Andrei
hal.structure.identifierEuropean Synchrotron Radiation Facility [Grenoble] [ESRF]
dc.contributor.authorWILHELM, Fabrice
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorHILLARD, Elizabeth
dc.date.issued2023-02-15
dc.identifier.issn2624-8549
dc.description.abstractEnConglomerate formation, where enantiomers within a racemic mixture self-segregate upon crystallization, is an advantageous property for obtaining chirally pure crystals and allows large-scale chiral resolution. However, the prevalence of conglomerates is low and difficult to predict. In this report, we describe our attempts to engineer conglomerates from racemate-forming compounds by integrating them into a conglomerate-forming matrix. In this regard, we found that Ni(II) and Fe(II) form molecular alloys with Zn(II) in [MxZn(1−x)(bpy)3](PF6)2 (where bpy = 2,2′-bipyridyl). Powder X-ray Diffraction (PXRD) and Energy-Dispersive X-ray spectroscopy (EDX) evidenced conglomerate crystallization with Ni(II) concentrations up to about 25%, while it was observed only for much lower concentrations of Fe(II). This can be attributed to the ability of [Ni(bpy)3](PF6)2 to access a metastable conglomerate phase, while no such phase has been detected in [Fe(bpy)3](PF6)2. Furthermore, the chiral phase appears to be favored in fast-growing precipitates, while the racemic phase is favored in slow re-crystallizations for both Ni(II) and Fe(II) molecular alloys. X-ray natural circular dichroism (XNCD) measurements on [Ni0.13Zn0.87(bpy)3](PF6)2 demonstrate the chirality of the nickel molecules within the zinc molecular matrix.
dc.description.sponsorshipNanocomposites hélicoïdaux pour l'induction de dichroïsme magnéto-chiral - ANR-19-CE09-0018
dc.description.sponsorshipÉtude expérimentale de la théorie microscopique du dichroïsme circulaire naturel aux rayons X - ANR-21-CE29-0032
dc.language.isoen
dc.publisherMDPI
dc.subject.encrystal engineering
dc.subject.enchirality
dc.subject.enconglomerate
dc.subject.enmolecular alloy
dc.subject.enPXRD
dc.title.enCrystal engineering of conglomerates: dilution of racemate-forming Fe(II) and Ni(II) congeners into conglomerate-forming [Zn(bpy)3](PF6)2
dc.typeArticle de revue
dc.identifier.doi10.3390/chemistry5010020
dc.subject.halChimie/Matériaux
bordeaux.journalChemistry
bordeaux.page255-268
bordeaux.volume5
bordeaux.issue1
bordeaux.peerReviewedoui
hal.identifierhal-03991899
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-03991899v1
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