SERDAN, Ugo; ROBIN, Lucas; MARCHIVIE, Mathieu; GONIDEC, Mathieu; ROSA, Patrick; DUVERGER-NÉDELLEC, Elen; POUGET, Emilie; SAINCTAVIT, Ph.; ARRIO, Marie-Anne; JUHIN, Amélie; ROGALEV, Andrei; WILHELM, Fabrice; HILLARD, Elizabeth

doi:10.3390/chemistry5010020

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SERDAN, Ugo
Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB]

ROBIN, Lucas
Chimie et Biologie des Membranes et des Nanoobjets [CBMN]

MARCHIVIE, Mathieu
Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB]

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Article de revue

Ce document a été publié dans

Chemistry. 2023-02-15, vol. 5, n° 1, p. 255-268

MDPI

Résumé en anglais

Conglomerate 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.< Réduire

Mots clés en anglais

crystal engineering

chirality

conglomerate

molecular alloy

PXRD

DOI

http://dx.doi.org/10.3390/chemistry5010020

Project ANR

Nanocomposites hélicoïdaux pour l'induction de dichroïsme magnéto-chiral - ANR-19-CE09-0018
Étude expérimentale de la théorie microscopique du dichroïsme circulaire naturel aux rayons X

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Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB) - UMR 5026