Crystal engineering of conglomerates: dilution of racemate-forming Fe(II) and Ni(II) congeners into conglomerate-forming [Zn(bpy)3](PF6)2 - CNRS - Centre national de la recherche scientifique Accéder directement au contenu
Article Dans Une Revue Chemistry Année : 2023

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

Résumé

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.

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Matériaux
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Dates et versions

hal-03991899 , version 1 (16-02-2023)

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Ugo Serdan, Lucas Robin, Mathieu Marchivie, Mathieu Gonidec, Patrick Rosa, et al.. Crystal engineering of conglomerates: dilution of racemate-forming Fe(II) and Ni(II) congeners into conglomerate-forming [Zn(bpy)3](PF6)2. Chemistry, 2023, 5 (1), pp.255-268. ⟨10.3390/chemistry5010020⟩. ⟨hal-03991899⟩
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