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Article

Crystal Engineering of Conglomerates: Dilution of Racemate-Forming Fe(II) and Ni(II) Congeners into Conglomerate-Forming [Zn(bpy)3](PF6)2

by
Ugo Serdan
1,
Lucas Robin
1,
Mathieu Marchivie
1,
Mathieu Gonidec
1,
Patrick Rosa
1,
Elen Duverger-Nédellec
1,
Emilie Pouget
2,
Philippe Sainctavit
3,
Marie-Anne Arrio
3,
Amélie Juhin
3,
Andrei Rogalev
4,
Fabrice Wilhelm
4 and
Elizabeth A. Hillard
1,*
1
Univ. Bordeaux, CNRS, Bordeaux INP, ICMCB, UMR 5026, F-33600 Pessac, France
2
Univ. Bordeaux, CNRS, Bordeaux INP, CBMN, UMR 5248, F-33600 Pessac, France
3
CNRS, Sorbonne Université, MNHN, IMPMC, UMR 7590, F-75252 Paris, France
4
European Synchrotron Radiation Facility (ESRF), F-38043 Grenoble, France
*
Author to whom correspondence should be addressed.
Chemistry 2023, 5(1), 255-268; https://doi.org/10.3390/chemistry5010020
Submission received: 15 December 2022 / Revised: 1 February 2023 / Accepted: 2 February 2023 / Published: 15 February 2023
(This article belongs to the Special Issue Coordination Chemistry: Current Developments and Future Perspectives — A Themed Issue in Honor of Professor Spyros P. Perlepes on the Occasion of His 70th Birthday)
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Abstract

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.
Keywords: crystal engineering; chirality; conglomerate; molecular alloy; PXRD crystal engineering; chirality; conglomerate; molecular alloy; PXRD
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MDPI and ACS Style

Serdan, U.; Robin, L.; Marchivie, M.; Gonidec, M.; Rosa, P.; Duverger-Nédellec, E.; Pouget, E.; Sainctavit, P.; Arrio, M.-A.; Juhin, A.; 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, 255-268. https://doi.org/10.3390/chemistry5010020

AMA Style

Serdan U, Robin L, Marchivie M, Gonidec M, Rosa P, Duverger-Nédellec E, Pouget E, Sainctavit P, Arrio M-A, Juhin A, 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):255-268. https://doi.org/10.3390/chemistry5010020

Chicago/Turabian Style

Serdan, Ugo, Lucas Robin, Mathieu Marchivie, Mathieu Gonidec, Patrick Rosa, Elen Duverger-Nédellec, Emilie Pouget, Philippe Sainctavit, Marie-Anne Arrio, Amélie Juhin, and et al. 2023. "Crystal Engineering of Conglomerates: Dilution of Racemate-Forming Fe(II) and Ni(II) Congeners into Conglomerate-Forming [Zn(bpy)3](PF6)2" Chemistry 5, no. 1: 255-268. https://doi.org/10.3390/chemistry5010020

APA Style

Serdan, U., Robin, L., Marchivie, M., Gonidec, M., Rosa, P., Duverger-Nédellec, E., Pouget, E., Sainctavit, P., Arrio, M.-A., Juhin, A., Rogalev, A., Wilhelm, F., & Hillard, E. A. (2023). Crystal Engineering of Conglomerates: Dilution of Racemate-Forming Fe(II) and Ni(II) Congeners into Conglomerate-Forming [Zn(bpy)3](PF6)2. Chemistry, 5(1), 255-268. https://doi.org/10.3390/chemistry5010020

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