Packing of Helices: Is Chirality the Highest Crystallographic Symmetry?

Gautier, Romain; Poeppelmeier, Kenneth R.

doi:10.3390/cryst6090106

Cited by 8 publications

(2 citation statements)

References 23 publications

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“…Both compounds 10 and 11 consist of the already known cationic unit of Fe(II) (i.e., [Fe(L) 3 ] 2+ unit; L = bipy or phen) and anionic unit of U(IV) (i.e., [UCl 6 ] 2– unit), although its combination as a single compound is reported in this study for the first time. Similar combination of cationic [M 1 (L) 3 ] m + unit and anionic [M 2 X 6 ] n − unit (X = halide) was also observed for a heterometallic Zn–Ta compound, [Zn(bipy) 3 ][TaF 6 ] 2 . The Fe–N distances in the cationic [Fe(L) 3 ] 2+ units (L = bipy or phen) are in good agreement with those found in the previous Fe(II)–U(VI) compounds of 4 and 5 , showing the same trend of bond lengthening originating from the higher stiffness of phen than that of bipy (Table ).…”

Section: Resultssupporting

confidence: 86%

Synthesis and Characterization of Heterometallic Iron–Uranium Complexes with a Bidentate N-Donor Ligand (2,2′-Bipyridine or 1,10-Phenanthroline)

et al. 2018

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The coordination chemistry of the diimine ligands, 2,2′-bipyridine (bipy) and 1,10-phenanthroline (phen), with d- and f-block metals has been extensively explored during the last century to yield many technological and industrial applications. Despite this long history, the chemistry of these diimine ligands in heterometallic systems containing multiple metals is poorly understood even to date. This study reports, for the first time, a systematic investigation into the coordination behavior bipy/phen in the heterometallic iron-uranium system covering all the combinations of the possible redox couples (i.e., Fe2+/Fe3+ and U4+/U6+) that are potentially relevant to the actual engineered or environmental systems. In total, 11 new compounds of pure uranium and heterometallic Fe–U complexes were successfully synthesized and structurally characterized. The synthesized compounds show an intriguing structural variety in terms of the nuclearity of the metal center (mono- and dinuclear arrangements for both Fe and U) and the manner of crystal packing based on different intra- and intermolecular interactions (e.g., π···π interactions, hydrogen bonding, etc.). The results also highlight the similarity of the fundamental coordination properties of bipy and phen toward Fe and U, regardless of the oxidation states of the metals, as well as the striking dissimilarity in their chemical behavior upon crystal packing.

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Section: Resultssupporting

confidence: 86%

Synthesis and Characterization of Heterometallic Iron–Uranium Complexes with a Bidentate N-Donor Ligand (2,2′-Bipyridine or 1,10-Phenanthroline)

et al. 2018

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“…Regarding the helicity in chiral space groups, a comparison of chiral structures built on helical arrangements indicates that handedness most likely stems from 3 1 /3 2 or 6 1 /6 5 units present in hexagonal arrangements. In tetragonal packings (the case of ACPA enantiomers), 4 n helices can either crystallize in chiral or achiral structures, which might likewise be related to the ability to obtain resolvable species crystallizing with noncentrosymmetric packing.…”

Section: Resultsmentioning

confidence: 99%

Revisiting HomochiralversusHeterochiral Interactions through a Long Detective Story of a Useful Azobis-Nitrile and Puzzling Racemate

García de la Concepción,

Flores-Jiménez,

Cuccia

et al. 2023

Crystal Growth & Design

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This paper documents and reinvestigates the solid-state and crystal structures of 4,4′-azobis-4-cyanopentanoic acid (ACPA), a water-soluble azobis-nitrile of immense utility as a radical initiator in living polymerizations and a labile mechanophore that can be embedded within long polymer chains to undergo selective scission under mechanical activation. Surprisingly, for such applications, both the commercially available reagent and their derivatives are used as “single initiators” when this azonitrile is actually a mixture of stereoisomers. Although the racemate and meso compounds were identified more than half a century ago and their enantiomers were separated by classical resolution, there have been confusing narratives dealing with their characterization, the existence of a conglomeratic phase, and fractional crystallization. Our results report on the X-ray crystal structures of all stereoisomers for the first time, along with further details on enantiodiscrimination and the always intriguing arguments accounting for the stability of homochiral versus heterochiral crystal aggregates. To this end, metadynamic (MTD) simulations on stereoisomer molecular aggregates were performed to capture the incipient nucleation events at the picosecond time scale. This analysis sheds light on the driving homochiral aggregation of ACPA enantiomers.

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Rare example of chiral and achiral polymorphs of a metal-oxide/organic hybrid compound

Luo

Chen

Maggard

2020

Journal of Solid State Chemistry

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Packing of Helices: Is Chirality the Highest Crystallographic Symmetry?

Cited by 8 publications

References 23 publications

Synthesis and Characterization of Heterometallic Iron–Uranium Complexes with a Bidentate N-Donor Ligand (2,2′-Bipyridine or 1,10-Phenanthroline)

Synthesis and Characterization of Heterometallic Iron–Uranium Complexes with a Bidentate N-Donor Ligand (2,2′-Bipyridine or 1,10-Phenanthroline)

Revisiting HomochiralversusHeterochiral Interactions through a Long Detective Story of a Useful Azobis-Nitrile and Puzzling Racemate

Rare example of chiral and achiral polymorphs of a metal-oxide/organic hybrid compound

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