Structural aspects of solid solutions of enantiomers: the 3-hydroxymethyl- and 3-carboxy-2,2,5,5-tetramethylpyrrolidinyl 1-oxyl systems as examples

Chion, B.; Lajzérowicz, J.; Bordeaux, D.; Collet, André; Jacques, Jean

doi:10.1021/j100514a010

Cited by 46 publications

(48 citation statements)

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“…When a racemic mixture condenses in 3D it may form a racemic compound, in which both enantiomers are present in the same single crystal; a conglomerate, in which the single crystals contain only one enantiomer, but the sample as a whole is racemic; and a solid solution, in which the condensate contains the two enantiomers in a nonordered arrangement [113]. Racemic crystals are by far more common as conglomerate formers, and only a few compounds tend to form solid solutions [113,114], also called a pseudoracemate [115]. Based on only eight examples, Wallach [116] came to the conclusion that racemate crystals tend to pack denser, which would explain their abundance.…”

Section: Racemic Mixturesmentioning

confidence: 99%

Molecular chirality at surfaces

Ernst

2012

Physica Status Solidi (b)

221

264

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With the adsorption of larger molecules being increasingly tackled by surface scientists, the aspect of chirality often plays a role. This paper gives a topical review of molecular chirality at surfaces and gives a phenomenological overview of different aspects of adsorption and self‐assembly of chiral and prochiral molecules and the principles of mirror‐symmetry breaking at a surface. After a brief introduction into the history of molecular chirality and the important role it played for understanding the spatial structure of molecules, definitions of chirality are presented. Topics treated here are principle ways to create single chiral adsorbates, chiral ensembles, and monolayers by achiral molecules, adsorption of intrinsically chiral molecules at achiral and chiral surfaces, long‐range symmetry breaking in two‐dimensional (2D) crystals due to additional chiral bias, chiral restructuring of solid surfaces under the influence of chiral molecules, switching the handedness of adsorbates, and chirality at the liquid/air interface. An outlook onto further potential research directions and recommendations for further reading, including nonsurface‐related sources of chiral topics completes this paper.

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Section: Racemic Mixturesmentioning

confidence: 99%

Molecular chirality at surfaces

Ernst

2012

Physica Status Solidi (b)

221

264

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“…Lastly, crystalline racemates may be solid solutions, with random dispersion of the two enantiomers throughout the crystal (Jacques et al, 1991). Solid solutions are rare (Huang et al, 2006), but it has been suggested that chiral molecules with a pseudo-element of symmetry are more likely to crystallize as solid solutions (Chion et al, 1978). Similarly, pseudosymmetric diastereomers or enantiomers that are similar in shape to a sufficient extent are more likely to crystallize as solid solutions (Barabas et al, 2000).…”

Section: Two-dimensional Solid Solution Racemate Built Of Infinite Ramentioning

confidence: 99%

An aza-cyclophane stacked in racemic columnar assemblies: whole-molecule disorder in a two-dimensional solid solution

Zeller

Lutz

Becker

2009

Acta Crystallogr Sect B

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The oxime derivative of [1.1.1]cyclophane cyclotriveratrylene (CTV) was ring expanded utilizing a Beckmann rearrangement to provide a ten-membered N-acetyl macrocyclic amide that crystallizes as a chloroform monosolvate in columnar assemblies manifesting an unusual disorder within the crystal. Columns made up of this structure consist of infinite columnar assemblies of alternating D and L enantiomers and therefore necessarily are made up of a racemate, yet the chiralities of individual molecules in adjacent columns are independent of one another, leading to the overall formation of a two-dimensional solid solution. The random arrangement of the columns within the structure leads to the emergence of a crystallographic mirror plane not reflected by the molecular symmetry, to a change of symmetry from Pna2(1) to Pnma and to whole-molecule disorder of the bowl-shaped molecules within the columns.

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“…About 35 years ago, Chion et al. underlined the role of two structural criteria regarding the formation of enantiomeric solid solutions: isosterism (i.e., the building units of opposite chirality are sterically equivalent) and isomorphism (i.e., substitution of one enantiomer by its counterpart in the crystal lattice preserves the main intermolecular interactions of the structure) . Since then, few crystal structures of enantiomeric solid solutions have been reported and thoroughly described .…”

Section: Introductionmentioning

confidence: 99%

“…About 35 years ago, Chion et al underlined the role of two structural criteria regarding the formation of enantiomerics olid solutions:i sosterism( i.e.,t he building units of opposite chirality are sterically equivalent) and isomorphism (i.e.,s ubstitution of one enantiomer by its counterparti nt he crystal lattice preserves the main intermolecular interactions of the structure). [22] Since then,f ew crystal structures of enantiomeric solid solutions have been reported and thoroughly described. [23][24][25][26][27][28][29][30][31][32][33] In some cases,i tc an be observed that isosterism and isomorphism criteria are actually satisfied in relation to ac onformational flexibility of the components, which provides as ufficientd egree of freedom in each enantiomer to mimic the conformation of its counterpart (i.e.,conformational mimicry).…”

Section: Introductionmentioning

confidence: 99%

Prenucleation Self‐Assembly and Chiral Discrimination Mechanisms during Solution Crystallisation of Racemic Diprophylline

Brandel

Cartigny

Coquerel

et al. 2016

Chemistry A European J

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This version is available at https://strathprints.strath.ac.uk/58510/ Strathprints is designed to allow users to access the research output of the University of Strathclyde. Unless otherwise explicitly stated on the manuscript, Copyright © and Moral Rights for the papers on this site are retained by the individual authors and/or other copyright owners. Please check the manuscript for details of any other licences that may have been applied. You may not engage in further distribution of the material for any profitmaking activities or any commercial gain. You may freely distribute both the url (https://strathprints.strath.ac.uk/) and the content of this paper for research or private study, educational, or not-for-profit purposes without prior permission or charge.Any correspondence concerning this service should be sent to the Strathprints administrator: strathprints@strath.ac.ukThe Strathprints institutional repository (https://strathprints.strath.ac.uk) is a digital archive of University of Strathclyde research outputs. It has been developed to disseminate open access research outputs, expose data about those outputs, and enable the management and persistent access to Strathclyde's intellectual output. FULL PAPER Pre-Nucleation Self-Assembly and Chiral Discrimination Mechanisms during Solution Crystallization of Racemic DiprophyllineClément Brandel,* [a] Yohann Cartigny, [a] Gérard Coquerel, [a] Joop H. ter Horst, [b] and Samuel Petit [a] Abstract: The crystallization behavior of (RS)-Diprophylline (DPL) in two different solvents is investigated in order to assess the incidence of solvated pre-associations on nucleation, crystal growth and chiral discrimination. In the solvated state, Raman spectroscopy shows that dimeric associations similar to those depicted in the crystalline solid solution (ssRII) predominate in isopropyl alcohol (IPA), which may account for the systematic spontaneous nucleation of this crystal form from this solvent. By contrast, spontaneous nucleation in dimethylformamide yields the stable racemic compound RI, consistently with the distinct features of the Raman spectrum collected in this solvent. A crystal growth study of ssRII in IPA reveals that the crystal habitus is impacted by the solution enantiomeric excess which is explained by an increased competition between homo and heterochiral pre-associations. This is supported by a molecular modelling study on the enantiomeric selectivity of the DPL crystal lattices. The combination of assessment methods on solution chemistry, nucleation and chiral discrimination provides methodological tools from which the occurrence of solid solutions can be rationalized.

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Structural aspects of solid solutions of enantiomers: the 3-hydroxymethyl- and 3-carboxy-2,2,5,5-tetramethylpyrrolidinyl 1-oxyl systems as examples

Abstract: Most equimolecular mixtures of enantiomers, i.e., tively few (there are ca. 250 inventoried cases1) are conracemates, crystallize as racemic compounds, while reíaglomerates, i.e., cases which permit spontaneous resolution.

Cited by 46 publications

References 1 publication

Molecular chirality at surfaces

Molecular chirality at surfaces

An aza-cyclophane stacked in racemic columnar assemblies: whole-molecule disorder in a two-dimensional solid solution

Prenucleation Self‐Assembly and Chiral Discrimination Mechanisms during Solution Crystallisation of Racemic Diprophylline

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