Self-sorting chiral subcomponent rearrangement during crystallization

Marie Hutin, Christopher J. Cramer, Laura Gagliardi, Abdul Rehaman Moughal Shahi, Gérald Bernardinelli, Radovan Cerny, Jonathan R. Nitschke

Research output: Contribution to journalArticlepeer-review

96 Scopus citations

Abstract

The incorporation of enantiopure 1-amino-2,3-propanediol as a subcomponent into a dicopper double helicate resulted in perfect chiral induction of the helicate's twist. DFT calculations allowed the determination of the helicity of the complex in solution. The same helical induction, in which S amines induced a Λ helical twist, was observed in the solid state by X-ray crystallography. Electronic structure calculations also revealed that the unusual deep green color of this class of complexes was due to a metal-to-ligand charge transfer excitation, in which the excited state possesses a valence delocalized Cu23+ core. The use of a racemic amine subcomponent resulted in the formation of a dynamic library of six diastereomeric pairs of enantiomers. Surprisingly, this library converted into a single pair of enantiomers during crystallization. We were able to observe this process reverse upon redissolution, as initial ligand exchange was followed by covalent imine metathesis.

Original languageEnglish (US)
Pages (from-to)8774-8780
Number of pages7
JournalJournal of the American Chemical Society
Volume129
Issue number28
DOIs
StatePublished - Jul 18 2007

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