Self-Sorting Chiral Subcomponent Rearrangement During Crystallization
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- 作者：Marie Hutin ; Christopher J. Cramer ; Laura Gagliardi ; Abdul Rehaman Moughal Shahi ; Gé ; rald Bernardinelli ; Radovan Cerny ; Jonathan R. Nitschke
- 刊名：Journal of the American Chemical Society
- 出版年：2007
- 出版时间：July 18, 2007
- 年：2007
- 卷：129
- 期：28
- 页码：8774 - 8780
- 全文大小：317K
- 年卷期：v.129,no.28(July 18, 2007)
- ISSN：1520-5126
文摘
The incorporation of enantiopure 1-amino-2,3-propanediol as a subcomponent into a dicopperdouble helicate resulted in perfect chiral induction of the helicate's twist. DFT calculations allowed thedetermination of the helicity of the complex in solution. The same helical induction, in which S aminesinduced a 
helical twist, was observed in the solid state by X-ray crystallography. Electronic structurecalculations 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 sixdiastereomeric pairs of enantiomers. Surprisingly, this library converted into a single pair of enantiomersduring crystallization. We were able to observe this process reverse upon redissolution, as initial ligandexchange was followed by covalent imine metathesis.
helical twist, was observed in the solid state by X-ray crystallography. Electronic structurecalculations 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 sixdiastereomeric pairs of enantiomers. Surprisingly, this library converted into a single pair of enantiomersduring crystallization. We were able to observe this process reverse upon redissolution, as initial ligandexchange was followed by covalent imine metathesis.