Self-Sorting Chiral Subcomponent Rearrangement During Crystallization
- 26 June 2007
- journal article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 129 (28), 8774-8780
- https://doi.org/10.1021/ja070320j
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.This publication has 39 references indexed in Scilit:
- Chiral Translation and Cooperative Self-Assembly of Discrete Helical Structures Using Molecular Recognition DyadsJournal of the American Chemical Society, 2006
- Novel Phenanthroline Ligands and Their Kinetically Locked Copper(I) Complexes with Unexpected Photophysical PropertiesInorganic Chemistry, 2006
- Selection Rules for Helicate Ligand Component Self-Assembly: Steric, pH, Charge, and Solvent EffectsJournal of the American Chemical Society, 2004
- Chiral and Achiral Crystal StructuresHelvetica Chimica Acta, 2003
- COSMO Implementation in TURBOMOLE: Extension of an efficient quantum chemical code towards liquid systemsPhysical Chemistry Chemical Physics, 2000
- Saccharide Sensing with Molecular Receptors Based on Boronic AcidAngewandte Chemie, 1996
- Fully optimized contracted Gaussian basis sets for atoms Li to KrThe Journal of Chemical Physics, 1992
- Density-functional exchange-energy approximation with correct asymptotic behaviorPhysical Review A, 1988
- Base-catalyzed isotopic exchange of molecular hydrogen. 4. Hydrogen isotope effects in the dimethyl sulfoxide-water systemJournal of the American Chemical Society, 1978
- LXXXIX.—The carbohydrates of the cereal strawsJournal of the Chemical Society, Transactions, 1897