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Published on: February 7, 2019
Perylene bisimide atropisomers: synthesis, resolution, and stereochemical assignment
Peter Osswald1, Matthias Reichert, Gerhard Bringmann
1Universität Würzburg, Institut für Organische Chemie, Am Hubland, 97074 Würzburg, Germany.
The Journal of Organic Chemistry
|March 29, 2007
Summary
Researchers synthesized novel macrocyclic perylene bisimides, achieving the first diastereomerically pure atropisomers. These compounds exhibit unique optical and chiroptical properties, paving the way for advanced materials.
Area of Science:
- Organic Chemistry
- Materials Science
- Supramolecular Chemistry
Background:
- Perylene bisimides (PBIs) are important chromophores with tunable photophysical properties.
- Macrocyclization of PBIs can lead to novel architectures with unique electronic and optical characteristics.
- Controlling stereochemistry in complex organic molecules is crucial for advanced applications.
Purpose of the Study:
- To synthesize macrocyclic perylene bisimide derivatives through etherification.
- To separate and characterize atropisomers of diagonally bridged macrocycles.
- To investigate the optical, chiroptical, and conformational properties of these novel compounds.
Main Methods:
- Macrocyclization of a tetra-hydroxyphenoxy-substituted perylene bisimide using diethylene glycol ditosylate.
- Separation of regioisomers and atropisomers using semipreparative High-Performance Liquid Chromatography (HPLC) on a chiral column.
- Determination of absolute configurations via Circular Dichroism (CD) spectroscopy and quantum chemical calculations.
- Characterization of optical and chiroptical properties using UV/vis, fluorescence, and CD spectroscopy.
- Exploration of conformational properties using temperature-dependent proton Nuclear Magnetic Resonance (1H NMR) studies.
Main Results:
- Successful synthesis of both diagonally and laterally bridged macrocyclic perylene bisimide regioisomers.
- Isolation and separation of atropo-diastereomers of the diagonally bridged macrocycle.
- Determination of the absolute configurations of the isolated epimers, (P,R,R)-6 and (M,R,R)-6.
- These represent the first reported examples of diastereomerically pure perylene bisimide atropisomers.
- Detailed investigation of their optical, chiroptical, and conformational behaviors.
Conclusions:
- The study demonstrates a viable route to diastereomerically pure macrocyclic perylene bisimide atropisomers.
- The synthesized compounds exhibit distinct stereochemical and photophysical properties.
- These findings contribute to the understanding of stereochemistry in complex PBI systems and offer potential for new chiral materials.
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