Journal article
Twisted perylene stereodimers reveal chiral molecular assembly codes
Journal of the American Chemical Society, Vol.130(26), pp.8271-8279
07/02/2008
Handle:
https://hdl.handle.net/2376/104318
PMID: 18540670
Abstract
Unique perylene diastereomeric linear and cyclic dimers were synthesized from twisted perylene monomers, revealing that pi-stacking stereoisomerism imparted specific intermolecular self-assembly and intramolecular folding. Only the homochiral twisted tetrachloroperylene monomers cyclized via a cooperative reaction, forming the homochiral diastereomers. The heterochiral tetrachloroperylene monomers proceeded through a stepwise reaction and yielded a linear heterochiral dimer, which equilibrated with the linear homochiral dimers. The linear homochiral dimers cyclized to produce the same cyclic homochiral diastereomers. These results demonstrated that homochiral and heterochiral self-assemblies were two distinct molecular codes, directing two specific chemical pathways. The homochiral cyclic dimers remain isomerically pure at -20 degrees C but can be interconverted to the heterochiral cyclic dimer meso compound at room temperature. The diastereomers were readily separated by HPLC. While driven by solvophobic forces, foldable linear dimers synthesized from the same twisted monomers using phosphoramidite chemistry folded into homodimer and heterodimer, confirming the inherent molecular codes, which were dictated by the perylene chirality, ultimately gauged the weak pi-stack forces, and directed self-assembly and folding.
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Details
- Title
- Twisted perylene stereodimers reveal chiral molecular assembly codes
- Creators
- Wei Wang - Washington State University, School of Chemical Engineering and BioengineeringAndrew D ShallerAlexander D Q Li
- Publication Details
- Journal of the American Chemical Society, Vol.130(26), pp.8271-8279
- Academic Unit
- Department of Chemistry
- Publisher
- United States
- Grant note
- GM065306 / NIGMS NIH HHS
- Identifiers
- 99900547075501842
- Language
- English
- Resource Type
- Journal article