Journal article
Molecular self-assembly inhibition leads to basket-shaped cyclophane formation with chiral dynamics
The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol.112(14), pp.3094-3103
04/10/2008
Handle:
https://hdl.handle.net/2376/112504
PMID: 18341307
Abstract
Planar perylene derivatives form macrocyclic dimers and concatenated dimer-dimer rings under the action of molecular self-assembly. If this underpinning principle is true, highly twisted perylene derivatives should be more frustrated toward formation of multimeric cyclic compounds such as macrocyclic dimers and concatenated dimer-dimers because of perturbation resulting from intermolecular pi-pi stacking. Indeed, 1,6,7,12- tetraphenoxy-substituted perylene is highly twisted and undergoes unimolecular cyclization rather than bimolecular or multimolecular cyclization. The resulting monocyclic monomer exhibits interesting conformation switching from one chiral structure (left-handedness) to another chiral structure (right-handedness) at room temperature. NMR studies of conformational dynamics reveal that such configuration change between the two enantiomers can be frozen at low temperature (-45 degrees C). An activation enthalpy barrier of 13.4 +/- 0.5 kcal.mol-1 for twisting the perylene plane in order to convert from one enantiomer to the other has been found.
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Details
- Title
- Molecular self-assembly inhibition leads to basket-shaped cyclophane formation with chiral dynamics
- Creators
- Wei Wang - Washington State University, School of Chemical Engineering and BioengineeringAlex D BainLi-Qiong WangGregory J ExarhosAlexander D Q Li
- Publication Details
- The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol.112(14), pp.3094-3103
- Academic Unit
- Department of Chemistry
- Publisher
- United States
- Grant note
- GM065306 / NIGMS NIH HHS
- Identifiers
- 99900547829901842
- Language
- English
- Resource Type
- Journal article