Cyclization and Catenation Directed by Molecular Self-Assembly

We report here that molecular self-assembly can effectively direct and enhance specific reaction pathways. Using perylene π−π stacking weak attractive forces, we succeeded in synthesizing perylene bisimide macrocyclic dimer and a concatenated dimer−dimer ring from dynamic self-assembly of monomeric...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2006-08, Vol.128 (34), p.11150-11159
Main Authors: Wang, Wei, Wang, LiQiong, Palmer, Bruce J, Exarhos, Gregory J, Li, Alexander D. Q
Format: Article
Language:English
Subjects:
CHEMICAL REACTION KINETICS
Chemistry
Condensed benzenic and aromatic compounds
CYCLIZATION
DIMERS
DISULFIDES
Exact sciences and technology
General and physical chemistry
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
Kinetics and mechanisms
Magnetic Resonance Spectroscopy
Models, Molecular
Molecular Structure
Organic chemistry
PERYLENE
Preparations and properties
Reactivity and mechanisms
Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization
Spectrophotometry, Ultraviolet
SYNTHESIS
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Summary:We report here that molecular self-assembly can effectively direct and enhance specific reaction pathways. Using perylene π−π stacking weak attractive forces, we succeeded in synthesizing perylene bisimide macrocyclic dimer and a concatenated dimer−dimer ring from dynamic self-assembly of monomeric bis-N,N‘-(2-(2-(2-(2-thioacetylethoxy)ethoxy)ethoxy)ethyl)perylenetetracarboxylic diimide. The monocyclic ring closure and the dimer−dimer ring concatenation were accomplished through formation of disulfide bonds, which was readily triggered by air oxidization under basic deacetylation conditions. The perylene cyclic dimer and its concatenated tetramer were characterized using both structural methods (NMR, mass spectroscopy) and photophysical measurements (UV−vis spectroscopy). Kinetic analyses offer informative insights about reaction pathways and possible mechanisms, which lead to the formation of complex concatenated rings. Molecular dynamic behaviors of both the monocyclic dimer and the concatenated dimer−dimer ring were modeled with the NWChem molecular dynamics software module, which shows distinct stacking activities for the monocyclic dimer and the concatenated tetramer.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja061826p