Twisted Macrocycles with Folded ortho-Phenylene Subunits
Autor: | Zacharias J. Kinney, C. Scott Hartley |
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Rok vydání: | 2017 |
Předmět: |
010405 organic chemistry
Chemistry Stereochemistry Imine Foldamer General Chemistry Nuclear magnetic resonance spectroscopy 010402 general chemistry 01 natural sciences Biochemistry Catalysis 0104 chemical sciences Folding (chemistry) Crystallography chemistry.chemical_compound Colloid and Surface Chemistry Phenylene Covalent bond Conformational isomerism |
Zdroj: | Journal of the American Chemical Society. 139(13) |
ISSN: | 1520-5126 |
Popis: | Many foldamers, oligomers that adopt well-defined secondary structures, are now known, including many exhibiting functional behavior. However, examples of foldamer subunits within larger architectures remain rare, despite the importance of higher-order structure in biomacromolecules. Here, we investigate the dynamic covalent assembly of short o-phenylenes, a simple class of aromatic foldamers, into twisted macrocycles. o-Phenylene tetramers have been combined with rod-shaped p-phenylene-, tolane-, and diphenylbutadiyene-based linkers using imine formation. Macrocyclization proceeds efficiently, inducing folding of the o-phenylenes. The resulting [3 + 3] macrocycles (three o-phenylenes and three linkers) are shape-persistent, triangular structures with twisted cores and internal diameters up to approximately 2 nm. The homochiral D3-symmetric and heterochiral C2-symmetric conformers can be distinguished by NMR spectroscopy. Analysis of the conformational distribution for the p-phenylene-linked macrocycle su... |
Databáze: | OpenAIRE |
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