Please use this identifier to cite or link to this item: https://doi.org/10.1021/ja100579z
Title: Synthesis, structural investigations, hydrogen-deuterium exchange studies, and molecular modeling of conformationally stablilized aromatic oligoamides
Authors: Yan, Y.
Qin, B.
Ren, C.
Chen, X.
Yip, Y.K.
Ye, R.
Zhang, D.
Su, H.
Zeng, H. 
Issue Date: 28-Apr-2010
Citation: Yan, Y., Qin, B., Ren, C., Chen, X., Yip, Y.K., Ye, R., Zhang, D., Su, H., Zeng, H. (2010-04-28). Synthesis, structural investigations, hydrogen-deuterium exchange studies, and molecular modeling of conformationally stablilized aromatic oligoamides. Journal of the American Chemical Society 132 (16) : 5869-5879. ScholarBank@NUS Repository. https://doi.org/10.1021/ja100579z
Abstract: Biasing the conformational preferences of aromatic oligoamides by internally placing intramolecular hydrogen bonds has led to a series of stably folded molecular strands. This article presents the results from extensive solid-state, solution, and computational studies on these folding oligomers. Depending on its backbone length, an oligoamide adopts a crescent or helical conformation. Surprisingly, despite the highly repetitive nature of the backbone, the internally placed, otherwise very similar intramolecular hydrogen bonds showed significantly different stabilities as demonstrated by hydrogen-deuterium exchange data. It was also observed that the hydrogen-bonding strength can be tuned by adjusting the substituents attached to the exterior of the aromatic backbones. Examining the amide hydrogen-deuterium exchange rates of trimers revealed that a six-membered hydrogen bond nearing the ester end is the weakest among all the four intramolecular hydrogen bonds of a molecule. This observation was verified by ab initio quantum mechanical calculations at the level of B3LYP/6-31G. Such a "weak point" creates the "battle of the bulge" where backbone twisting is centered, which is consistently observed in the solid-state structures of the four trimer molecules studied. In the solid state, the oligomers assemble into interesting one-dimensional structures. A pronounced columnar packing of short oligomers (i.e., dimers, trimers, and tetramer) and channel-like, potentially ion-conducting stacks of longer oligomers (i.e., tetramer, pentamer, and hexamer) were observed. © 2010 American Chemical Society.
Source Title: Journal of the American Chemical Society
URI: http://scholarbank.nus.edu.sg/handle/10635/77199
ISSN: 00027863
DOI: 10.1021/ja100579z
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