Extremely strong tubular stacking of aromatic oligoamide macrocycles

Authors

• Mark A. Kline, State University of New York at Buffalo
• Xiaoxi Wei, State University of New York at Buffalo
• Ian J. Horner, State University of New York at Buffalo
• Rui Liu, State University of New York at Buffalo
• Shuang Chen, University of Nebraska-Lincoln
• Si Chen, Argonne National LaboratoryFollow
• Ka Yi Yung, State University of New York at Buffalo
• Kazuhiro Yamato, State University of New York at Buffalo
• Zhonghou Cai, Argonne National LaboratoryFollow
• Frank V. Bright, State University of New York at BuffaloFollow
• Xiao Cheng Zeng, University of Nebraska-LincolnFollow
• Bing Gong, State University of New York at BuffaloFollow

Document Type

Article

Date of this Version

2015

Citation

Chemical Science, 2015, 6, 152. DOI: 10.1039/c4sc02380c

Comments

© The Royal Society of Chemistry 2015. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

Abstract

As the third-generation rigid macrocycles evolved from progenitor 1, cyclic aromatic oligoamides 3, with a backbone of reduced constraint, exhibit extremely strong stacking with an astoundingly high affinity (estimated lower limit of K_dimer > 10¹³ M^–1 in CHCl₃), which leads to dispersed tubular stacks that undergo further assembly in solution. Computational study reveals a very large binding energy (–49.77 kcal mol^–1) and indicates highly cooperative local dipole interactions that account for the observed strength and directionality for the stacking of 3. In the solid-state, X-ray diffraction (XRD) confirms that the aggregation of 3 results in well-aligned tubular stacks. The persistent tubular assemblies of 3, with their non-deformable sub-nm pore, are expected to possess many interesting functions. One such function, transmembrane ion transport, is observed for 3.

Includes supplemental material.