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Title: Symmetry-Breaking Charge Separation in a Nanoscale Terrylenediimide Guanine-Quadruplex Assembly

Abstract

Guanine-quadruplex (G-quadruplex) assemblies provide a useful platform for studying the spatial, structural, and photophysical effects of intermolecular interactions. Coupling a single guanine moiety to terrylenediimide (TDI)—a chromophore with a large extended $$π$$-surface—produces a structure (GTDI) that assembles in plate-like tetramers, with the potential of undergoing tunable $$π$$-stacking. We report that at high concentrations (3 x 10-3 M), GTDI self-assembles into a nearly monodisperse G-quadruplex structure of 16 layers, with strong $$π$$-overlap between TDI moieties, observed by small- and wide-angle X-ray scattering. Transient absorption spectroscopy reveals that excitation of TDI in the G-quadruplex results in symmetry-breaking charge separation to form ion pairs within the structure, owing to the strong $$π$$-overlap enforced by the hydrogen-bonding. These assemblies yield important insights into the interplay of noncovalent interactions in the assembly of ordered chromophoric arrays.

Authors:
 [1];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Northwestern Univ., Evanston, IL (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1608330
Grant/Contract Number:  
AC02-06CH11357; FG02-99ER14999
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 44; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Absorption; G-Quadruplex; Scattering; Chemical structure; Guanine

Citation Formats

Powers-Riggs, Natalia E., Zuo, Xiaobing, Young, Ryan M., and Wasielewski, Michael R. Symmetry-Breaking Charge Separation in a Nanoscale Terrylenediimide Guanine-Quadruplex Assembly. United States: N. p., 2019. Web. doi:10.1021/jacs.9b10108.
Powers-Riggs, Natalia E., Zuo, Xiaobing, Young, Ryan M., & Wasielewski, Michael R. Symmetry-Breaking Charge Separation in a Nanoscale Terrylenediimide Guanine-Quadruplex Assembly. United States. https://doi.org/10.1021/jacs.9b10108
Powers-Riggs, Natalia E., Zuo, Xiaobing, Young, Ryan M., and Wasielewski, Michael R. Thu . "Symmetry-Breaking Charge Separation in a Nanoscale Terrylenediimide Guanine-Quadruplex Assembly". United States. https://doi.org/10.1021/jacs.9b10108. https://www.osti.gov/servlets/purl/1608330.
@article{osti_1608330,
title = {Symmetry-Breaking Charge Separation in a Nanoscale Terrylenediimide Guanine-Quadruplex Assembly},
author = {Powers-Riggs, Natalia E. and Zuo, Xiaobing and Young, Ryan M. and Wasielewski, Michael R.},
abstractNote = {Guanine-quadruplex (G-quadruplex) assemblies provide a useful platform for studying the spatial, structural, and photophysical effects of intermolecular interactions. Coupling a single guanine moiety to terrylenediimide (TDI)—a chromophore with a large extended $π$-surface—produces a structure (GTDI) that assembles in plate-like tetramers, with the potential of undergoing tunable $π$-stacking. We report that at high concentrations (3 x 10-3 M), GTDI self-assembles into a nearly monodisperse G-quadruplex structure of 16 layers, with strong $π$-overlap between TDI moieties, observed by small- and wide-angle X-ray scattering. Transient absorption spectroscopy reveals that excitation of TDI in the G-quadruplex results in symmetry-breaking charge separation to form ion pairs within the structure, owing to the strong $π$-overlap enforced by the hydrogen-bonding. These assemblies yield important insights into the interplay of noncovalent interactions in the assembly of ordered chromophoric arrays.},
doi = {10.1021/jacs.9b10108},
journal = {Journal of the American Chemical Society},
number = 44,
volume = 141,
place = {United States},
year = {2019},
month = {10}
}

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Figures / Tables:

Figure 1 Figure 1: Deprotection of Boc3GTDI and GTDI4 assembly.

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