TY - JOUR
T1 - Symmetry-Breaking Charge Separation in a Nanoscale Terrylenediimide Guanine-Quadruplex Assembly
AU - Powers-Riggs, Natalia E.
AU - Zuo, Xiaobing
AU - Young, Ryan M.
AU - Wasielewski, Michael R.
N1 - Funding Information:
This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-FG02-99ER14999 (M.R.W.). N.E.P.-R. was supported by a NSF Graduate Research Fellowship (DGE-1324585). X-ray scattering measurements were performed at Beamline 12-ID-B of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.
Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/11/6
Y1 - 2019/11/6
N2 - 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. At high concentrations (3 × 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- A nd 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.
AB - 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. At high concentrations (3 × 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- A nd 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.
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U2 - 10.1021/jacs.9b10108
DO - 10.1021/jacs.9b10108
M3 - Article
C2 - 31647646
AN - SCOPUS:85074223740
SN - 0002-7863
VL - 141
SP - 17512
EP - 17516
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 44
ER -