TY - JOUR
T1 - Solvent independent symmetry-breaking charge separation in terrylenediimide guanine-quadruplex nanoparticles
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 No. DE-FG02-99ER14999 (M.R.W.). N.E.P.-R. was supported by the NSF Graduate Research Fellowship (Grant No. DGE-1324585). We thank J. M. Alzola for collection of GIWAXS data. The use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357.
PY - 2020/11/28
Y1 - 2020/11/28
N2 - G-quadruplex assemblies are a promising tool for self-assembling π-stacked chromophore arrays to better understand their photophysics. We have shown that coupling a single guanine moiety to terrylenediimide (TDI) produces a structure (GTDI) that self-assembles in tetrahydrofuran (THF) into a nearly monodisperse guanine-quadruplex structure having 16 π-stacked layers (GTDI4)16. The TDI surfaces were determined to have a high degree of cofacial overlap and underwent quantitative symmetry-breaking charge separation (SB-CS) upon photoexcitation. Here, we more deeply examine the relationship between solvent and aggregate formation and develop insights into structure-function relationships over a variety of solvent polarities and hydrogen-bonding capabilities. At high concentrations, GTDI assembles into guanine-quadruplex structures (GTDI4)16 in THF and toluene, as well as (GTDI4)9 in pyridine and benzonitrile. Transient absorption spectroscopy shows that SB-CS occurs in all solvents, regardless of their static dielectric constants, but the SB-CS yield is determined by structure. Solvent polarity independent SB-CS generation is also observed in GTDI films, where there is a complete absence of solvent.
AB - G-quadruplex assemblies are a promising tool for self-assembling π-stacked chromophore arrays to better understand their photophysics. We have shown that coupling a single guanine moiety to terrylenediimide (TDI) produces a structure (GTDI) that self-assembles in tetrahydrofuran (THF) into a nearly monodisperse guanine-quadruplex structure having 16 π-stacked layers (GTDI4)16. The TDI surfaces were determined to have a high degree of cofacial overlap and underwent quantitative symmetry-breaking charge separation (SB-CS) upon photoexcitation. Here, we more deeply examine the relationship between solvent and aggregate formation and develop insights into structure-function relationships over a variety of solvent polarities and hydrogen-bonding capabilities. At high concentrations, GTDI assembles into guanine-quadruplex structures (GTDI4)16 in THF and toluene, as well as (GTDI4)9 in pyridine and benzonitrile. Transient absorption spectroscopy shows that SB-CS occurs in all solvents, regardless of their static dielectric constants, but the SB-CS yield is determined by structure. Solvent polarity independent SB-CS generation is also observed in GTDI films, where there is a complete absence of solvent.
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U2 - 10.1063/5.0027471
DO - 10.1063/5.0027471
M3 - Article
C2 - 33261490
AN - SCOPUS:85097038041
VL - 153
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 20
M1 - 204302
ER -