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

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.9b10108· OSTI ID:1608330
 [1];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Northwestern Univ., Evanston, IL (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States)
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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.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
AC02-06CH11357; FG02-99ER14999
OSTI ID:
1608330
Journal Information:
Journal of the American Chemical Society, Vol. 141, Issue 44; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 21 works
Citation information provided by
Web of Science

Figures / Tables (33)

Figure 1(p. 1)figure Figure 1
Figure 2(p. 2)figure Figure 2
Figure 3(p. 3)figure Figure 3
Figure 4(p. 3)figure Figure 4
Figure 5(p. 4)figure Figure 5
Scheme 1(p. 7)figure Scheme 1
Synthesis of S1(p. 8)figure Synthesis of S1
Synthesis of S3(p. 8)figure Synthesis of S3
Synthesis of S3.5(p. 9)figure Synthesis of S3.5
Synthesis of S4(p. 9)figure Synthesis of S4
Synthesis of Boc3GTDI(p. 10)figure Synthesis of Boc3GTDI
Synthesis of GTDI(p. 11)figure Synthesis of GTDI
Figure S1(p. 13)figure Figure S1
Figure S2(p. 15)figure Figure S2
Figure S3(p. 15)figure Figure S3
Figure S4(p. 16)figure Figure S4
Table S1(p. 16)table Table S1
Figure S5(p. 17)figure Figure S5
Figure S6(p. 18)figure Figure S6
Figure S7(p. 19)figure Figure S7
Figure S8(p. 20)figure Figure S8
Figure S9(p. 21)figure Figure S9
Figure S10(p. 22)figure Figure S10
Figure S11(p. 25)figure Figure S11
Figure S12(p. 26)figure Figure S12
Figure S13(p. 27)figure Figure S13
Figure S14(p. 28)figure Figure S14
Figure S15(p. 29)figure Figure S15
Figure S16(p. 30)figure Figure S16
Figure S17(p. 30)figure Figure S17
Figure S18(p. 31)figure Figure S18
Figure S19(p. 32)figure Figure S19
Figure S20(p. 32)figure Figure S20

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Absorption
G-Quadruplex
Scattering
Chemical structure
Guanine