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Cryo-electron microscopy has delivered a resolution revolution for biological self-assemblies, yet only a handful of structures have been solved for synthetic supramolecular materials. Particularly for chromophore supramolecular aggregates, high-resolution structures are necessary for understanding and modulating the long-range excitonic coupling. Here, we present a 3.3 Å structure of prototypical biomimetic light-harvesting nanotubes derived from an amphiphilic cyanine dye (C8S3-Cl). Helical 3D reconstruction directly visualizes the chromophore packing that controls the excitonic properties. Our structure clearly shows a brick layer arrangement, revising the previously hypothesized herringbone arrangement. Furthermore, we identify a new non-biological supramolecular motif—interlocking sulfonates—that may be responsible for the slip-stacked packing and J-aggregate nature of the light-harvesting nanotubes. This work shows how independently obtained native-state structures complement photophysical measurements and will enable accurate understanding of (excitonic) structure–function properties, informing materials design for light-harvesting chromophore aggregates.
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How to reprogram the excitonic properties and solid-state morphologies of π-conjugated supramolecular polymers
The development of supramolecular tools to modulate the excitonic properties of non-covalent assemblies paves the way to engineer new classes of semicondcuting materials relevant to flexible electronics. While controlling the assembly pathways of organic chromophores enables the formation of J-like and H-like aggregates, strategies to tailor the excitonic properties of pre-assembled aggregates through post-modification are scarce. In the present contribution, we combine supramolecular chemistry with redox chemistry to modulate the excitonic properties and solid-state morphologies of aggregates built from stacks of water-soluble perylene diimide building blocks. The n-doping of initially formed aggregates in an aqueous medium is shown to produce π–anion stacks for which spectroscopic properties unveil a non-negligible degree of electron–electron interactions. Oxidation of the n-doped intermediates produces metastable aggregates where free exciton bandwidths (Ex BW ) increase as a function of time. Kinetic data analysis reveals that the dynamic increase of free exciton bandwidth is associated with the formation of superstructures constructed by means of a nucleation-growth mechanism. By designing different redox-assisted assembly pathways, we highlight that the sacrificial electron donor plays a non-innocent role in regulating the structure–function properties of the final superstructures. Furthermore, supramolecular architectures formed via a nucleation-growth mechanism evolve into ribbon-like and fiber-like materials in the solid-state, as characterized by SEM and HRTEM. Through a combination of ground-state electronic absorption spectroscopy, electrochemistry, spectroelectrochemistry, microscopy, and modeling, we show that redox-assisted assembly provides a means to reprogram the structure–function properties of pre-assembled aggregates.
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- Award ID(s):
- 1941410
- PAR ID:
- 10211906
- Date Published:
- Journal Name:
- Physical Chemistry Chemical Physics
- ISSN:
- 1463-9076
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Exciton delocalization plays a prominent role in the photophysics of molecular aggregates, ultimately governing their particular function or application. DNA is a compelling scaffold in which to template molecular aggregates and promote exciton delocalization. As individual dye molecules are the basis of exciton delocalization in molecular aggregates, their judicious selection is important. Motivated by their excellent photostability and spectral properties, here we examine the ability of squaraine dyes to undergo exciton delocalization when aggregated via a DNA Holliday junction (HJ) template. A commercially available indolenine squaraine dye was chosen for the study given its strong structural resemblance to Cy5, a commercially available cyanine dye previously shown to undergo exciton delocalization in DNA HJs. Three types of DNA-dye aggregate configurations—transverse dimer, adjacent dimer, and tetramer—were investigated. Signatures of exciton delocalization were observed in all squaraine-DNA aggregates. Specifically, strong blue shift and Davydov splitting were observed in steady-state absorption spectroscopy and exciton-induced features were evident in circular dichroism spectroscopy. Strongly suppressed fluorescence emission provided additional, indirect evidence for exciton delocalization in the DNA-templated squaraine dye aggregates. To quantitatively evaluate and directly compare the excitonic Coulombic coupling responsible for exciton delocalization, the strength of excitonic hopping interactions between the dyes were obtained by simultaneous fitting the experimental steady-state absorption and CD spectra via a Holstein-like Hamiltonian in which, following the theoretical approach of Kühn, Renger, and May, the dominant vibrational mode is explicitly considered. The excitonic hopping strength within indolenine squaraines was found to be comparable to that of the analogous Cy5 DNA-templated aggregate. The squaraine aggregates adopted primarily an H-type (dyes oriented parallel to each other) spatial arrangement. Extracted geometric details of dye mutual orientation in the aggregates enabled close comparison of aggregate configurations and the elucidation of the influence of dye angular relationship on excitonic hopping interactions in squaraine aggregates. These results encourage the application of squaraine-based aggregates in next generation systems driven by molecular excitons.more » « less
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Molecular aggregates with long-range excitonic couplings have drastically different photophysical properties compared to their monomer counterparts. From Kasha's model for one-dimensional systems, positive or negative excitonic couplings lead to blue or red-shifted optical spectra with respect to the monomers, labeled H-and J-aggregates, respectively. The overall excitonic couplings in higher dimensional systems are much more complicated and cannot be simply classified from their spectral shifts alone. Here, we provide a unified classification for extended 2D aggregates using temperature dependent peak shifts, thermal broadening, and quantum yields. We discuss the examples of six 2D aggregates with J-like absorption spectra but quite drastic changes in quantum yields and superradiance. We find the origin of the differences is, in fact, a different excitonic band structure where the bright state is lower energy than the monomer but still away from the band edge. We call this an “I-aggregate.” Our results provide a description of the complex excitonic behaviors that cannot be explained solely on Kasha's model. Furthermore, such properties can be tuned with the packing geometries within the aggregates providing supramolecular pathways for controlling them. This will allow for precise optimizations of aggregate properties in their applications across the areas of optoelectronics, photonics, excitonic energy transfer, and shortwave infrared technologies.more » « less
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- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D0CP04819D
