Exploring the design of superradiant J-aggregates from amphiphilic monomer units

Excitonic chromophore aggregates have wide-ranging applicability in fields such as imaging and energy harvesting; however their rational design requires adapting principles of self-assembly to the requirements of excited state coupling. Using the well-studied amphiphilic cyanine dye C8S3 as a templa...

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Bibliographic Details
Published in:Nanoscale 2023-02, Vol.15 (8), p.3841-3849
Main Authors: Bailey, Austin D, Deshmukh, Arundhati P, Bradbury, Nadine C, Pengshung, Monica, Atallah, Timothy L, Williams, Jillian A, Barotov, Ulugbek, Neuhauser, Daniel, Sletten, Ellen M, Caram, Justin R
Format: Article
Language:English
Subjects:
Aggregates
Chromophores
Cyanine dyes
Energy harvesting
Infrared analysis
Red shift
Self-assembly
Tubes
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Summary:Excitonic chromophore aggregates have wide-ranging applicability in fields such as imaging and energy harvesting; however their rational design requires adapting principles of self-assembly to the requirements of excited state coupling. Using the well-studied amphiphilic cyanine dye C8S3 as a template-known to assemble into tubular excitonic aggregates-we synthesize several redshifted variants and study their self-assembly and photophysics. The new pentamethine dyes retain their tubular self-assembly and demonstrate nearly identical bathochromic shifts and lineshapes well into near-infrared wavelengths. However, detailed photophysical analysis finds that the new aggregates show a significant decline in superradiance. Additionally, cryo-TEM reveals that these aggregates readily form short bundles of nanotubes that have nearly half the radii of their trimethine comparators. We employ computational screening to gain intuition on how the structural components of these new aggregates affect their excitonic states, finding that the narrower tubes are able to assemble into a larger number of arrangements, resulting in more disordered aggregates ( i.e. less superradiant) with highly similar degrees of redshift. Excitonic chromophore aggregates have wide-ranging applicability in fields such as imaging and energy harvesting; however their rational design requires adapting principles of self-assembly to the requirements of excited state coupling.
ISSN:2040-3364
2040-3372
DOI:10.1039/d2nr05747f