Exploring the Design of Superradiant J-Aggregates from Amphiphilic Monomer Units

24 January 2023, Version 4
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

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.

Keywords

J-aggregate
Cyanine dye
Superradiance

Supplementary materials

Title
Description
Actions
Title
Supporting Information for Exploring the Design of Superradiant J-Aggregates from Amphiphilic Monomer Units
Description
Synthesis, photophysical characterization, and computational screening details.
Actions

Comments

Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.