Frenkel excitons in heat-stressed supramolecular nanocomposites enabled by tunable cage-like scaffolding

Ng, K. Y Simon; Webster, Megan; Carbery, William P.; Visaveliya, Nikunjkumar; Gaikwad, Pooja; Jang, Seogjoo; Kretzschmar, Ilona; Eisele, Dörthe M.

doi:10.1038/s41557-020-00563-4

“…C8S3 was first introduced to the literature in 1997 22 and has since been studied extensively as a model system for as exciton transport, antenna effects, superradiance and quantum coherence. 14,[23][24][25][26][27][28][29][30] Recent work used synthetic modifications on the C8S3 monomer to affect aggregation properties; larger halogen substitutions have been shown to increase the tube diameter, while placement of the halogen atoms was found to be critical in achieving H-vs. J-aggregation. 31,32 Here, we expand this body of work by synthesizing elongated C8S3 dyes with redshifted absorption and emission.…”

Section: Introductionmentioning

confidence: 99%

Tubular J-aggregates of cyanine dyes in the near-infrared

Bailey

¹

,

Deshmukh

²

,

Atallah

³

et al. 2021

Preprint

View full text Add to dashboard Cite

Developing improved organic infrared emitters has wide-ranging applicability in fields such as bioimaging or energy harvesting. We synthesize redshifted analogues of C8S3, a well-known cyanine dye that self assembles into tubular aggregates which have attracted widespread attention as artificial photosynthetic complexes. Despite the elongated dye structure, the new pentamethine dyes retain their tubular self-assembly and emit at near-infrared wavelengths. Cryo-electron microscopy and detailed photophysical characterization of the new aggregates reveal similar absorption lineshapes with ~100 nm of redshift, as well as supramolecular morphologies that resemble their trimethine counterparts; the pentamethine aggregates generally show more disorder and decreased superradiance, suggesting that more ordered structures yield more robust photophysical properties. These results provide design principles of superradiant organic emitters, expand the chemical space of near-infrared aggregates, and introduce two additional wavelength-specific antennae as model systems for study.

show abstract

“…Amphiphilic C8S3 molecules selfassemble into uniform double-layer nanotubes (NTs) in an aqueous solution. [26][27][28][29] Upon self-assembly, the characteristic absorption peak of the C8S3 monomer evolves from a broad peak into two red-shifted, narrow peaks, corresponding to the formation of a supramolecular J-aggregate system with strong exciton transfer. Moreover, the two layers of the NT can be separated through selective chemistry.…”

mentioning

confidence: 99%

“…Several research groups have reported another method of coating C8S3 NTs through a sol-gel hydrolysis process with 3-aminopropyltriethoxysilane and tetraethoxysilane as silica precursors. 27,29,33 Though the silica shell increases the mechanical stiffness of the NTs and improved the stability against elevated temperatures and photobleaching, the coating remained non-uniform and difficult to control as evidenced by the transmission electron microscopy (TEM) imaging. Bawendi and coworkers 34 stabilized the C8S3 NTs in a sucrose glass matrix, which reduced light and oxidative damage and enabled the observation of exciton−exciton annihilation signatures under weak excitation flux.…”

mentioning

confidence: 99%

Mussel-Inspired Surface Coating to Stabilize and Functionalize Supramolecular J-Aggregate Nanotubes Composed of Amphiphilic Cyanine Dyes

Zhang

¹

,

Lou

²

,

Zhang

³

et al. 2022

Preprint

0

View full text Add to dashboard Cite

We report a mussel-inspired strategy of polydopamine coating to stabilize and functionalize J-aggregate nanotubes formed by supramolecular self-assembly of an amphiphilic cyanine dye called C8S3 in aqueous media. Optimization of the coating condition by changing the incubation time in a slightly basic media of dopamine with different concentrations leads to conformal wrapping of the polydopamine layer with controllable thickness on the surface of the nanotubes. Compared to noncoated pristine C8S3 nanotubes, these polydopamine-coated nanotubes show enhanced stability against dilution, heating and photobleaching. Moreover, the polydopamine layer wrapping around the nanotubes serve as an adhesive for adsorption of a variety of metal ions and electroless deposition of the metal nanoparticles. Such stabilized and functionalized nanotube composites may offer a robust synthetic J-aggregate system to mimic the structure and function of light-harvesting complexes and reaction centers in photosynthetic systems.

show abstract

“…Amphiphilic C8S3 molecules selfassemble into uniform double-layer nanotubes (NTs) in an aqueous solution. [26][27][28][29] Upon self-assembly, the characteristic absorption peak of the C8S3 monomer evolves from a broad peak into two red-shifted, narrow peaks, corresponding to the formation of a supramolecular J-aggregate system with strong exciton transfer. Moreover, the two layers of the NT can be separated through selective chemistry.…”

mentioning

confidence: 99%

Mussel-Inspired Surface Coating to Stabilize and Functionalize Supramolecular J-Aggregate Nanotubes Composed of Amphiphilic Cyanine Dyes

Zhang

¹

,

Lou

²

,

Zhang

³

et al. 2022

Preprint

0

View full text Add to dashboard Cite

We report a mussel-inspired strategy of polydopamine coating to stabilize and functionalize J-aggregate nanotubes formed by supramolecular self-assembly of an amphiphilic cyanine dye called C8S3 in aqueous media. Optimization of the coating condition by changing the incubation time in a slightly basic media of dopamine with different concentrations leads to conformal wrapping of the polydopamine layer with controllable thickness on the surface of the nanotubes. Compared to noncoated pristine C8S3 nanotubes, these polydopamine-coated nanotubes show enhanced stability against dilution, heating and photobleaching. Moreover, the polydopamine layer wrapping around the nanotubes serve as an adhesive for adsorption of a variety of metal ions and electroless deposition of the metal nanoparticles. Such stabilized and functionalized nanotube composites may offer a robust synthetic J-aggregate system to mimic the structure and function of light-harvesting complexes and reaction centers in photosynthetic systems.

show abstract

Frenkel excitons in heat-stressed supramolecular nanocomposites enabled by tunable cage-like scaffolding

Cited by 30 publications

References 47 publications

Tubular J-aggregates of cyanine dyes in the near-infrared

Tubular J-aggregates of cyanine dyes in the near-infrared

Mussel-Inspired Surface Coating to Stabilize and Functionalize Supramolecular J-Aggregate Nanotubes Composed of Amphiphilic Cyanine Dyes

Mussel-Inspired Surface Coating to Stabilize and Functionalize Supramolecular J-Aggregate Nanotubes Composed of Amphiphilic Cyanine Dyes

Contact Info

Product

Resources

About