Design Principles for Two-Dimensional Molecular Aggregates Using Kasha’s Model: Tunable Photophysics in Near and Short-Wave Infrared
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Abstract
Technologies which utilize near-infrared (NIR) (700–1000 nm) and short-wave infrared (1000–2000 nm) electromagnetic radiation have applications in deep-tissue imaging, telecommunications, and satellite telemetry due to low scattering and decreased background signal in this spectral region. It is therefore necessary to develop materials that absorb light efficiently beyond 1000 nm. Transition dipole moment coupling (e.g., J-aggregation) allows for red-shifted excitonic states and provides a pathway to highly absorptive electronic states in the infrared. We present aggregates of two cyanine dyes whose absorption peaks red-shift dramatically upon aggregation in water from ∼800 to 1000 nm and 1050 nm, respectively, with sheet-like morphologies and high molar absorptivities (ε ≈ 10 5 M –1 cm –1 ). We use Frenkel exciton theory to extend Kasha’s model for J- and H-aggregations and describe the excitonic states of two-dimensional aggregates whose slip is controlled by steric hindrance in the assembled structure. A consequence of the increased dimensionality is the phenomenon of an intermediate “I-aggregate”, one which red-shifts yet displays spectral signatures of band-edge dark states akin to an H-aggregate. We distinguish between H-, I-, and J-aggregates by showing the relative position of the bright (absorptive) state within the density of states using temperature-dependent spectroscopy. I-aggregates hold potential for applications such as charge injection moieties for semiconductors and donors for energy transfer in NIR and short-wave infrared. Our results can be used to better design chromophores with predictable and tunable aggregation with new photophysical properties.
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In some cases, J-aggregation can lead to over 100 nm red shift of both absorption and fluorescence compared to monomer dye.
“In some cases, it can lead to over 100 nm red shift of both absorption end fluorescence compared to monomer dye.107”
From The Pursuit of Shortwave Infrared-Emitting Nanoparticles with Bright Fluorescence through Molecular Design and Excited-State Engineering of Molecular Aggregates (2022) · cites this paper as [107]
The Introduction (p. 3) describes J-aggregation as producing red-shifted absorption, and Results and Discussion (p. 5) reports J-like absorption peaks near 1000–1050 nm. But the paper does not establish a shift of over 100 nm for both absorption and fluorescence relative to the monomer; its studied aggregates had little to no direct emission (Introduction, p. 3; Conclusions, p. 8). (LLM, conf=0.86)
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- [7](7) Cosco, E. D.; Caram, J. R.; Bruns, O. T.; Franke, D.; Day, R. A.; Farr, E. P.; Bawendi, M. G.; Sletten, E. M. Flavylium Polymethine Fluorophores for Nearand Shortwave Infrared Imaging. Angew. Chem., Int. Ed. 2017 , 56 , 13126 -13129. -
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Shortwave Infrared Imaging with J-Aggregates Stabilized in Hollow Mesoporous Silica Nanoparticles
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- Authors
- Deshmukh, A. P., Koppel, D., Chuang, C., Cadena, D. M., Cao, J., & Caram, J. R.
- Affiliations
- University of California, Los Angeles (US)
- University of Toronto (CA)
- Massachusetts Institute of Technology (US)
- Corresponding author
- Caram, Justin R.
- Venue
- The Journal of Physical Chemistry C
- Publisher
- American Chemical Society (ACS)
- Published
- 2019-07-09
- Volume
- 123
- Issue
- 30
- Pages
- 18702-18710
- ISSN
- 1932-7447 (ISSN-L)
- 1932-7455
- OpenAlex
- W2960246949
- Cited by
- 72
- References
- 69
- Citations by year
- 2026: 13 · 2025: 9 · 2024: 10 · 2023: 9 · 2022: 4 · 2021: 18 · 2020: 6 · 2019: 3
- FWCI
- 5.12
- Type
- journal article
- Language
- en
- Open access
- green
- doi.org
- Licence
- Locations
- The Journal of Physical Chemistry C (publishedVersion)
- ChemRxiv (acceptedVersion, cc-by-nc-nd)
- eScholarship (California Digital Library) (submittedVersion)
- Figshare (submittedVersion, cc-by-nc-nd)
- Funders
- University of California, Los Angeles
- Henry Luce Foundation
- Topics
- Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Photochemistry and Electron Transfer Studies
- Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Spectroscopy and Quantum Chemical Studies
- Physical Sciences › Materials Science › Materials Chemistry › Luminescence and Fluorescent Materials
- Keywords
- cyanine dyes, J-aggregation, H-aggregation, Frenkel excitons, near-infrared absorption, steric hindrance, chromophore design, charge injection
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