Designing Highly Luminescent Molecular Aggregates via Bottom-Up Nanoscale Engineering
Coupling of excitations between organic fluorophores in J-aggregates leads to coherent delocalization of excitons across multiple molecules, resulting in materials with high extinction coefficients, long-range exciton transport, and, in particular, short radiative lifetimes. Despite these favorable...
| Main Authors: | , , , |
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| Format: | Article |
| Language: | English |
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American Chemical Society (ACS)
2022
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| Online Access: | https://hdl.handle.net/1721.1/140302 |
| _version_ | 1826201724205924352 |
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| author | Barotov, Ulugbek Klein, Megan D. Wang, Lili Bawendi, Moungi G. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Barotov, Ulugbek Klein, Megan D. Wang, Lili Bawendi, Moungi G. |
| author_sort | Barotov, Ulugbek |
| collection | MIT |
| description | Coupling of excitations between organic fluorophores in J-aggregates leads to coherent delocalization of excitons across multiple molecules, resulting in materials with high extinction coefficients, long-range exciton transport, and, in particular, short radiative lifetimes. Despite these favorable optical properties, uses of J-aggregates as high-speed light sources have been hindered by their low photoluminescence (PL) quantum yields (QYs). Here, we take a bottom-up approach to design a novel J-aggregate system with a large extinction coefficient, a high QY, and a short lifetime. To achieve this goal, we first select a J-aggregating cyanine chromophore and reduce its nonradiative pathways by rigidifying the backbone of the cyanine dye. The resulting conformationally restrained cyanine dye exhibits strong absorbance at 530 nm and fluorescence at 550 nm with 90% QY and 2.3 ns lifetime. We develop optimal conditions for the self-assembly of highly emissive J-aggregates. Cryogenic transmission electron microscopy (cryo-TEM) and dynamic light scattering (DLS) reveal micron-scale extended structures with two-dimensional (2D) sheetlike morphology, indicating a long-range structural order. These novel J-aggregates have strong, red-shifted absorption at 600 nm, resonant fluorescence with no Stokes shift, 50% QY, and 220 ps lifetime at room temperature. We further stabilize these aggregates in a glassy sugar matrix and study their excitonic behavior using temperature-dependent absorption and fluorescence spectroscopy. These temperature-dependent studies confirm J-type excitonic coupling and superradiance. Our results have implications for the development of a new generation of organic fluorophores that combine high speed, high QY, and solution processing. |
| first_indexed | 2024-09-23T11:56:03Z |
| format | Article |
| id | mit-1721.1/140302 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T11:56:03Z |
| publishDate | 2022 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1403022024-06-07T17:52:22Z Designing Highly Luminescent Molecular Aggregates via Bottom-Up Nanoscale Engineering Barotov, Ulugbek Klein, Megan D. Wang, Lili Bawendi, Moungi G. Massachusetts Institute of Technology. Department of Chemistry Coupling of excitations between organic fluorophores in J-aggregates leads to coherent delocalization of excitons across multiple molecules, resulting in materials with high extinction coefficients, long-range exciton transport, and, in particular, short radiative lifetimes. Despite these favorable optical properties, uses of J-aggregates as high-speed light sources have been hindered by their low photoluminescence (PL) quantum yields (QYs). Here, we take a bottom-up approach to design a novel J-aggregate system with a large extinction coefficient, a high QY, and a short lifetime. To achieve this goal, we first select a J-aggregating cyanine chromophore and reduce its nonradiative pathways by rigidifying the backbone of the cyanine dye. The resulting conformationally restrained cyanine dye exhibits strong absorbance at 530 nm and fluorescence at 550 nm with 90% QY and 2.3 ns lifetime. We develop optimal conditions for the self-assembly of highly emissive J-aggregates. Cryogenic transmission electron microscopy (cryo-TEM) and dynamic light scattering (DLS) reveal micron-scale extended structures with two-dimensional (2D) sheetlike morphology, indicating a long-range structural order. These novel J-aggregates have strong, red-shifted absorption at 600 nm, resonant fluorescence with no Stokes shift, 50% QY, and 220 ps lifetime at room temperature. We further stabilize these aggregates in a glassy sugar matrix and study their excitonic behavior using temperature-dependent absorption and fluorescence spectroscopy. These temperature-dependent studies confirm J-type excitonic coupling and superradiance. Our results have implications for the development of a new generation of organic fluorophores that combine high speed, high QY, and solution processing. 2022-02-11T19:48:45Z 2022-02-11T19:48:45Z 2021-12-29 2022-02-11T19:43:41Z Article http://purl.org/eprint/type/JournalArticle 1932-7447 1932-7455 https://hdl.handle.net/1721.1/140302 Ulugbek Barotov, Megan D. Klein, Lili Wang, and Moungi G. Bawendi, Designing Highly Luminescent Molecular Aggregates via Bottom-Up Nanoscale Engineering, The Journal of Physical Chemistry C 2022 126 (1), 754-763 en 10.1021/acs.jpcc.1c09033 The Journal of Physical Chemistry C Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf American Chemical Society (ACS) Other repository |
| spellingShingle | Barotov, Ulugbek Klein, Megan D. Wang, Lili Bawendi, Moungi G. Designing Highly Luminescent Molecular Aggregates via Bottom-Up Nanoscale Engineering |
| title | Designing Highly Luminescent Molecular Aggregates via Bottom-Up Nanoscale Engineering |
| title_full | Designing Highly Luminescent Molecular Aggregates via Bottom-Up Nanoscale Engineering |
| title_fullStr | Designing Highly Luminescent Molecular Aggregates via Bottom-Up Nanoscale Engineering |
| title_full_unstemmed | Designing Highly Luminescent Molecular Aggregates via Bottom-Up Nanoscale Engineering |
| title_short | Designing Highly Luminescent Molecular Aggregates via Bottom-Up Nanoscale Engineering |
| title_sort | designing highly luminescent molecular aggregates via bottom up nanoscale engineering |
| url | https://hdl.handle.net/1721.1/140302 |
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