Symmetry Breaking Charge Transfer in DNA-Templated Perylene Dimer Aggregates
Molecular aggregates are of interest to a broad range of fields including light harvesting, organic optoelectronics, and nanoscale computing. In molecular aggregates, nonradiative decay pathways may emerge that were not present in the constituent molecules. Such nonradiative decay pathways may inclu...
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| Format: | Article |
| Language: | English |
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MDPI AG
2022-10-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/19/6612 |
| _version_ | 1797477885213147136 |
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| author | Katelyn M. Duncan Donald L. Kellis Jonathan S. Huff Matthew S. Barclay Jeunghoon Lee Daniel B. Turner Paul H. Davis Bernard Yurke William B. Knowlton Ryan D. Pensack |
| author_facet | Katelyn M. Duncan Donald L. Kellis Jonathan S. Huff Matthew S. Barclay Jeunghoon Lee Daniel B. Turner Paul H. Davis Bernard Yurke William B. Knowlton Ryan D. Pensack |
| author_sort | Katelyn M. Duncan |
| collection | DOAJ |
| description | Molecular aggregates are of interest to a broad range of fields including light harvesting, organic optoelectronics, and nanoscale computing. In molecular aggregates, nonradiative decay pathways may emerge that were not present in the constituent molecules. Such nonradiative decay pathways may include singlet fission, excimer relaxation, and symmetry-breaking charge transfer. Singlet fission, sometimes referred to as excitation multiplication, is of great interest to the fields of energy conversion and quantum information. For example, endothermic singlet fission, which avoids energy loss, has been observed in covalently bound, linear perylene trimers and tetramers. In this work, the electronic structure and excited-state dynamics of dimers of a perylene derivative templated using DNA were investigated. Specifically, DNA Holliday junctions were used to template the aggregation of two perylene molecules covalently linked to a modified uracil nucleobase through an ethynyl group. The perylenes were templated in the form of monomer, transverse dimer, and adjacent dimer configurations. The electronic structure of the perylene monomers and dimers were characterized via steady-state absorption and fluorescence spectroscopy. Initial insights into their excited-state dynamics were gleaned from relative fluorescence intensity measurements, which indicated that a new nonradiative decay pathway emerges in the dimers. Femtosecond visible transient absorption spectroscopy was subsequently used to elucidate the excited-state dynamics. A new excited-state absorption feature grows in on the tens of picosecond timescale in the dimers, which is attributed to the formation of perylene anions and cations resulting from symmetry-breaking charge transfer. Given the close proximity required for symmetry-breaking charge transfer, the results shed promising light on the prospect of singlet fission in DNA-templated molecular aggregates. |
| first_indexed | 2024-03-09T21:24:06Z |
| format | Article |
| id | doaj.art-d1e2a38dff3747cfa99c26fa032c35a5 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T21:24:06Z |
| publishDate | 2022-10-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-d1e2a38dff3747cfa99c26fa032c35a52023-11-23T21:14:18ZengMDPI AGMolecules1420-30492022-10-012719661210.3390/molecules27196612Symmetry Breaking Charge Transfer in DNA-Templated Perylene Dimer AggregatesKatelyn M. Duncan0Donald L. Kellis1Jonathan S. Huff2Matthew S. Barclay3Jeunghoon Lee4Daniel B. Turner5Paul H. Davis6Bernard Yurke7William B. Knowlton8Ryan D. Pensack9Micron School of Materials Science & Engineering, Boise State University, Boise, ID 83725, USAMicron School of Materials Science & Engineering, Boise State University, Boise, ID 83725, USAMicron School of Materials Science & Engineering, Boise State University, Boise, ID 83725, USAMicron School of Materials Science & Engineering, Boise State University, Boise, ID 83725, USAMicron School of Materials Science & Engineering, Boise State University, Boise, ID 83725, USAMicron School of Materials Science & Engineering, Boise State University, Boise, ID 83725, USAMicron School of Materials Science & Engineering, Boise State University, Boise, ID 83725, USAMicron School of Materials Science & Engineering, Boise State University, Boise, ID 83725, USAMicron School of Materials Science & Engineering, Boise State University, Boise, ID 83725, USAMicron School of Materials Science & Engineering, Boise State University, Boise, ID 83725, USAMolecular aggregates are of interest to a broad range of fields including light harvesting, organic optoelectronics, and nanoscale computing. In molecular aggregates, nonradiative decay pathways may emerge that were not present in the constituent molecules. Such nonradiative decay pathways may include singlet fission, excimer relaxation, and symmetry-breaking charge transfer. Singlet fission, sometimes referred to as excitation multiplication, is of great interest to the fields of energy conversion and quantum information. For example, endothermic singlet fission, which avoids energy loss, has been observed in covalently bound, linear perylene trimers and tetramers. In this work, the electronic structure and excited-state dynamics of dimers of a perylene derivative templated using DNA were investigated. Specifically, DNA Holliday junctions were used to template the aggregation of two perylene molecules covalently linked to a modified uracil nucleobase through an ethynyl group. The perylenes were templated in the form of monomer, transverse dimer, and adjacent dimer configurations. The electronic structure of the perylene monomers and dimers were characterized via steady-state absorption and fluorescence spectroscopy. Initial insights into their excited-state dynamics were gleaned from relative fluorescence intensity measurements, which indicated that a new nonradiative decay pathway emerges in the dimers. Femtosecond visible transient absorption spectroscopy was subsequently used to elucidate the excited-state dynamics. A new excited-state absorption feature grows in on the tens of picosecond timescale in the dimers, which is attributed to the formation of perylene anions and cations resulting from symmetry-breaking charge transfer. Given the close proximity required for symmetry-breaking charge transfer, the results shed promising light on the prospect of singlet fission in DNA-templated molecular aggregates.https://www.mdpi.com/1420-3049/27/19/6612perylenedimer aggregateDNA nanotechnologysinglet fissioncharge transfer |
| spellingShingle | Katelyn M. Duncan Donald L. Kellis Jonathan S. Huff Matthew S. Barclay Jeunghoon Lee Daniel B. Turner Paul H. Davis Bernard Yurke William B. Knowlton Ryan D. Pensack Symmetry Breaking Charge Transfer in DNA-Templated Perylene Dimer Aggregates Molecules perylene dimer aggregate DNA nanotechnology singlet fission charge transfer |
| title | Symmetry Breaking Charge Transfer in DNA-Templated Perylene Dimer Aggregates |
| title_full | Symmetry Breaking Charge Transfer in DNA-Templated Perylene Dimer Aggregates |
| title_fullStr | Symmetry Breaking Charge Transfer in DNA-Templated Perylene Dimer Aggregates |
| title_full_unstemmed | Symmetry Breaking Charge Transfer in DNA-Templated Perylene Dimer Aggregates |
| title_short | Symmetry Breaking Charge Transfer in DNA-Templated Perylene Dimer Aggregates |
| title_sort | symmetry breaking charge transfer in dna templated perylene dimer aggregates |
| topic | perylene dimer aggregate DNA nanotechnology singlet fission charge transfer |
| url | https://www.mdpi.com/1420-3049/27/19/6612 |
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