Rotaxane rings promote oblique packing and extended lifetimes in DNA-templated molecular dye aggregates
| Autor: | Christopher K. Wilson, Bernard Yurke, Olga A. Mass, Ryan D. Pensack, Jonathan S. Huff, Paul H. Davis, Matthew S. Barclay, Ewald A. Terpetschnig, Simon K. Roy, William B. Knowlton, Daniel B. Turner, Donald L. Kellis, Jeunghoon Lee |
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| Rok vydání: | 2021 |
| Předmět: |
Organic electronics
Rotaxane Materials science Absorption spectroscopy Exciton 02 engineering and technology General Chemistry 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences Biochemistry Article 0104 chemical sciences Chemistry chemistry.chemical_compound chemistry Chemical physics Materials Chemistry Environmental Chemistry 0210 nano-technology Quantum information science Absorption (electromagnetic radiation) QD1-999 Nanoscopic scale DNA |
| Zdroj: | Commun Chem Communications Chemistry, Vol 4, Iss 1, Pp 1-11 (2021) |
| ISSN: | 2399-3669 |
| DOI: | 10.1038/s42004-021-00456-8 |
| Popis: | Molecular excitons play a central role in natural and artificial light harvesting, organic electronics, and nanoscale computing. The structure and dynamics of molecular excitons, critical to each application, are sensitively governed by molecular packing. Deoxyribonucleic acid (DNA) templating is a powerful approach that enables controlled aggregation via sub-nanometer positioning of molecular dyes. However, finer sub-Angstrom control of dye packing is needed to tailor excitonic properties for specific applications. Here, we show that adding rotaxane rings to squaraine dyes templated with DNA promotes an elusive oblique packing arrangement with highly desirable optical properties. Specifically, dimers of these squaraine:rotaxanes exhibit an absorption spectrum with near-equal intensity excitonically split absorption bands. Theoretical analysis indicates that the transitions are mostly electronic in nature and only have similar intensities over a narrow range of packing angles. Compared with squaraine dimers, squaraine:rotaxane dimers also exhibit extended excited-state lifetimes and less structural heterogeneity. The approach proposed here may be generally useful for optimizing excitonic materials for a variety of applications ranging from solar energy conversion to quantum information science. DNA templating is a useful strategy to control the positioning and aggregation of molecular dyes on a sub-nanometer scale, but sub-angstrom control is desirable for the precise tailoring of excitonic properties. Here, the authors show that templating squaraine dyes functionalized with rotaxane rings promotes an elusive oblique packing arrangement and extended excited-state lifetimes. |
| Databáze: | OpenAIRE |
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