Confinement-Driven Photophysics in Cages, Covalent-Organic Frameworks, Metal-Organic Frameworks, and DNA.
In: Journal of the American Chemical Society, Jg. 142 (2020-03-11), Heft 10, S. 4769-4783
academicJournal
Zugriff:
Photophysics tunability through alteration of framework aperture (metal-organic framework (MOF) = variable; guest = constant) was probed for the first time in comparison with previously explored concepts (MOF = constant; guest = variable). In particular, analysis of the confinement effect on a photophysical response of integrated 5-(3-chlorobenzylidene)-2,3-dimethyl-3,5-dihydro-4 H -imidazol-4-one (Cl-BI) chromophore allowed us to establish a photophysics-aperture relationship. To shed light on the observed correlation, the framework confined environment was replicated using a molecular cage, Pd 6 (TPT) 4 (TPT = 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine), thus allowing for utilization of crystallography, spectroscopy, and theoretical simulations to reveal the effect a confined space has on the chromophore's molecular conformation (including disruption of strong hydrogen bonding and novel conformer formation) and any associated changes on a photophysical response. Furthermore, the chosen Cl- o HBI@Pd 6 (TPT) 4 (Cl- o HBI = 5-(5-chloro-2-hydroxybenzylidene)-2,3-dimethyl-3,5-dihydro-4 H -imidazol-4-one, chromophore) system was applied as a tool for targeted cargo delivery of a chromophore to the confined space of DNA, which resulted in promotion of chromophore-DNA interactions through a well-established intercalation mechanism. Moreover, the developed principles were applied toward utilizing a HBI-based chromophore as a fluorescent probe on the example of macrophage cells. For the first time, suppression of non-radiative decay pathways of a chromophore was tested by anchoring the chromophore to a framework metal node, portending a potential avenue to develop an alternative to natural biomarkers. Overall, these studies are among the first attempts to demonstrate the unrevealed potential of a confined scaffold environment for tailoring a material's photophysical response.
Titel: |
Confinement-Driven Photophysics in Cages, Covalent-Organic Frameworks, Metal-Organic Frameworks, and DNA.
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Autor/in / Beteiligte Person: | Dolgopolova, EA ; Berseneva, AA ; Faillace, MS ; Ejegbavwo, OA ; Leith, GA ; Choi, SW ; Gregory, HN ; Rice, AM ; Smith, MD ; Chruszcz, M ; Garashchuk, S ; Mythreye, K ; Shustova, NB |
Zeitschrift: | Journal of the American Chemical Society, Jg. 142 (2020-03-11), Heft 10, S. 4769-4783 |
Veröffentlichung: | Washington, DC : American Chemical Society ; <i>Original Publication</i>: Easton, Pa. [etc.], 2020 |
Medientyp: | academicJournal |
ISSN: | 1520-5126 (electronic) |
DOI: | 10.1021/jacs.9b13505 |
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