Covalent Grafting of Eosin Y to the Giant Keplerate {Mo132} through an Organosilicon Linker in Homogeneous Regime
Электронный научный архив УРФУ
Информация об архиве | Просмотр оригинала| Поле | Значение | |
| Заглавие |
Covalent Grafting of Eosin Y to the Giant Keplerate {Mo132} through an Organosilicon Linker in Homogeneous Regime
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| Автор |
Denikaev, A.
Kim, G. Greshnyakov, E. Moskalenko, N. Grzhegorzhevskii, K. |
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| Тематика |
CONJUGATION
ELECTRON TRANSFER EOSIN Y FLUORESCENCE KEPLERATE PHOTOCATALYSIS POLYOXOMETALATES SUPRAMOLECULAR STRUCTURE |
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| Описание |
The template effect of giant polyoxometalates (POM) shows promising results towards the supramolecular design of hybrid materials suitable for photocatalytic reactions. Here, we demonstrate a novel synthetic approach for covalently grafting the xanthene dye eosin Y (EY) to the nanoscale Keplerate POM {Mo132} via an organosilicon linker (3-aminopropyltrimethoxysilane, APTMS) in a homogeneous regime. Using a phase transfer agent, tetrabutylammonium bromide, we solubilize the Keplerate POM modified with six {Si(CH2)3NH2} groups, {Mo132}@Si6, in a series of organic solvents—acetonitrile, acetone, tetrahydrofuran, and dichloromethane—to perform post-functionalization by using an NHS-ester of EY. Both IR and Raman spectroscopy affirm the preservation of the POM’s structure and showcase an amide bond formation between POM and EY in the obtained conjugate {Mo132}@Si6@EY@TBA. Grafting’s success is observed through significant downfield shifting of EY’s aromatic protons’ signals on the 1H NMR spectrum as compared to the spectra of EY and EY-NHS. The current synthetic approach enables us to exercise precise control of the stoichiometry in the POM-dye conjugates—1:1 for the POM-EY system—as confirmed by elemental analysis. Comprehensive photophysical analysis of {Mo132}@Si6@EY@TBA by means of UV-Vis and steady-state and time-resolved fluorescence measurements points to an existing strong interaction between molecular orbitals of EY and {Mo132}, leading to a photoinduced electron transfer, partial fluorescence quenching, and elongation of the excited state’s lifetime. These findings demonstrate that using APTMS as an organosilicon linker in tandem with the Keplerate POM as a nanoscale template can be readily applied as a routine synthetic procedure for grafting various organic dyes or other organic molecules bearing a carboxylic group in their structure to the giant POM surface in a variety of aprotic organic solvents. © 2023 by the authors.
Russian Science Foundation, RSF: 21-73-00311; Ministry of Science and Higher Education of the Russian Federation: 075-15-2021-677 The authors would like to acknowledge Alisa Shmidt for edits and feedback during the writing process and Yulia Gannochenko for graphical abstract’s design. The equipment of the Ural Center for Shared Use “Modern nanotechnology” Ural Federal University (Reg. no. 2968), which is supported by the Ministry of Science and Higher Education RF (project no. 075-15-2021-677), was used. Fluorescent, NMR, and CNH studies were carried out using the equipment of the Center for Joint Use “Spectroscopy and Analysis of Organic Compounds” at the Postovsky Institute of Organic Synthesis of the Russian Academy of Sciences (Ural Branch). This research was supported by the Russian Scientific Foundation, project no. 21-73-00311. |
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| Дата |
2024-04-05T16:26:52Z
2024-04-05T16:26:52Z 2023 |
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| Тип |
Article
Journal article (info:eu-repo/semantics/article) |info:eu-repo/semantics/publishedVersion |
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| Идентификатор |
Denikaev, A, Kim, G, Greshnyakov, E, Moskalenko, N & Grzhegorzhevskii, K 2023, 'Covalent Grafting of Eosin Y to the Giant Keplerate {Mo132} through an Organosilicon Linker in Homogeneous Regime', Inorganics, Том. 11, № 6, 239. https://doi.org/10.3390/inorganics11060239
Denikaev, A., Kim, G., Greshnyakov, E., Moskalenko, N., & Grzhegorzhevskii, K. (2023). Covalent Grafting of Eosin Y to the Giant Keplerate {Mo132} through an Organosilicon Linker in Homogeneous Regime. Inorganics, 11(6), [239]. https://doi.org/10.3390/inorganics11060239 2304-6740 Final All Open Access, Gold https://www.scopus.com/inward/record.uri?eid=2-s2.0-85163749161&doi=10.3390%2finorganics11060239&partnerID=40&md5=05ba37e885eb49da07c347f177d81386 https://www.mdpi.com/2304-6740/11/6/239/pdf?version=1685436120 http://elar.urfu.ru/handle/10995/130594 10.3390/inorganics11060239 85163749161 001017286800001 |
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| Язык |
en
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| Связанные ресурсы |
info:eu-repo/grantAgreement/RSF//21-73-00311
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| Права |
Open access (info:eu-repo/semantics/openAccess)
cc-by https://creativecommons.org/licenses/by/4.0/ |
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| Формат |
application/pdf
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| Издатель |
MDPI
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| Источник |
Inorganics
Inorganics |
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