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Synthesis of Technetium Carboxylates: Wheel-Like Octanuclear Clusters (Tc<sub>8</sub>(μ-O)<sub>8</sub>(RCOO)<sub>16</sub>, Where R = CF<sub>3</sub>, C<sub>6</sub>H<sub>5</sub>)─Potential Nanobuilding Units for Tc-MOFsстатья
Статья опубликована в высокорейтинговом журнале
Статья опубликована в журнале из списка Web of Science и/или ScopusДата последнего поиска статьи во внешних источниках: 24 июля 2024 г.
- Авторы: Volkov Mikhail A., Abkhalimov Evgeny V., Novikov Anton P., Nevolin Iurii M., Grigoriev Mikhail S.
- Журнал: Inorganic Chemistry
- Том: 63
- Номер: 29
- Год издания: 2024
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 13613
- Последняя страница: 13623
- DOI: 10.1021/acs.inorgchem.4c01818
- Аннотация: Herein, we studied the behavior of TcO4– in trifluoroacetic anhydride (TFAA) under visible light irradiation in situ by UV–vis spectroscopy. One carboxylate of Tc(VII) C2F3O5Tc (1) and two wheel-like carboxylate clusters of Tc(IV) Tc8(μ-O)8(CF3COO)16 (2, 3) and Tc8(μ-O)8(C6H5COO)16 (4) were synthesized and analyzed using pXRD, TGA, UV–vis spectroscopy, and SCXRD techniques. According to SCXRD, it was found that Tc(IV) trifluoroacetate exists in two crystalline modifications. By UV–vis spectroscopy and DFT calculations, it was shown that the primary compound in the reaction system is trifluoroacetate Tc(VII). A technetium trifluoroacetate(VII) and Tc intermediates of unidentified nature both show photosensitivity. The influence of intermolecular noncovalent interactions on the volatility of trifluoroacetate and benzoate Tc(IV) is shown. The main regularities of chemical transformations of technetium in nonaqueous solutions of carboxylates have been revealed. The obtained data on the kinetics of the process suggest that technetium in trifluoroacetic anhydride can simultaneously exist in the form of Tc(VII), Tc(VI), Tc(V), and Tc(IV). Under laser ionization or prolonged heating, the formation of the Tc(II,III)-cluster is observed.
- Добавил в систему: Абхалимов Евгений Владиленович