Long-Sought Redox Isomerization of the Europium(III/II) Complex Achieved by Molecular Reorientation at the Interface

Shokurov, A.V.; Kutsybala, D.S.; Martynov, A.G.; Bakirov, A.V.; Shcherbina, M.A.; Chvalun, S.N.; Gorbunova, Y.G.; Tsivadze, A.Y.; Zaytseva, A.V.; Novikov, D.; Arslanov, V.V.; Selektor, S.L.

Авторы: Shokurov Alexander V., Kutsybala Daria S., Martynov Alexander G., Bakirov Artem V., Shcherbina Maxim A., Chvalun Sergei N., Gorbunova Yulia G., Tsivadze Aslan Yu, Zaytseva Anna V., Novikov Dmitri, Arslanov Vladimir V., Selektor Sofiya L.
Журнал: Langmuir
Том: 36
Номер: 6
Год издания: 2020
Издательство: American Chemical Society
Местоположение издательства: United States
Первая страница: 1423
Последняя страница: 1429
DOI: 10.1021/acs.langmuir.9b03403
Аннотация: Redox isomerism, that is, the change of a metal cation valence state in organic complexes, can find promising applications in multistable molecular switches for various molecular electronic devices. However, despite a large number of studies devoted to such processes in organic complexes of multivalent lanthanides, redox-isomeric transformations were never observed for europium. In the present work, we demonstrate the unique case of redox isomerization of Eu(III)/Eu(II) complexes on the example of Eu(III) double-decker octa-butoxyphthalocyaninate (Eu[(BuO)8Pc]2) under ambient conditions (air and room temperature). It is shown that assumption ofthe face-on orientation on the aqueous subphase surface, in which two of each phthalocyanine decks in Eu[(BuO)8Pc]2 are located in different media (air and water), leads to the intramolecular electron transfer that results in the formation of a divalent Eu(II) cation in the complex. Lateral compression of the thus-formed monolayer results in the reorientation of bisphthalocyaninate to the edge-on state, in which the ligands can be considered identical, and occurrence of the reverse redox-isomeric transformation into the complex with a trivalent Eu cation. Both redox-isomeric states were directly observed by X-ray absorption near-edge structure spectroscopy in ultrathin films formed under different conditions.
Добавил в систему: Селектор София Львовна

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Long-Sought Redox Isomerization of the Europium(III/II) Complex Achieved by Molecular Reorientation at the Interfaceстатья