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

    Year: 2020

    Journal: Langmuir, Volume 36, FEB 18, page 1423–1429

    Authors: Shokurov, AV; Kutsybala, DS; Martynov, AG; Bakirov, AV; Shcherbina, MA; Chvalun, SN; Gorbunova, YG; Tsivadze, AY; Zaytseva, AV; Novikov, D; Arslanov, VV; Selektor, SL

    Organizations: Russian Foundation for Basic ResearchRussian Foundation for Basic Research (RFBR) [18-33-20187 mol_a_ved]; Russian Science FoundationRussian Science Foundation (RSF) [19-73-20236]

    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 double-decker octa-n-butoxyph-thalocyaninate (Eu[BuO)(8)Pc](2)) under ambient conditions (air and room temperature). It is shown that assumption of the face-on orientation on the aqueous subphase surface, in which two of each phthalocyanine decks in Eu[(BuO)(8)Pc](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.
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