Journal Article

PUBDB-2020-00906

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Long-Sought Redox Isomerization of the Europium(III/II) Complex Achieved by Molecular Reorientation at the Interface

Shokurov, A. V. (Corresponding author) ; Kutsybala, D. S. ; Martynov, A. G. ; Bakirov, A. V.Extern* ; Shcherbina, M. A. ; Chvalun, S. N.Extern* ; Gorbunova, Y. G. ; Tsivadze, A. Y. ; Zaytseva, A. V. ; Novikov, D.DESY* ; Arslanov, V. V. ; Selektor, S. L.

2020
ACS Publ. Washington, DC

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Please use a persistent id in citations: doi:10.1021/acs.langmuir.9b03403  doi:10.3204/PUBDB-2020-00906

Abstract: 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)8Pc]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)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.

Note: © American Chemical Society

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Contributing Institute(s):

1. DOOR-User (DOOR ; HAS-User)
2. Experimentebetreuung PETRA III (FS-PET-D)

Research Program(s):

1. 6214 - Nanoscience and Materials for Information Technology (POF3-621) (POF3-621)
2. 6G3 - PETRA III (POF3-622) (POF3-622)
3. FS-Proposal: I-20190325 (I-20190325) (I-20190325)

Experiment(s):

1. PETRA Beamline P23 (PETRA III)

Appears in the scientific report 2020

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Database coverage:
; ; Clarivate Analytics Master Journal List ; Current Contents - Physical, Chemical and Earth Sciences ; Ebsco Academic Search ; IF < 5 ; JCR ; NCBI Molecular Biology Database ; Nationallizenz ; SCOPUS ; Science Citation Index ; Science Citation Index Expanded ; Web of Science Core Collection

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