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Symmetry, volume 14, issue 2, pages 340

Interface Asymmetry Induced and Surface Pressure Controlled Valence Tautomerism in Monolayers of bis-Phthalocyaninates of Lanthanides

Publication type: Journal Article
Publication date: 2022-02-07
Journal: Symmetry
Quartile SCImago
Q2
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Impact factor: 2.7
ISSN: 20738994
Chemistry (miscellaneous)
Physics and Astronomy (miscellaneous)
General Mathematics
Computer Science (miscellaneous)
Abstract

Supramolecular systems based on transition metal complexes capable of reversible redox isomerization due to intramolecular electron transfer are one of the most interesting objects from the viewpoint of molecular switches’ design. In the present work, a comparative analysis of valence transformation of lanthanide complexes (Sm, Er, Tm and Yb) with donor-substituted bis-phthalocyaninates occurring during the formation and compression–extension of Langmuir monolayers was carried out using data of UV–Vis–NIR spectroscopy. It is shown that the numerical values of the Q-band positions in the absorption spectra for the extended monolayers of the complexes under study depend linearly on the ionic radius of the metal center, if the metals have an oxidation state of +2. This makes it possible to draw a direct analogy between the behavior of the studied compounds and analogous europium and cerium complexes, for which direct evidence of the valence tautomerism in such planar systems was obtained earlier. This led to the conclusion that the intramolecular electron transfer from the phthalocyanine ligand to the central metal ion [Ln3+(R4Pc2−)(R4Pc•−)]0→[Ln2+(R4Pc•−)2]0 occurs when solutions of donor-substituted bis-phthalocyaninates of samarium, erbium, thulium, and ytterbium are deposited onto the water subphase, and the reverse redox-isomeric transition is observed in most cases when the monolayer is compressed to high surface pressures. The first of these switches is related to the asymmetry of the air/water interface, and the second one is controlled by the lateral compression–expansion of the monolayer. It has been demonstrated that when bis-phthalocyanine monolayers of lanthanides with variable valence are transferred to solid substrates, the valence state of the metal center, and consequently, the redox-isomeric state of the complex, do not change. This means that we are able to form films with a predetermined state of the complex. Note that the redox-isomeric state of complexes should affect the entire range of physicochemical properties of such films.

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Kutsybala D. S. et al. Interface Asymmetry Induced and Surface Pressure Controlled Valence Tautomerism in Monolayers of bis-Phthalocyaninates of Lanthanides // Symmetry. 2022. Vol. 14. No. 2. p. 340.
GOST all authors (up to 50) Copy
Kutsybala D. S., Shokurov A. V., Martynov A. G., Yagodin A. V., Arslanov V. V., Gorbunova Y. G., Selektor S. L. Interface Asymmetry Induced and Surface Pressure Controlled Valence Tautomerism in Monolayers of bis-Phthalocyaninates of Lanthanides // Symmetry. 2022. Vol. 14. No. 2. p. 340.
RIS |
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TY - JOUR
DO - 10.3390/sym14020340
UR - https://doi.org/10.3390%2Fsym14020340
TI - Interface Asymmetry Induced and Surface Pressure Controlled Valence Tautomerism in Monolayers of bis-Phthalocyaninates of Lanthanides
T2 - Symmetry
AU - Kutsybala, Daria S
AU - Shokurov, Alexander V
AU - Martynov, Alexander G.
AU - Yagodin, Alexey V.
AU - Arslanov, Vladimir V.
AU - Selektor, Sofiya L
AU - Gorbunova, Yulia G.
PY - 2022
DA - 2022/02/07 00:00:00
PB - Multidisciplinary Digital Publishing Institute (MDPI)
SP - 340
IS - 2
VL - 14
SN - 2073-8994
ER -
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@article{2022_Kutsybala,
author = {Daria S Kutsybala and Alexander V Shokurov and Alexander G. Martynov and Alexey V. Yagodin and Vladimir V. Arslanov and Sofiya L Selektor and Yulia G. Gorbunova},
title = {Interface Asymmetry Induced and Surface Pressure Controlled Valence Tautomerism in Monolayers of bis-Phthalocyaninates of Lanthanides},
journal = {Symmetry},
year = {2022},
volume = {14},
publisher = {Multidisciplinary Digital Publishing Institute (MDPI)},
month = {feb},
url = {https://doi.org/10.3390%2Fsym14020340},
number = {2},
pages = {340},
doi = {10.3390/sym14020340}
}
MLA
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Kutsybala, Daria S., et al. “Interface Asymmetry Induced and Surface Pressure Controlled Valence Tautomerism in Monolayers of bis-Phthalocyaninates of Lanthanides.” Symmetry, vol. 14, no. 2, Feb. 2022, p. 340. https://doi.org/10.3390%2Fsym14020340.
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