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Donor-acceptor complexes of main group 14 elements with α-diimines and catecholate ligands

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Abstract

A series of new six-coordinate silicon, germanium, and tin complexes based on 3,6-di-tert-butyl-o-benzoquinone with N-donor ligands (1,10-phenanthroline and 2,2′-bipyridine) were synthesized and structurally and spectrally characterized. According to the results of electrochemical measurements, the complexes can be oxidized or reduced (they are redox amphoteric) due to the presence of redox-active ligands. The electronic absorption spectra of the compounds show absorption in the 450–500 nm range, which accounts for their intense color. This absorption band is blue-shifted with increasing solvent polarity. The combination of the spectral characteristics and results of quantum chemical calculations indicates that the synthesized silicon, germanium, and tin complexes can be considered as donor-acceptor chromophores with photoinduced ligand-to-ligand charge transfer between the diimine moiety and catechols.

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Acknowledgements

This study was performed using the equipment of the Center for Collective Use, Analytical Center of the G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, supported by the grant “Provision of the Development of Material and Technical Infrastructure of Centers for Collective Use of Research Equipment” (unique identifier RF-2296.61321X0017, Agreement No. 075-15-2021-670) and the Center for Collective Use of Physical Investigation Methods, N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences.

Funding

The study was financially supported by the Russian Science Foundation (Project No. 22-13-00351).

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Authors and Affiliations

  1. G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 ul. Tropinina, 603137, Nizhniy Novgorod, Russian Federation

    K. V. Arsenyeva, A. V. Klimashevskaya, M. V. Arsenyev, A. V. Cherkasov, A. V. Maleeva, O. Yu. Trofimova & A. V. Piskunov

  2. N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 31 Leninsky prosp., 119991, Moscow, Russian Federation

    I. A. Yakushev

  3. National Research Center “Kurchatov Institute”, 1 pl. Akad. Kurchatova, 123182, Moscow, Russian Federation

    P. V. Dorovatovskii

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  1. K. V. Arsenyeva
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  2. A. V. Klimashevskaya
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Dedicated to Academician of the Russian Academy of Sciences M. P. Egorov on the occasion of his 70th birthday.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, Vol. 73, No. 1, pp. 117–130, January, 2024.

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Arsenyeva, K.V., Klimashevskaya, A.V., Arsenyev, M.V. et al. Donor-acceptor complexes of main group 14 elements with α-diimines and catecholate ligands. Russ Chem Bull 73, 117–130 (2024). https://doi.org/10.1007/s11172-024-4123-z

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