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Quantum chemical study of the unusual structure of 3d metal complexes in the gas phase

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Abstract

Based on the previous experimental and theoretical studies of the unusual dome-shaped structures of Pd II and NiII 3,5-di(tert-butyl)-2-oxyazobenzene complexes, gas-phase quantum chemical calculations were performed for related model CuII, CoII, FeII, MnII, CrII, and ZnII complexes. The calculations were carried out with full geometry optimization at the TPSSh/def2tzvp(Cu,Co,Fe,Mn,Cr,Zn)/6-311G*(C,N,O,H) level of theory. All compounds were calculated in the low-spin and high-spin states — singlet and triplet for FeII, CrII, ZnII and doublet and quartet for CuII, MnII, CoII. Metal complexes with a closed shell (Zn), a half-filled shell (Cr), and a half-filled d-subshell (Mn) have a tetrahedral structure in the gas-phase ground energy state, whereas CuII-, CoII-, and FeII-based complexes have an unusual dome-shaped structure.

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Funding

This work was performed within the framework of the state assignment (No. AAAA-A19-119092390076-7) for the Institute of Problems of Chemical Physics of the Russian Academy of Sciences.

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Authors and Affiliations

  1. Institute of Problems of Chemical Physics, Russian Academy of Sciences, 1 prosp. Akad. Semenova, 142432, Chernogolovka, Moscow Region, Russia

    S. M. Aldoshin, K. V. Bozhenko, A. N. Utenyshev & V. V. Tkachev

  2. Peoples’ Friendship University of Russia (RUDN University), 6 ul. Miklukho-Maklaya, 117198, Moscow, Russia

    K. V. Bozhenko

Authors
  1. S. M. Aldoshin
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  2. K. V. Bozhenko
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  3. A. N. Utenyshev
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  4. V. V. Tkachev
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Corresponding author

Correspondence to K. V. Bozhenko.

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Dedicated to Academician of the Russian Academy of Sciences R. Z. Sagdeev on the occasion of his 80th birthday.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2324–2331, December, 2021.

We are grateful to the Supercomputer Center of the Voronezh State University for providing computational resources for this work.

This paper does not contain descriptions of studies on animals or humans.

The authors declare no competing interests.

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Aldoshin, S.M., Bozhenko, K.V., Utenyshev, A.N. et al. Quantum chemical study of the unusual structure of 3d metal complexes in the gas phase. Russ Chem Bull 70, 2324–2331 (2021). https://doi.org/10.1007/s11172-021-3348-3

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  • DOI: https://doi.org/10.1007/s11172-021-3348-3

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