Stabilization of Zn(IV) and N12 backbone in Zn(N12): A quantum-chemical study by DFT method
https://doi.org/10.26907/2542-064X.2025.1.24-36
Abstract
The potential existence of a zinc–nitrogen compound with Zn : N = 1 : 12, a ratio previously unknown for these elements, was shown using three versions of density functional theory (DFT): DFT M06/TZVP, DFT B3PW91/TZVP, and DFT OPBE/TZVP. Its structural parameters were determined: the group of ZnN4 atoms has a tetragonal-pyramidal geometry with a significant (exceeding 60°) deviation from coplanarity, and the bond lengths between the nitrogen atoms and the zinc atom exhibit slight variations. The group of N4 atoms is also non-coplanar, and the non-bond angles in it, formed by three neighboring atoms, deviate very significantly from 90°. A similar non-coplanarity occurs in the four five-membered rings, each containing the metal atom and four nitrogen atoms. The thermodynamic parameters and NBO values were calculated. The results obtained using the above three quantum-chemical methods are in good agreement.
Supporting agencies: All quantum-chemical calculations were performed at the Joint Supercomputer Center of Russian Academy of Sciences – Branch of Federal Scientific Center “Scientific Research Institute for System Analysis of the Russian Academy of Sciences” (http://www.jscc.ru), which is acknowledged for the technical support. D.V. Chachkov’s work was funded as part of the state assignment to the National Research Center “Kurchatov Institute” (project no. FNEF-2024-0016).
About the Authors
D. V. Chachkov
Kazan Department of Joint Supercomputer Center of Russian Academy of Sciences – Branch of Federal Scientific Center “Scientific Research Institute for System Analysis of National Research Center “Kurchatov Institute”
Russian Federation
Competing Interests:
Russian Federation
Denis V. Chachkov, Cand. Sci. (Chemistry), Leading Researcher, Laboratory of Supercomputer Modeling, Department of Supercomputer Systems and Parallel Computing
Kazan
Competing Interests:
The authors declare no conflicts of interest.
O. V. Mikhailov
Kazan National Research Technological University
Russian Federation
Competing Interests:
Russian Federation
Oleg V. Mikhailov, Dr. Sci. (Chemistry), Full Professor, Department of Analytical Chemistry, Certification and Quality Management
Kazan
Competing Interests:
The authors declare no conflicts of interest.
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For citations:
Chachkov D.V., Mikhailov O.V. Stabilization of Zn(IV) and N12 backbone in Zn(N12): A quantum-chemical study by DFT method. Uchenye Zapiski Kazanskogo Universiteta Seriya Estestvennye Nauki. 2025;167(1):24-36. (In Russ.) https://doi.org/10.26907/2542-064X.2025.1.24-36
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