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Computational design of magnetically active trinuclear heterometallic complexes on the basis of 1,3,5-triazapentadiene ligands

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Abstract

A series of trinuclear mixed-ligand complexes of iron(II) 2,6-di(pyrazol-1-yl)pyridine moieties with linkers on the basis of 1,3,5-triazapentadiene transition metal (M = Co, Ni, Cu, Zn) bischelates has computationally been designed using the density functional theory TPSSh/6-311++G(d,p) calculations. The systems possessing complete (M = Co, Ni) and partial (M = Cu, Zn) two-step spin-crossover phenomenon at ferrous ions have been revealed. Two spin-state switching mechanisms determining by spin-crossover at iron centers and configurational isomerism at cobalt ion may simultaneously occur in solution of corresponding heterometallic compound (M = Co). The nature of the exchange interactions between paramagnetic metal centers is controlled by variation of a metal in bischelate linker (M = Co, Ni, Cu, Zn). Energy and magnetic characteristics of electromeric forms of the complexes with nickel and copper central metal ions (M = Co, Ni) allow to consider them as promising candidates for the design of molecular switches.

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Acknowledgements

This work has been supported by Russian Foundation for Basic Research (Grant No. 16-33-60019 mol_a_dk).

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  1. Institute of Physical and Organic Chemistry at Southern Federal University, Stachka Avenue, 194/2, 344090, Rostov-on-Don, Russian Federation

    Alyona A. Starikova

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Correspondence to Alyona A. Starikova.

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11696_2017_195_MOESM1_ESM.doc

Electronic Supplementary Material associated with this article (details of the DFT calculations, including optimized geometries and energy parameters of the complexes I (Co, Ni, Cu, Zn) and III (Co, Ni, Cu, Zn)), and also the shape of natural magnetic orbital of the electromer 12 HSFeII-Cu-HSFeII can be found in the online version of this paper (DOI: 10.1007/s11696-017-0195-7). (DOC 4410 kb)

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Starikova, A.A. Computational design of magnetically active trinuclear heterometallic complexes on the basis of 1,3,5-triazapentadiene ligands. Chem. Pap. 72, 821–828 (2018). https://doi.org/10.1007/s11696-017-0195-7

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  • DOI: https://doi.org/10.1007/s11696-017-0195-7

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