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Spin crossover in monoadducts of Co(Salen) with pyridine and imidazole: a quantum chemical study

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Abstract

Complexation of N,N′-ethylene- and N,N′-butylene-bis(salicylideneiminato)cobalt(II) (Co(salen)) with nitrogen-containing heterocyclic ligands (pyridine, imidazole) and investigation into the mechanism responsible for the spin crossover behavior of these complexes have been computationally studied using the DFT B3LYP*/6-311++G(d,p) method. The results of calculations of geometric characteristics and energy parameters are in good agreement with an available experimental data. An addition of a base molecule to Co(salen) has been shown to be accompanied by the narrowing of the energy gap between the high-spin and the low-spin electronic states up to the values typical for spin crossover cobalt complexes. According to the calculations, the energy barrier of spin-forbidden rearrangement of a monoadduct of N,N′-butylene-bis(salicylideneiminato) Co(II) with pyridine does not exceed of 6 kcal/mol. This finding allows one to consider the adducts of Co(salen) with nitrogen-centered ligands as the prospective spin crossover systems. The computational investigation into the spatial and electronic structure of N,N′-butylene-bis(salicylideneiminato) Co(II) dimer predicts the simultaneous existence in a crystal cell of two types of molecules with different metal spin states.

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Acknowledgments

This work has been supported by the Russian Science Foundation (Grant 14-13-00573).

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Authors and Affiliations

  1. Southern Scientific Center of the Russian Academy of Sciences, 41 Chehova Ave, 344006, Rostov on Don, Russian Federation

    A. G. Starikov & V. I. Minkin

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

    V. I. Minkin & A. A. Starikova

Authors
  1. A. G. Starikov
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  2. V. I. Minkin
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  3. A. A. Starikova
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Correspondence to V. I. Minkin.

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Starikov, A.G., Minkin, V.I. & Starikova, A.A. Spin crossover in monoadducts of Co(Salen) with pyridine and imidazole: a quantum chemical study. Struct Chem 25, 1865–1871 (2014). https://doi.org/10.1007/s11224-014-0473-8

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  • DOI: https://doi.org/10.1007/s11224-014-0473-8

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