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Heterometallic complexes combining [Mn<sup>III</sup>(salpn)]<sup>+</sup> and [Fe(CN)<sub>6</sub>]<sup>4−</sup> units as the products of reactions between [Mn<sup>III</sup>(salpn)(H<sub>2</sub>O)C(CN)<sub>3</sub>] and [Fe(CN)<sub>6</sub>]<sup>3−/4−</sup>статья
- Авторы: Kopotkov Vyacheslav A., Yagubskii Eduard B., Simonov Sergey V., Zorina Leokadiya V., Starichenko Denis V., Korolyov Alexander V., Ustinov Vladimir V., Shvachko Yuri N.
- Журнал: New Journal of Chemistry
- Том: 38
- Номер: 9
- Год издания: 2014
- Издательство: Royal Society of Chemistry
- Местоположение издательства: United Kingdom
- Первая страница: 4167
- Последняя страница: 4176
- DOI: 10.1039/c4nj00427b
- Аннотация: The reaction of [Fe(III)(CN)6]3− with neutral [Mn(salpn)(H2O)C(CN)3] (salpn: N,N′-propylenebis(salicylideneiminato)) (1) produces two new heterometallic complexes [{MnIII(salpn)(H2O)}2{MnIII(salpn)(H2O)0.7(CH3OH)0.3}2FeII(CN)6]·n(H2O/CH3OH) (2) and [{MnIII(salpn)}4{MnIII(salpn)(H2O)}2FeII(CN)6]{C(CN)3}2·4H2O (3), which are characterized by single-crystal X-ray diffraction. In this reaction, the [C(CN)3]− ligand reduces Fe(III) to Fe(II). Complex 3 can be prepared directly using hexacyanoferrate(II). One more complex containing the hexacyanoferrate(II), [{MnIII(salpn)(CH3OH)0.67(H2O)0.33}6FeII(CN)6]{ClO4}2·8H2O (4), is obtained in the reaction of [Fe(II)(CN)6]4− with the cationic complex [Mn2(salpn)2(H2O)2](ClO4)2. The iron(II) centers in the complexes 2 and 4 are linked via cyano-bridges with the four and six [MnIII(salpn)]+ fragments, respectively. The structure of 3 consists of the cyano-bridged [MnIII6FeII] repeating units linked by double phenolate bridges into a one-dimensional polymeric chain. The magnetic properties of 3 indicate a ferromagnetic coupling between MnIII centers in the double phenolate-bridged [MnIII(salpn)]2 dinuclear subunits. Quantum calculations within the Heisenberg–Van Vleck model are performed giving the exchange constant J = 0.64 cm−1 and the zero-field splitting parameter D = −3.5 ± 0.5 cm−1. The ac-susceptibility obeys the Arrhenius law with the activation energy Ea = 11.89 cm−1.
- Добавил в систему: Копотков Вячеслав Александрович