Large magnetic anisotropy of chromium(III) ions in a bis(ethylenedithio)tetrathiafulvalenium salt of chromium bis(dicarbollide), (ET)2[3,3′-Cr(1,2-C2B9H11)2]

Čižmár, E.; Daniela, Š.; Kazheva, O.N.; Alexandrov, G.G.; Kravchenko, A.V.; Chekulaeva, L.A.; Kosenko, I.D.; Sivaev, I.B.; Bregadze, V.I.; Fedorchenko, A.V.; Starodub, V.A.; Buravov, L.I.; Dyachenko, O.A.; Alexander, F.

Авторы: Erik Čižmár, Daniela Šoltésová, Kazheva Olga N., Alexandrov Grigorii G., Kravchenko Andrey V., Chekulaeva Lyubov A., Kosenko Irina D., Sivaev Igor B., Bregadze Vladimir I., Fedorchenko Alexey V., Starodub Vladimir A., Buravov Lev I., Dyachenko Oleg A., Alexander Feher
Журнал: Transition Metal Chemistry
Том: 43
Номер: 7
Год издания: 2018
Издательство: Springer Nature
Местоположение издательства: Switzerland
Первая страница: 647
Последняя страница: 655
DOI: 10.1007/s11243-018-0253-1
Аннотация: The synthesis of a radical-cation salt based on a derivative of tetrathiafulvalene, (ET)2[3,3′-Cr(1,2-C2B9H11)2] (ET = bis(ethylenedithio)tetrathiafulvalenium), was accomplished by electrochemical anodic oxidation of ET in the presence of (Me4N)[3,3´-Cr(1,2-C2B9H11)2] in the galvanostatic regime. An electric conductivity σ (293 K) = 7 × 10−3 Ohm−1 cm−1 with semiconductor activation energy Ea ≅ 0.1 eV in the range of 127–300 K was observed. The crystal structure of (ET)2[3,3′-Cr(1,2-C2B9H11)2] was determined by X-ray diffraction at 173 K, revealing the presence of structural tetramers in radical-cation stacks. The magnetic properties of the complex were investigated in the temperature range 1.8–300 K using magnetometry and EPR, showing that the magnetic structure of (ET)2[3,3′-Cr(1,2-C2B9H11)2] consists of two independent magnetic subsystems. Cation radicals form a rectangular magnetic lattice in the ab-plane with significant antiferromagnetic exchange interactions. The chromium bis(dicarbollide) anions are characterized by unusually strong positive zero-field splitting of the Cr(III) ions, which was confirmed by ab initio calculations.
Добавил в систему: Сиваев Игорь Борисович

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Large magnetic anisotropy of chromium(III) ions in a bis(ethylenedithio)tetrathiafulvalenium salt of chromium bis(dicarbollide), (ET)2[3,3′-Cr(1,2-C2B9H11)2]статья

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