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]

被引：4

作者：

Cizmar, Erik ^{[1
]}

Soltesova, Daniela ^{[1
]}

Kazheva, Olga N. ^{[2
]}

Alexandrov, Grigorii G. ^{[3
]}

Kravchenko, Andrey V. ^{[4
]}

Chekulaeva, Lyubov A. ^{[5
]}

Kosenko, Irina D. ^{[5
]}

Sivaev, Igor B. ^{[5
]}

Bregadze, Vladimir I. ^{[5
]}

Fedorchenko, Alexey V. ^{[1
,6
]}

Starodub, Vladimir A. ^{[7
]}

Buravov, Lev I. ^{[2
]}

Dyachenko, Oleg A. ^{[2
]}

Feher, Alexander ^{[1
]}

机构：

[1] Safarik Univ, Fac Sci, Inst Phys, Pk Angelinum 9, Kosice 04154, Slovakia

[2] Russian Acad Sci, Inst Problems Chem Phys, Semenov Av 1, Chernogolovka 142432, Moscow District, Russia

[3] Russian Acad Sci, NS Kurnakov Inst Gen & Inorgan Chem, Leninskii Av 31, Moscow 119991, Russia

[4] Kharkov Natl Univ, 4 Svobody Sq, UA-61077 Kharkov, Ukraine

[5] Russian Acad Sci, AN Nesmeyanov Inst Organoelement Cpds, Vavilov Str 28, Moscow 119991, Russia

[6] NAS Ukraine, B Verkin Inst Low Temp Phys & Engn, Nauky Av 47, Kharkov, Ukraine

[7] Jan Kochanowski Univ, Inst Chem, 15 G Swietokrzyska Str, PL-25406 Kielce, Poland

来源：

TRANSITION METAL CHEMISTRY | 2018年 / 43卷 / 07期

关键词：

D O I：

10.1007/s11243-018-0253-1

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

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)[3,3A '-Cr(1,2-C2B9H11)(2)] in the galvanostatic regime. An electric conductivity sigma (293 K) = 7 x 10(-3) Ohm(-1) cm(-1) with semiconductor activation energy E-a congruent to 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.

引用

页码：647 / 655

页数：9

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