Journal
TRANSITION METAL CHEMISTRY
Volume 43, Issue 7, Pages 647-655Publisher
SPRINGER
DOI: 10.1007/s11243-018-0253-1
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Funding
- Slovak Research and Development Agency [APVV-14-0073, APVV-14-0078]
- ERDF EU projects [ITMS26220120047]
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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.
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