Nonelectrochemical Synthesis, Crystal Structure, and Physical Properties of the Radical Salt [ET]2[CuCl4] (ET = Bis(ethylenedithio)tetrathiafulvalene)
Inorganic Chemistry2013Vol. 52(24), pp. 14376–14381
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Bárbara Rodríguez-García, Sara Goberna‐Ferrón, Yong‐Sung Koo, Jordi Benet‐Buchholz, José Ramón Galán‐Mascarós
Abstract
The radical salt [ET]2[CuCl4] was obtained by chemical oxidation of bis(ethylenedithio)tetrathiafulvalene (ET) with the tetranuclear copper(II) halide cluster [Cu4OCl10](4-). Although a complex mixture of anions forms in solution during the redox reaction, only this product is obtained as large (>3 mm) single crystals. X-ray diffraction analysis determined that the ET molecules stack in the solid state forming dimerized 1D chains along the a axis, interleaved by [CuCl4](2-) anions. The ET dimers show very short S···S contacts (620 K (430 cm(-1)). The Cu(2+) (S = 1/2) centers are magnetically isolated and yield a narrow EPR line in the X-band at g = 2.01. The ET moieties are EPR silent.
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