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Titolo: Synthesis, crystal structure, and physical properties of (BEDT-TTF)[Ni(tdas)(2)] (BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene; tdas=1,2,5-thiadiazole-3,4-dithiolate): First monomeric [Ni(tdas)2](-) monoanion
Data di pubblicazione: 2004
Abstract: We report the synthesis, structure, and physical properties of (BEDT-TTF)[Ni(tdas)2] [BEDT-TTF, or ET, is bis- (ethylenedithio)tetrathiafulvalene; tdas is 1,2,5-thiadiazole-3,4-dithiolate], which is the first example of a salt containing monomeric [Ni(tdas)2]- monoanions. This salt, which crystallizes in the monoclinic space group P21/c with a = 17.2324(6) Å, b = 13.2740(5) Å, c = 10.9467(4) Å, â = 96.974(2)°, and V = 2485.5(2) Å3, forms a layered structure. One layer contains dimerized BEDT-TTF electron donor molecules and isolated [Ni(tdas)2]- monoanions, while the second layer contains chains of [Ni(tdas)2]- monoanions. Conductivity measurements show that (BEDTTTF)[ Ni(tdas)2] has a semiconductor-to-semiconductor transition near 200 K, while magnetic measurements indicate that it is an S = 1/2 paramagnet with weak antiferromagnetic coupling. Reflectance spectra reveal bands in the near-infrared region (6600 and 10600 cm-1) which are typical of (BEDT-TTF)2 2+ dimers. From these data, we can conclude that the unpaired electron lies on the [Ni(tdas)2]- anions. Tight-binding band structure calculations were used to analyze the electronic structure of this salt.
Tipologia:1.1 Articolo in rivista

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