Synthesis, crystal structure and physical properties of (BEDT-TTF)[Ni(tdas){sub 2}]: the first monomeric [Ni(tdas){sub 2}]{super -} monoanion, (BEDT-TTF = bis (ethylenedithio)tetrathiafulvalene; tdas = 1,2,5-thiadiazole-3,4-dithiolate).
We report the synthesis, structure, and physical properties of (BEDT-TTF)[Ni(tdas){sub 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){sub 2}]{sup -} monoanions. This salt, which crystallizes in the monoclinic space group P2{sub 1}/c with a = 17.2324(6) {angstrom}, b = 13.2740(5) {angstrom}, c = 10.9467(4) {angstrom}, {beta} = 96.974(2){sup o}, and V = 2485.5(2) {angstrom}{sup 3}, forms a layered structure. One layer contains dimerized BEDT-TTF electron donor molecules and isolated [Ni(tdas){sub 2}]{sup -} monoanions, while the second layer contains chains of [Ni(tdas){sub 2}]{sup -} monoanions. Conductivity measurements show that (BEDT-TTF)[Ni(tdas){sub 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 (6.6 x 10{sup 3} and 10.6 x 10{sup 3} cm{sup -1}) which are typical of (BEDT-TTF){sub 2}{sup 2+} dimers. From these data, we can conclude that the unpaired electron lies on the [Ni(tdas){sub 2}]{sup -} anions. Tight-binding band structure calculations were used to analyze the electronic structure of this salt.
- Research Organization:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC); FOR
- DOE Contract Number:
- DE-AC02-06CH11357
- OSTI ID:
- 961434
- Report Number(s):
- ANL/MSD/JA-47768; INOCAJ; TRN: US201012%%1497
- Journal Information:
- Inorg. Chem., Vol. 43, Issue 6 ; Mar. 22, 2004; ISSN 0020-1669
- Country of Publication:
- United States
- Language:
- ENGLISH
Similar Records
Effects of anion size and disorder on spin resonance in the BEDT-TTF (bis(ethylenedithio)tetrathiafulvalene) salts
Single-crystal X-ray and neutron diffraction investigations of the temperature dependence of the structure of the Tc = 10 K organic superconductor. kappa. -(ET) sub 2 Cu(NCS) sub 2. [where ET or BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene, C sub 10 H sub 8 S sub 8]