A New Conducting Molecular Solid Based on the Magnetic [Ni(dmf)6]2+ Cation and on [Ni(dsit)2]22− (dsit=1,3-dithiole-2-thione-4,5-diselenolate) Showing an Unprecedented Anion Packing
✍ Scribed by S. Curreli; P. Deplano; M.L. Mercuri; L. Pilia; A. Serpe; F. Bigoli; M.A. Pellinghelli; E. Coronado; C.J. Gómez-Garcıa; E. Canadell
- Book ID
- 102606814
- Publisher
- Elsevier Science
- Year
- 2002
- Tongue
- English
- Weight
- 442 KB
- Volume
- 168
- Category
- Article
- ISSN
- 0022-4596
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✦ Synopsis
The synthesis, X-ray structure, magnetic and transport properties of the compound Ni(dmf) 6 [Ni(dsit) 2 ] 2 (dmf=dimethylformamide, dsit=1,3-dithiole-2-thione-4,5-diselenolate) are described. This compound crystallizes in the monoclinic space group P2 1 =c; with a=18.709(6), b=22.975(5), c=20.418(5) ( A, b=99.31(2)1 and Z=6; its structure consists of [Ni(dsit) 2 ] 2 2À dimers and isolated [Ni(dmf) 6 ] 2+ cations both centrosymmetric and non-centrosymmetric. The dimers are packed forming chains along the [101] direction with short Se?Se interdimer contacts. Additional interchains S?S contacts render this structure a three-dimensional character, never observed so far in other [Ni(dsit) 2 ] À salts. This compound exhibits semiconducting behavior with a room temperature conductivity (1 S cm À1 ) much higher than those reported for other salts of the [Ni(dsit) 2 ] À anion. Tight-binding band structure calculations were used to analyze the origin of the semiconducting properties of this salt. The magnetic susceptibility shows Curie behavior with C=1.25 emu K mol À1 , typical of isolated Ni(II) ions as expected for the octahedrally coordinated [Ni(dmf) 6 ] 2+ cations. # 2002 Elsevier Science (USA)