A New Conducting Molecular Solid Based on the Magnetic [Ni(dmf)6] Cation and on [Ni(dsit)2]2 (dsit=1,3-dithiole-2-thione-4,5-diselenolate) Showing an Unprecedented Anion Packing |
| |
Authors: | S CurreliP Deplano ML Mercuri L PiliaA Serpe F BigoliMA Pellinghelli E CoronadoCJ Gómez-Garc?a E Canadell |
| |
Institution: | a Dipartimento di Chimica Inorganica e Analitica, Università di Cagliari, S.S. 554, Bivio per Sestu, I09042, Monserrato, Cagliari, Italyb Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Università di Parma, Parco Area delle Scienze 17A, I-43100, Parma, Italyc Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, C/Dr. Moliner 50, E-46100, Burjasot, Valencia, Spaind ICMAB (CSIC), Campus de la UAB, 08193, Bellaterra, Spain |
| |
Abstract: | The synthesis, X-ray structure, magnetic and transport properties of the compound Ni(dmf)6Ni(dsit)2]2 (dmf=dimethylformamide, dsit=1,3-dithiole-2-thione-4,5-diselenolate) are described. This compound crystallizes in the monoclinic space group P21/c, with a=18.709(6), b=22.975(5), c=20.418(5) Å, β=99.31(2)° and Z=6; its structure consists of Ni(dsit)2]22− 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]− salts. This compound exhibits semiconducting behavior with a room temperature conductivity (1 S cm−1) much higher than those reported for other salts of the Ni(dsit)2]− 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−1, typical of isolated Ni(II) ions as expected for the octahedrally coordinated Ni(dmf)6]2+ cations. |
| |
Keywords: | molecular conductors dsit magnetic properties band structure calculations M(dsit)2 complexes diselenolenes |
本文献已被 ScienceDirect 等数据库收录! |
|