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Two New Families of Charge Transfer Solids Based on [M(mnt)2]n− and the Donors BMDT-TTF and EDT-TTF: Conducting and Magnetic Properties

✍ Scribed by M. Mas-Torrent; H. Alves; E.B. Lopes; M. Almeida; K. Wurst; J. Vidal-Gancedo; J. Veciana; C. Rovira


Publisher
Elsevier Science
Year
2002
Tongue
English
Weight
528 KB
Volume
168
Category
Article
ISSN
0022-4596

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✦ Synopsis


Two new families of charge transfer solids based on transition metal bis-maleonitrile dithiolate complexes [M(mnt) 2 ] nÀ and two tetrathiatulvalene (TTF) derivatives containing external sulfur atoms have been synthesized and characterized as (BMDT-TTF) 2 [M(mnt) 2 ] and (EDT-TTF)[M(mnt) 2 ], where BMDT-TTF stands for bis(methylenedithio)-tetrathiafulvalene, EDT-TTF for ethylenedithio-tetrathiafulvalene and M=Au, Pt and Ni. The salts of the series (BMDT-TTF) 2 [M(mnt) 2 ] are quasiisostructural and crystallize forming mixed ADDA stacks along a+b. In the (BMDT-TTF) 2 [Au(mnt) 2 ] salt, the anion complex is diamagnetic and has a formal charge of À1, whereas in Ni salt the anion has a charge of À2, being also diamagnetic. The magnetic properties of the Au salt follow a 1D antiferromagnetic Heisenberg model modified with a molecular field. The salt with Ni displays very strong antiferromagnetic interactions. The (EDT-TTF)[M(mnt) 2 ] salts with M=Ni and Pt are isostructural and crystallize forming alternated DADA stacks. The anions, with a formal charge of À1, are paramagnetic with a spin 1 2 : Their magnetic susceptibility can be successfully simulated within the antiferromagnetic uniform chain model of Heisenberg. Lastly, (EDT-TTF)[Au(mnt) 2 ] crystallizes in the triclinic space group P(-1) forming also alternated stacks along c in which the EDT-TTF molecules are 50% disordered. # 2002 Elsevier Science (USA)