Tetrathiafulvalene and Tetramethyltetraselenafulvalene Salts with [M(dcdmp)2] Anions (M = Au, Cu, and Ni): High Conductivity and Unusual Stoichiometries

Four new charge transfer salts based on tetrathiafulvalene (TTF) or tetramethyltetraselenafulvalene (TMTSF) donors and transition metal complexes [M(dcdmp)2] (dcdmp = 2,3-dicyano-5,6-dimercaptopyrazine), TMTSF5[Cu(dcdmp)2]4 (1), (TMTSF)2[Ni(dcdmp)2] (2), and (TTF)7[M(dcdmp)2]6 (M = Au (3) and Cu (4)) were prepared by electrocrystallization. These compounds are characterized by a rich variety of crystal structures with unusual donor/acceptor stoichiometries. In spite of the uncommon structural types observed, these salts can be highly conducting. Compound 1 crystallizes with segregated TMTSF stacks, showing 1D metallic properties with a room temperature conductivity of 134 S/cm. Compound 2 crystallizes in an out-of-registry mixed column arrangement of donor dimers and acceptors. Compounds 3 and 4 appear in single crystal X-ray diffraction as isostructural and composed of columns of TTF hexamers that are disrupted by a single TTF layer and surrounded by [M(dcdmp)2]− monoanionic pairs, aligning perpendicular...

[1]  Rafaela A. L. Silva,et al.  Synthesis and Characterization of Charge Transfer Salts Based on [M(dcdmp)2] (M = Au, Cu and Ni) with TTF Type Donors , 2018 .

[2]  Rafaela A. L. Silva,et al.  DT-TTF Salts with [Cu(dcdmp)2]−: The Richness of Different Stoichiometries , 2016 .

[3]  S. Brown.  Organic superconductors: The Bechgaard salts and relatives , 2015 .

[4]  E. Lopes,et al.  Bilayer Molecular Metals Based on Dissymmetrical Electron Donors. , 2015, Inorganic chemistry.

[5]  Hisashi Tanaka,et al.  Molecular Inorganic Conductors and Superconductors , 2010 .

[6]  M. Almeida,et al.  Dithiolene complexes containing N coordinating groups and corresponding tetrathiafulvalene donors , 2010 .

[7]  A. Neves,et al.  Cation and ligand roles in the coordination of FeIII bisdithiolene complexes; the crystal structures of (BrBzPy)2[Fe(qdt)2]2 and [Fe(α-tpdt)2]22− salts , 2009 .

[8]  L. Pereira,et al.  Synthesis and characterization of copper complexes with the 2,3-dicyano-5,6-dimercaptopyrazine ligand: Magnetic properties of a ferrocenium salt , 2005 .

[9]  Takehiko Mori.  Organic conductors with unusual band fillings. , 2004, Chemical reviews.

[10]  I. Santos,et al.  5,6-Dicyano-2,3-dithiopyrazine (dcdmp) chemistry: synthesis and crystal structure of Au(III)(dcdmp)2 complexes and 2,3,7,8-tetracyano-1,4,6,9-tetraazothianthrene , 2004 .

[11]  Christoph Janiak,et al.  A critical account on π–π stacking in metal complexes with aromatic nitrogen-containing ligands , 2000 .

[12]  S. Kitagawa,et al.  Structural, Spectroscopic and Magnetic Properties of Charge-Transfercomplex, (TMTSF)[Cr(Cl4SQ)2(Cl4Cat)]· 0.5CH2Cl2 , 1999 .

[13]  Y. Yamashita,et al.  Synthesis, structure and properties of the novel conducting dithiolato-metal complexes having dicyanopyrazine moieties , 1994 .

[14]  S. Ravy,et al.  On the band electronic structure of X [M (dmit)2]2 (X = TTF, (CH3)4N ; M = Ni, Pd) molecular conductors and superconductors , 1989 .

[15]  R. Hoffmann,et al.  Conjugated one and two dimensional polymers , 1979, Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences.

[16]  R. Hoffmann,et al.  The band structure of the tetracyanoplatinate chain , 1978 .

[17]  J. F. Kwak,et al.  Apparatus for thermopower measurements on organic conductors , 1975 .

[18]  John P. Ferraris,et al.  Electron transfer in a new highly conducting donor-acceptor complex , 1973 .

[19]  R. Hoffmann.  An Extended Hückel Theory. I. Hydrocarbons , 1963 .