Conductive and superconductive materials derived from dmit-complexes

doi:10.1016/0378-4363(86)90127-0

Physica B+C

Volume 143, Issues 1–3, November 1986, Pages 313-315

https://doi.org/10.1016/0378-4363(86)90127-0 Get rights and content

Abstract

Recent results on the synthesis, structure and properties of conductive and superconductive materials derived from the transition metal complexes [M(dmit)₂]ⁿ⁻ are described.

References (7)

K. Bechgaard et al.
Phys. Rev. Lett.
(1981)
S.S.P. Parkin et al.
Phys. Rev. Lett.
(1983)
L. Valade et al.
J. Chem. Soc. Dalton Trans.
(1985)

There are more references available in the full text version of this article.

Cited by (10)

Main group metal 1,3-dithiole-2-thione-4,5-dithiolate (DMIT) compounds. II. Synthesis and structures of tetrabutylammonium butyl- and phenyl-bis(1,3-dithiole-2-thione-4,5-dithiolato)stannates, [Bu<inf>4</inf>N][RSn(DMIT)<inf>2</inf>] (R Bu or Ph)
1992, Journal of Organometallic Chemistry
Structures have been determined for [BU₄N][RSn(DMIT)₂] (III; R  Bu and IV; R = Ph), obtained from [Bu₄N]₂[Zn(DMIT)₂] and RSnCl₃. These complexes are isostructural. In the spirocyclic anions, the tin atoms are pentacoordinate and have geometries between trigonal bipyramidal (TBP) and rectangular pyramidal: the distortions away from TBP geometry are calculated to be ca 48 and 70% for II and IV respectively. The S atoms in the chelate ligands form the quasi-basal planes with the R groups in axial sites. The DMIT ligands, while individually planar, are not coplanar: the angles between the DMIT mean planes are 19.2 and 10.8° for III and IV respectively.
The anions are packed side by side in the c direction with S … S separations close to the sum of the van der Waals radii. In the a and b directions, there are arrays of alternating cation and anion units.
The chemistry of 1,3-dithiole-2-thione-4,5-dithiolate (dmit)
1992, Coordination Chemistry Reviews
Organotin-DMIT complexes: crystal structure of [Bu<inf>4</inf>N][Me<inf>2</inf>SnCl(DMIT)]
1991, Journal of Organometallic Chemistry
Molecular metals and superconductors derived from metal complexes of 1,3-dithiol-2-thione-4,5-dithiolate (dmit)
1991, Coordination Chemistry Reviews
Effect of cation on the structures, magnetic properties and specific heats of salts of bis(5,6-dihydro-1,4-dithiin-2,3-dithiolato)nickelate(III): the crystal structure of[(CH-<inf>3</inf>)<inf>4</inf>N] [Ni(DDDT)<inf>2</inf>]
1989, Inorganica Chimica Acta
The structure of the tetramethylammonium salt of Ni(DDDT)₂^- (DDDT^2-=5,6-lihydro-l,4-dithiin-2,3-dithiolate) has been determined by X-ray crystallography. The crystal belongs to the orthorhombic space group Pbca with unit cell dimensions a=0.543(2), b=13.937(5), c=27.518(7) Å, Z=8. The NiS₄ core exhibits square planar coordination with an average NiS bond length 2.146(2) Å. The crystal packing can be described as interlocking colums consisting of alternating cations and anions. The columns form a zigzag pattern when viewed down the y axis. The shortest S···S contact is 3.57 Å with a total of four contacts less than 3.8 Å. The X-ray powder diffraction spectrum of this salt showed the presence of only one crystallographic species, while that of the tetrabutylammonium salt indicated the possibility of a third polymorph. Magnetic susceptibility data for [(CH₃)₄N] [Ni(DDDT)₂] were fit to the Curie-Weiss law by expanding the Weiss constant as an infinite series. The specific heats of the [(CH₃)₄N]⁺, [(C₂H₅)₄N]⁺ and [(C₄H₉)₄N]⁺ salts of Ni(DDDT)₂⁻ were measured between 1 and 25 K. Similar specific heats were observed above 4 K but the values differed significantly below this temperature.
(n-Bu<inf>4</inf>N)<inf>x</inf>[Pd(dmit)<inf>2</inf>] (x = 0.5 and 0.33): Metal-like conductivity v.s. stacking of "true" dimers with metal-metal bond; Comparison with δ-TTF[Pd(dmit)<inf>2</inf>]<inf>2</inf>
1988, Synthetic Metals
(n-Bu₄N)_0.5[Pd(dmit)₂] (I) and (n-Bu₄N)_0.33[Pd(dmit)₂] (II) have been isolated as single-crystals allowing four-probe conductivity measurements and crystal structure determination. Their temperature-dependent conductivities exhibit a metal-like behavior followed by a transition towards a semi-conductive state. This behavior is reminiscent of that previously reported for δ-TTF[Pd(dmit)₂]₂ (III). Transition temperatures are (I): 120K, (II): 240K and (III): 120K. The transition is irreversible for (I) and reversible for (II) and for (III). The three compounds have a similar structure made of stacked [Pd(dmit)₂]₂^2x− dimers with Pd-Pd bond lengths ranging from 3.04 to 33.11Å. The stacks are arranged in layers, and close S…S contacts form a two-dimensional network. The cations lie between these layers. The n-Bu₄N groups are highly disordered.

View all citing articles on Scopus

View full text

Conductive and superconductive materials derived from dmit-complexes

Abstract

Phys. Rev. Lett.

Phys. Rev. Lett.

J. Chem. Soc. Dalton Trans.