Physical properties of (TMTSF)2TaF6: Influence of the anion size

The physical properties of (TMTSF)₂TaF₆ are discussed through transport and magnetic measurements. A crossover between two different regimes is observed around 100K and a spin density wave ground state appears below 11 K. The phase diagram under magnetic field is determined. Finally, the properties of this compound are compared with that of the other members of the TMTSF series and the influence of the anion size is discussed.     

Interplay between chains of S = 5/2 localised spins and two-dimensional sheets of organic donors in the synthetically built magnetic multilayer λ ‒ (BETS)2FeCl4

In order to understand the magnetic field-induced restoration of a highly conductive state in , static (SQUID) and dynamic (ESR and AFR) magnetization measurements were performed on polycrystalline samples and single crystals, respectively. In addition, cantilever and resistivity measurements under steady fields were performed. While the metal-insulator transition curve of the () phase diagram exhibits a first order character, a “spin-flop” transition line divides the insulating state when the magnetic field is applied along the easy axis of magnetization. The effects of a RKKY-type indirect exchange and of applied magnetic field are described within the framework of a generalized Kondo lattice, namely two chains of localised spins coupled through the itinerant spins of the 2D sheets of BETS. The calculations, which can incorporate intramolecular electron correlations within a mean field theory, are in qualitative agreement with the field induced transition from the antiferromagnetic insulating ground state to a canted one, i.e. a not fully oriented paramagnetic, but metallic state. Received: 6 August 1997 / Received: 5 November 1997 / Accepted: 10 November 1997     

A study of the apparatus function of a grid Fabry-Perot interferometer used as a F.I.R. spectrometer: Computing of the spectrum

Influences of various parameters on the apparatus function of a F.I.R. grid Fabry-Perot spectrometer are analysed. A pseudo-deconvolution method allowing an improvement of experimental results is tested by simulation and then applied to data concerning the isotopic HCl doublet at 41 cm^–1.     

A density functional study of the highly adaptable molecular structure of Mo(V) and W(V) dithiolene complexes: from three-dimensional antiferromagnet to spin ladder

Cp2M(dithiolene) (M = MoIV, WIV) d2 complexes exhibit a folding (theta) of the MS2C2 metallacycle along the S-S axis upon oxidation to the d1 paramagnetic cation. The evolution of the peculiar unfolded structure (theta = 0 degree) of Cp2Mo(dmit).+ (dmit2-, 2-thioxo-1,3-dithiole-4,5-dithiolate) in its AsF6- salt toward the introduction of heavy atoms (W, Se) is examined here by substituting dsit2- (dsit2-, 2-thioxo-1,3-dithiole-4,5-diselenolate) for dmit2- and/or W for Mo in those AsF6- salts. While [Cp2Mo(dsit).+][AsF6-] (orthorhombic, Cmcm, a = 9.071(2), b = 20.868(4), c = 10.243(2) A, V = 1938.9(7) A3, Z = 4) and [Cp2W(dmit).+][AsF6-] (orthorhombic, Cmcm, a = 9.0295(15), b = 20.568(2), c = 10.2641(12) A, V = 1906.2(4) A3, Z = 4) crystallize with an unfolded geometry and are isostructural with [Cp2Mo(dmit).+][AsF6-], the introduction of both W and dsit2- in Cp2W(dsit) stabilizes a fully different structure for [Cp2W(dsit).+][AsF6-] (monoclinic, P2(1)/c, a = 6.8442, b = 15.9923(13), c = 17.6594(16) A, beta = 90.934(11) degrees, V = 1932.6(3) A3, Z = 4) with the Cp2W(dsit).+ cation in a folded geometry (theta = 30.1(1) degrees). DFT calculations show that the variety of folding angles and hence of molecular structures found in those open-shell d1 Cp2M(dithiolene).+ complexes is attributable to a very low energy cost (< 1 kcal mol-1) for folding around the minimal energy folding angle. The molecular geometry of those complexes and hence their frontier orbitals are therefore highly related to the actual crystal structure they adopt. The unfolded complexes exhibit, in their AsF6- salts, a three-dimensional set of intermolecular interactions in the solid state, confirmed by the presence of an antiferromagnetic ground state (TNéel = 3.5(5) K in [Cp2W(dmit).+][AsF6-]). On the other hand, the folding of Cp2W(dsit).+ in [Cp2W(dsit).+][AsF6-] leads to the formation of a rare spin-ladder system with a spin gap of 90-100 K, as deduced from the temperature dependence of its magnetic susceptibility.     

(EDT-TTF-CONH2)6[Re6Se8(CN)6], a metallic Kagome-type organic-inorganic hybrid compound: electronic instability, molecular motion, and charge localization

(EDT-TTF-CONH2)6[Re6Se8(CN)6], space group R, was prepared by electrocrystallization from the primary amide-functionalized ethylenedithiotetrathiafulvalene, EDT-TTF-CONH2 (E(1/2)1 = 0.49 V vs SCE in CH3CN), and the molecular cluster tetraanion, [Re6Se8(CN)6]4- (E(1/2) = 0.33 V vs SCE in CH3CN), equipped with hydrogen bond donor and hydrogen bond acceptor functionalities, respectively. Its Kagome topology is unprecedented for any TTF-based materials. The metallic state observed at room temperature has a strong two-dimensional character, in coherence with the Kagome lattice symmetry, and the presence of minute amounts of [Re6Se8(CN)6](3-)* identified by electron spin spectroscopy. A structural instability toward a distorted form of the Kagome topology of lesser symmetry is observed at ca. 180 K. The low-temperature structure is associated with a localized, electrically insulating electronic ground state and its magnetic susceptibility accounted for by a model of uniform chains of localized S = 1/2 spins in agreement with the 100 K triclinic crystal structure and band structure calculations. A sliding motion, within one out of the three (EDT-TTF-CONH2)2 dimers coupled to the [Re6Se8(CN6)(3-)*]/[Re6Se8(CN6)4-] proportion at any temperature, and the electronic ground state of the organic-inorganic hybrid material are analyzed on the basis of ESR, dc conductivity, 1H spin-lattice relaxation, and static susceptibility data which qualify a Mott localization in [EDT-TTF-CONH2]6[Re6Se8(CN)6]. The coupling between the metal-insulator transition and a structural transition allows for the lifting of a degeneracy due to the ternary axis in the high temperature, strongly correlated metallic phase which, in turn, leads to Heisenberg chains at low temperature.     

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