Patrick Batail

Directing the Structures and Collective Electronic Properties of Organic Conductors: The Interplay of π‐Overlap Interactions and Hydrogen Bonds

A single, amide-functionalized EDT-TTF core is expressed into markedly different and unprecedented stoichiometries and structures with contrasted collective electronic properties (uniform chain of spins versus two-dimensional metallic character) when associated with isosteric monoanions of different symmetries (Oh vs. Td; see scheme).

Complex Fluids Based on the Flexible One‐Dimensional Mineral Polymers [K(MPS4)]∞ (M=Ni, Pd): Autofragmentation to Concave, Cyclic (PPh4)3[(NiPS4)3]

A remarkable autofragmentation/rearrangement sequence results in the unprecedented formation of inorganic concave cyclic anion [(NiPS4 )3 ]3- (structure shown on the right) upon dissolving the potassium salt of the charged mineral polymer 1∞ [NiPS4 ]- in DMF; the initial complex fluid has a transient anisotropic texture that can be identified by optical microscopy under polarized light. In contrast, the complex fluid that results upon dissolving 1∞ [PdPS4 ]- is stable up to 323 K as persistent, flexible, charged chains.

Neutral and Cationic Hexanuclear Rhenium Phosphine Clusters with μ3-(Phosphido-Chalcogenido), μ3-(Arsenido-Chalcogenido), and μ3-(Imido or Oxo-Chalcogenido) Hetero Ligand Shells

Reactions of dry THF/MeCN solutions of Ca[Re6SCl(Cla)6] with silylated derivatives E(SiMe3)2 (Eu200a=u200aPhAs, PSiMe3, HN, O, S) and addition of trialkylphosphine PPr3 afford in high yields and at room temperature either the neutral clusters [Re6SX(PPr3)] (1: Xu200a=u200aAs, 2: Xu200a=u200aP) or the ionic compounds [Re6SX(PPr3)]2+u200a· [Re6S6Cl8]2– (3: Xu200a=u200aNH, 4: Xu200a=u200aO, 5: Xu200a=u200aS). The compounds 1–5 were characterised by X-ray crystal structure analysis. A di-substitution reaction occurs on the {Re6SCl}4+ cluster core, where the two inner μ3-chloro ligands Cli are substituted by X (Xu200a=u200aAs, P, NH, O, S) and all six terminal chloro ligands Cla are exchanged by terminal PPr3-ligands. n n n nNeutrale und kationische hexanukleare Rhenium–Phosphin-Cluster mit μ3-(Phosphido-Chalcogenido), μ3-(Arsenido-Chalcogenido) und μ3-(Imido oder Oxo-Chalcogenido) hetero-Ligandenspharen n n n nReaktionen von Ca[Re6SCl(Cla)6], gelost in trockenem THF/MeCN, mit silylierten Derivativen E(SiMe3)2 (Eu200a=u200aPhAs, PSiMe3, HN, O, S) und Trialkylphosphin PPr3 ergaben bei Raumtemperatur in hohen Ausbeuten die neutralen oder ionischen Clusterverbindungen [Re6SX(PPr3)] (1: Xu200a=u200aAs, 2: Xu200a=u200aP) bzw. [Re6SX(PPr3)]2+[Re6S6Cl8]2– (3: Xu200a=u200aNH, 4: Xu200a=u200aO, 5: Xu200a=u200aS). 1–5 wurden mittels Rontgenstrukturanalyse charakterisiert. Eine zweifache Substitution erfolgte am {Re6SCl}4+-Clusterkern, bei welchem die beiden inneren μ3-Chlorliganden Cli durch X (Xu200a=u200aAs, P, NH, O, S) und alle sechs terminalen Chlorliganden Cla durch terminale PPr3-Liganden ersetzt wurden.

Heat conduction in κ-(BEDT-TTF)2X superconductors

Abstract We present the first study of thermal conductivity of a quasi two dimensional organic superconductor. κ-(BEDT-TTF) 2 Cu(NCS) 2 presents features which have already been detected in the high T c cuprates. Notably we observed an increase of the thermal conductivity at the superconducting transition which is suppressed by a moderate magnetic field. At low temperatures we clearly resolved a residual electronic contribution close to the universal limit value which is consistent with an anisotropic pairings with lines of nodes in the superconducting gap function.

Crystal engineering and [C-H •••O] hydrogen bonds at the organic/inorganic interface. The bi-continuous hybrid composite, κ(2/3-3)-(EDT-TTF)8[Ca(H2O)4]2(TeW6O24)· 7H2O2

Les trente molecules deau participanr a la formulation du compose decrit dans le titre et obtenu par electrocristallisation sont confinees a linterface organique/inorganique ou elles deviennent soigneusement ordonnees et participent, au meme titre que les anions couronnes dAnderson, a la construction dun polymere de coordination bidimensionnel a partir des premieres et deuxiemes spheres de coordination des atomes de calcium. Elles sont egalement engagees dans un ensemble de liaisons hydrogene [C-H…O] dont on demontre quil organise, in fine, la distribution des electrons au sein des couches dethylenedithiotetrathiafulavalenium (EDT-TTF) qui adoptent, quant a elles, un mode nouveau de pavage de la couche du type kappa.

1H NMR Measurement of the Magnetic Field Penetration Depth λab in the Organic Superconductor κ-(BEDT-TTF)2Cu[N(CN)2]Br

Abstract The in-plane magnetic field penetration depth λ ab of the organic superconductor κ-(BEDT-TTF) 2 Cu[N(CN) 2 ]Br has been derived from the temperature dependence of the 1 H NMR line shape: λ ab (T = 0 K) = 4920 ± 100 A. Its linear low temperature behavior is consistent with an anisotropic superconducting gap with lines of nodes.

Synthesis and solubility in water of Cs3Re6S7Cl7, the missing octahedral thiochloride rhenium(III) cluster salt

Abstract In the isostructural and isoelectronic series of molecular anions [Re 6 (Y 4+ n X 4− n )X 6 n− (X = halogen, Y = chalcogen, n = 0–4), (Cs + ) 3 [Re 6 S 7 Cl 7 3− , the first n = 3 mineral salt has been obtained in quantitative amounts by high temperature solid state synthesis. It is found to be soluble in water where a metathesis of the alkaline cation affords ( n -Bu 4 N) 3 Re 6 S 7 Cl 7 in high yields. With this last compound, and for the first time in a Re-X-Y system, the completed series ( n = 0–4) of molecular precursors is now available for solution chemistry.

Isotopic shifts and Raman line shapes of the organic superconductor β-(BEDT-TTF)2I3

Abstract The behavior vs. temperature of the vibrational modes of normal and 13C enriched β-(BEDT-TTF)2I3 single crystals is reported. The Raman isotopic shift evidences that the inter-ring Cue5fbC stretching mainly participates to the lowest component of the Cue5fbC band. Comparison of this line with spectra of ET crystals evinces that the charge transfer comes from the central Cue5fbC bond. The line shape was fitted at low temperatures using Fano functions with negative asymmetry parameters q. This observation is to be linked to the occurrence of a strong electron-phonon coupling. We thus assume, near Tc, that the phonons couple with a continuum of electronic origin. We conclude that internal Cue5fbC vibrations may contribute for superconductivity in these systems.