Marc Fourmigué

Mixed cyclopentadienyl/dithiolene complexes

Abstract Heteroleptic metal complexes with both cyclopentadienyl and dithiolene ligands are organized into four different classes of different Cp/dithiolene ratio: 2:1 complexes, of general formula Cp 2 M(dithiolene) 0,+1 (M=Ti, Zr, Hf, V, Nb, Mo, W); 1:2 complexes, of general formula CpM(dithiolene) −1,0 2 (M=Ti, V, Ta, Mo, W, Re); 1:1 complexes, of general formula CpM(dithiolene) (M=Co, Rh, Ir, Ni); bimetallic 1:1 complexes of general formula [CpM(dithiolene)] 2 (M=V, Cr, Mo, Fe, Ru). The synthetic procedures, electrochemical properties, structural characteristics, NMR data, magnetic properties and reactivity of those classes of complexes are described and compared, with particular attention to the geometrical changes upon electron count and the effects of the non-innocent character of the dithiolene ligands on the structures and reactivity of the complexes.

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).

Interplay of Structural Flexibility and Crystal Packing in a Series of Paramagnetic Cyclopentadienyl/Dithiolene Mo and W Complexes: Evidence for Molecular Spin Ladders

The structural flexibility of [Cp2M(dithiolene)] complexes (M=Mo, W; dithiolene=dmit2−, dmid2−, dsit2−; the [CpMo(dmid)] complex is depicted on the right) is manifested in various folding angles of the MS2C2 metallacycle in a series of charge-transfer salts with TCNQF4. The evolution of the electronic structures with the folding angle induces different geometries for the dimeric [{Cp2M(dithiolene)+.}2] entities. The organization of these entities in the solid state reveals one-dimensional intermolecular interactions, as confirmed by the magnetic behavior of these salts, which are characteristic of a spin chain or a rare spin ladder motif (shown on the right).

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.

CCDC 1559436: Experimental Crystal Structure Determination

Related Article: Agathe Filatre-Furcate, Thierry Roisnel, Marc Fourmigue, Olivier Jeannin, Nathalie Bellec, Pascale Auban-Senzier, Dominique Lorcy|2017|Chem.-Eur.J.|23|16004|doi:10.1002/chem.201703172

CCDC 1484998: Experimental Crystal Structure Determination

Related Article: Toshiki Higashino, Olivier Jeannin, Tadashi Kawamoto, Dominique Lorcy, Takehiko Mori, and Marc Fourmigue|2015|Inorg.Chem.|54|9908|doi:10.1021/acs.inorgchem.5b01678

Unsymmetrically-Substituted Tetrathiafulvalenes (TTF) as Key Intermediates in the Preparation of Functionalized TTF Derivatives

Following the preparation of tetrathiafulvalene (TTF) and symmetrically substituted analogs such as TMTTF, TMTSF or BEDT-TTF [1], unsymmetrically substituted TTFs have been investigated recently for several reasons: n n(i) n nTTFs lacking a center of symmetry (such as EDT-TTF or MDT-TTF) are expected to organize in the solid state into head-to-tail (centrosymmetrical) dimers, which may favor the formation of the so-called к-phases in their corresponding cation-radical salts. n n n n n(ii) n nModel molecules such as TMDSDTF [2] have also been prepared and the properties of their cation-radical salts investigated and compared to those of the “pure” TMTTF or TMTSF salts.