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International audience; The occurrence of isostructural conducting radical cation salts of diversely substituted tetrathiafulvalene (TTF) precursors with the same anion is most often limited to very similar derivatives such as tetramethyl-tetrathiafulvalene (TMTTF) and tetramethyl-tetraselenafulvalene (TMTSF). Here we show that the use of the oxo-bis[pentafluorotantalate(V)] dianion [Ta2F10O]2− affords upon electrocrystallization of TMTTF, TMTSF, bis(ethylenedithio)-tetrathiafulvalene (BEDT-TTF), racemic dimethyl-ethylenedithio-tetrathiafulvalene ((rac)-DM-EDT-TTF), and enantiopure (S,S)-DM-EDT-TTF a series of mixed valence crystalline radical cation salts with the same 3 : 1 stoichiometry. The donor layers show similar features in the five materials, such as alternation of trimeric units within stacks which arrange in parallel columns of β-type. The anion arranges either parallel or perpendicular to the stack direction and establishes numerous intermolecular CH⋯F hydrogen bonds. Thus, the [Ta2F10O]2− dianion, most likely because of its shape and propensity to engage in hydrogen bonding, is the first one to be able to induce the same type of structural arrangement for a broad series of different donors, a result which is important in the crystal engineering of molecular conductors. All the compounds are band gap semiconductors, according to single crystal resistivity measurements and extended Hückel band structure calculations. The room temperature conductivity values are relatively high, i.e. 0.25–1.1 S cm−1, except for the TMTTF salt, whose conductivity value is two orders of magnitude smaller than its isostructural TMTSF counterpart, in agreement with the band gap energy value. As a general feature of these materials, variations in the inter- and intra-trimer interactions modulate their band structure, i.e. energy dispersion and band gaps. The preparation of this series of radical cation salts with a sturdy 3 : 1 stoichiometry might question previous assignments of the anion as [Ta2F11]− in radical cation salts of TMTSF and BEDT-TTF.

The occurrence of isostructural conducting radical cation salts of diversely substituted tetrathiafulvalene (TTF) precursors with the same anion is most often limited to very similar derivatives such as tetramethyltetrathiafulvalene (TMTTF) and tetramethyl-tetraselenafulvalene (TMTSF). Here we show that the use of the oxo-bis[pentafluorotantalate(V)] dianion [Ta2F10O]2 affords upon electrocrystallization of TMTTF, TMTSF, bis(ethylenedithio)-tetrathiafulvalene (BEDT-TTF), racemic dimethyl-ethylenedithio-tetrathiafulvalene ((rac)- DM-EDT-TTF), and enantiopure (S,S)-DM-EDT-TTF a series of mixed valence crystalline radical cation salts with the same 3 : 1 stoichiometry. The donor layers show similar features in the five materials, such as alternation of trimeric units within stacks which arrange in parallel columns of b-type. The anion arranges either parallel or perpendicular to the stack direction and establishes numerous intermolecular CH/F hydrogen bonds. Thus, the [Ta2F10O]2 dianion, most likely because of its shape and propensity to engage in hydrogen bonding, is the first one to be able to induce the same type of structural arrangement for a broad series of different donors, a result which is important in the crystal engineering of molecular conductors. All the compounds are band gap semiconductors, according to single crystal resistivity measurements and extended Huckel band structure calculations. The room temperature conductivity ¨ values are relatively high, i.e. 0.25–1.1 S cm 1 , except for the TMTTF salt, whose conductivity value is two orders of magnitude smaller than its isostructural TMTSF counterpart, in agreement with the band gap energy value. As a general feature of these materials, variations in the inter- and intra-trimer interactions modulate their band structure, i.e. energy dispersion and band gaps. The preparation of this series of radical cation salts with a sturdy 3 : 1 stoichiometry might question previous assignments of the anion as [Ta2F11] in radical cation salts of TMTSF and BEDT-TTF., This work was supported in France by the National Agency for Research (ANR, Project 15-CE29-0006-01 ChiraMolCo), the CNRS and the University of Angers. Work at Bellaterra (Spain) was supported by the Spanish MICIU through Grant PGC2018-096955-B-C44 and the MINECO through the Severo Ochoa Centers of Excellence Program under Grant SEV-2015-0496 as well as by Generalitat de Catalunya (2017SGR1506).

Puzzled by the unusual conducting behavior of the as described (TMTSF)3Ta2F11 radical cation salt[1] (TMTSF = tetramethyl-tetraselenafulvalene) and the potential interest of the Ta2F11 monoanion in other molecular conductors, we have decided to revisit and extend the family of TTF radical cation salts containing this particular anion. During our investigation it turned out that the real anionic species was in fact the Ta2OF10 dianion.In this work we describe the structures, conductivity and band structure calculations of the (TMTXF)2Ta2OF10 hybrid salts (X = S or Se). We also present the new (DM-EDT-TTF)3Ta2OF10 materials based on the chiral donor dimethyl-ethylenedithio-tetrathiafulvalene (DM-EDT-TTF).

International audience; A detailed investigation of the charge-ordered charge-transfer salt δ−(EDT−TTF−CONMe2)2Br by thermal-expansion measurements and dielectric spectroscopy reveals three dynamic processes of relaxational character. The slowest one exhibits the characteristics of glassy freezing and is ascribed to the conformational dynamics of terminal ethylene groups of the organic molecules. Such a process was previously found for related charge-transfer salts where, however, the anions form polymerlike chains, in contrast to the spherical anions of the present material. Dielectric spectroscopy reveals two additional relaxational processes. The characteristics of the faster one are consistent with excitations of a one-dimensional Wigner lattice as recently observed in this material by infrared spectroscopy, which are also accompanied by conformational changes of the molecules. However, at low temperature the ethylene-group relaxation exhibits the cooperativity-induced dramatic slowing down that is typical for glassy freezing, while the defect-related Wigner-lattice excitation follows thermally activated behavior as expected for single-dipole relaxations.

Two racemic tetrathiafulvalene‐[2.2]paracyclophane electron donors EDT‐TTF‐[2.2]paracyclophane 1 and (COOMe)2‐TTF‐[2.2]paracyclophane 2 have been synthesized via the phosphite mediated cross coupling strategy. Chiral HPLC allowed the optical resolution of the (RP) and (SP) enantiomers for both compounds. Solid‐state structures of (RP)‐1 and (rac)‐2 have been determined by single crystal X‐ray analysis. Intermolecular π‐π and S•••S interactions are disclosed in the packing. Single crystal X‐ray analysis of (RP)‐1 combined with experimental and theoretical circular dichroism spectra allowed the assignment of the absolute configuration of the enantiomers of 1 and 2.

The quantum critical state of organic quantum spin liquids (QSL) exhibits large sensitivity even to weak perturbations. For example, the antisymmetric exchange, the Dzyaloshinskii-Moriya (DM) interaction, which is present in all spin systems without inversion symmetry, could result in a phase transition from the quantum critical phase to an antiferromagnetic phase already at moderate magnetic fields. Using the combination of multi-frequency Electron Spin Resonance spectroscopy (ESR) in the 1-500 GHz frequency range and muon spin rotation (mSR), we studied the influence of the DM interaction in two-dimensional and quasi-one-dimensional organic QSL candidates.In the triangular lattice QSL, k-(ET)2Ag2(CN)3 (J’/J=0.94, J=175 K), our ESR measurements found a static staggered moment of 6×10-3 mB at T=1.5 K and at B=15 T [1]. The magnetic field dependence of the ESR linewidth, which measures the spectral density of the antiferromagnetic fluctuations, proves that this staggered moment stems from the DM interaction (DM0=4 K) in a perfectly crystalline two-dimensional structure. In a new quasi-one-dimensional QSL candidate, (EDT-TTF-CONH2)2+BABCO-, which is a weak Mott insulator with a distorted triangular lattice (J’/J=3, J=360 K), our combined ESR and mSR study confirmed the absence of magnetic ordering down to 20 mK [2]. This remarkable observation is partially attributed to a unique structural motif of the (EDT-TTF-CONH2)2+BABCO- salt. Here, the (EDT-TTF-CONH2)2+ conducting layers are separated by the highly disordered BABCO- molecular rotors. Importantly, despite the presence of a sizable DM interaction (DM0=0.6 K), the staggered moment is smaller than 4×10-4 mB at T=1.5 K and B=15 T. The magnetic field dependence of the ESR linewidth does not show the effect of the DM interaction. Instead, the linear dependence is indicative of the presence of fast spin fluctuations, which is supported by longitudinal-field mSR measurements that reveal the spin excitations to possess one-dimensional diffusive character. The quenching of the effect of the DM interaction is explained by the strong disorder introduced by the anion layer.Despite the fact that the magnitude of the DM interaction is 2 to 3 orders of magnitude weaker than the symmetric exchange, it can substantially alter the phase diagram of QSLs. Our work gives a novel explanation to the field-induced phase transitions, and it demonstrates that high-frequency ESR is a powerful technique to study the spin dynamics of QSLs.

International audience; The 1/4-filled organic compound, δ-(EDT-TTF-CONMe2)2AsF6 is a frustrated two-dimensional triangular magnetic system as shown by high-frequency (111.2 and 222.4 GHz) electron spin resonance (ESR) and structural data in the literature. The material gradually orders antiferromagnetically below 40 K, but some magnetically disordered domains persist down to 4 K. We propose that in defect free regions frustration prevents true magnetic order down to at least 4 K in spite of the large first- and second-neighbor exchange interactions along chains and between chains, respectively. The antiferromagnetic (AFM) order gradually developing below 40 K nucleates around structural defects that locally cancel frustration. Two antiferromagnetic resonance modes mapped in the principal planes at 4 K are assigned to the very weakly interacting one-dimensional molecular chains in antiferromagnetic regions.

International audience; Transport measurements were performed on the organic layered compound alpha-(BEDT-TTF)(2)I-3 under hydrostatic pressure. The carrier types, densities, and mobilities are determined from the magnetoconductance of alpha-(BEDT-TTF)(2)I-3. While evidence of high-mobility massless Dirac carriers has already been given, we report here their coexistence with low-mobility massive holes. This coexistence seems robust as it has been found up to the highest studied pressure. Our results are in agreement with recent DFT calculations of the band structure of this system under hydrostatic pressure. A comparison with graphene Dirac carriers has also been done.

National audience; 1,4-Bis(carboxylatoethynyl)bicyclo[2.2.2]octane: un rotor ultra-rapide dans un sel dilué est freiné au sein d’un métal multifonctionnel1L’objectif de ce travail est la conception de systèmes dans lesquels les propriétés dynamiques d’une machine moléculaire seraient corrélées aux propriétés électroniques que l’on rencontre habituellement dans les matériaux conçus au laboratoire par la technique d’électrocristallisation. Pour cela un sel dilué de formulation [nBu4N+]2[BABCO][BABCO–]2 a été préparé à partir du 1,4-di(ethynyl)bicyclo[2.2.2]octane synthétisé en neuf étapes2. Des expériences de temps de relaxation spin-réseau du 1H sur cristal statique montrent que deux environnements différents des rotors sont associés à des énergies d’activation et des fréquences de rotation différentes.Ce sel a été engagé dans un processus d’électrocristallisation avec le donneur d’électrons de type π EDT-TTF-CONH2 pour donner un nouveau métal organique cristallin : (EDT-TTF-CONH2)2[BABCO–], pour la première fois avec une fonctionnalité dynamique. Une seule position d’équilibre est observée pour le rotor dont on observe que l’énergie d’activation est grandement augmentée: ceci pourrait être attribué à des contraintes à la rotation accrues, expression d’un réseau dense d’interactions non covalentes (liaisons hydrogènes et interactions dihydrogène attractives3).Ce matériau organique métallique ouvre la voie à d’autres systèmes multifonctionnels amphidynamiques.1C. Lemouchi, C. Mézière, L. Zorina, E. Canadell, P. Wzietek, P. Auban-Senzier, C. Pasquier, P. Batail, soumis2C. Lemouchi, C. Vogelsberg, S. Simonov, L. Zorina, P. Batail, S. Brown, M. A. Garcia-Garibay, J. Am. Chem. Soc., 133, 6371-6379 (2011).3J. Echeverrıa, G. Aullon, D. Danovich, S. Shaik, S. Alvarez, Nature Chem., 2011, DOI: 10.1038/nchem.1004

We present a multifrequency electron spin resonance study in the range of 4-420 GHz of the quasi-one-dimensional, nondimerized, quarter-filled Mott insulators, delta-(EDT-TTF-CONMe2)(2)X (X=AsF6, Br). In the high-temperature orthorhombic phase above T similar to 190 K, the magnitude and the temperature dependence of the high-temperature spin susceptibility are described by a S=1/2 Heisenberg antiferromagnetic chain with J(AsF6)=298 K and J(Br)=474 K coupling constants for X=AsF6 and Br, respectively. We estimate from the temperature dependence of the linewidth (Delta H) an exchange anisotropy, J'/J of similar to 2 X 10(-3). The frequency dependence of Delta H and the g shift have an unusual quadratic dependence in all crystallographic orientations that we attribute to an antisymmetric exchange (Dzyaloshinskii-Moriya) interaction.

Date du colloque : 10/2010; National audience; L'électrocristallisation est devenue à ce jour une technique incontournable pour la préparation de cristaux moléculaires d'espèces radicalaires, obtenus sur l'électrode par oxydation ou réduction électrochimique de précurseurs moléculaires. C’est un outil à fort potentiel car il n'est pas limité à la seule préparation de cristaux conducteurs mais peut être mis en œuvre facilement pour différents types de cristaux isolants de molécules électro-actives [1].Une collaboration active entre les laboratoires de Rennes et Angers s’est développée autour de cette technique d’élaboration de monocristaux qui ont l’avantage d’être très purs. Les études physiques sont actuellement menées au niveau international entre différents partenaires, notamment dans le cadre de l’ANR blanche intitulée « ¾-Filled » coordonnée par le Laboratoire de Physique des Solides d’Orsay.Cette activité commune a été soutenue par le réseau CRISTECH avec un financement de 4000 € qui a permis l’achat de deux générateurs de micro-courant pour renouveler et étoffer le parc à Angers ainsi qu’une enceinte thermostatée à Rennes pour équiper le service installé plus récemment. L’affiche présente le principe sur lequel repose cette technique particulière de cristallogénèse, les molécules type qui peuvent être engagées, le matériel nécessaire ainsi que les paramètres qui influent sur la croissance.Deux exemples d’études récentes qui ont pu voir le jour grâce à cette technique sont également mis en exergue. L’une sur le système δ-(EDT-TTF-CONMe2)2X avec X = AsF6– ou Br–, un isolant de Mott à bande ¾ remplie [2] et [3]. L’autre concerne des sels d'un autre tétrathiafulvalène dissymétrique, à savoir o-DMTTF qui cristallise dans une structure quadratique très originale avec des anions halogénures comme Cl–, Br– et I– [4]. En particulier, nous avons pu accéder à deux séries de solutions solides [(o-DMTTF)2(X)x(Y)1–x] avec X, Y = Cl–/Br– ou Br–/I–, dans lesquelles des phénomènes d'insertion préférentielle de Br– ont été mis en évidence[1] P. Batail et al., Chem. Mater., 10, 3005 (1998).[2] L. Zorina et al., J. of Mater. Chem., 19, 6980 (2009)[3] P. Auban-Senzier et al., Phys. Rev. Lett., 102, 257001 (2009)[4] M. Fourmigué et al., Dalton Trans, 4652 (2008)

International audience; An investigation of the P-T phase diagram of the quarter-filled organic conductors, [EDT-TTF-CONMe2]2X is reported on the basis of transport and NMR studies of two members, X=AsF6 and Br of the family. The strongly insulating character of these materials in the low-pressure regime has been attributed to a remarkably stable charge-ordered state confirmed by 13C NMR and the only existence of 1/4 Umklapp e-e scattering favoring a charge ordering instead of the 1D Mott localization seen in (TMTTF)2X and (TMTSF)2X which are 1/4-filled compounds with dimerization. A nonmagnetic insulating phase instead of the spin density wave state is stabilized in the deconfined regime of the phase diagram. This sequence of phases observed under pressure may be considered as a generic behavior for 1/4-filled conductors with correlations.

International audience; Infrared reflection measurements of the half-filled two-dimensional organic conductorskappa-(BEDT-TTF)2Cu[N(CN)2]BrxCl1−x (BEDT-TTF denotes bis-(ethylenedithio)tetrathiafulvalene] were performedas a function of temperature (5 K300 K) and Br substitution (x=0%, 40%, 73%, 85%, and 90%)in order to study the metal-insulator transition. We can distinguish absorption processes due to itinerant andlocalized charge carriers. The broad midinfrared absorption has two contributions: transitions between the twoHubbard bands and intradimer excitations from the charges localized on the (BEDT-TTF)2 dimer. Since thelatter couple to intramolecular vibrations of BEDT-TTF, the analysis of both electronic and vibrational featuresprovides a tool to disentangle these contributions and to follow their temperature and electronic-correlationdependence. Calculations based on the cluster model support our interpretation.