1,4-Bis(carboxylatoethynyl)bicyclo[2.2.2]octane : un rotor ultra-rapide dans un cristal de sel dilué est freiné au sein d’un métal multifonctionnel

1,4-Bis(carboxylatoethynyl)bicyclo[2.2.2]octane : un rotor ultra-rapide dans un sel dilué est freiné au sein d’un métal multifonctionnel1 L’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, soumis 2C. 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.100

Evidence for the coexistence of Dirac and massive carriers in a-(BEDT-TTF)2I3 under hydrostatic pressure

Transport measurements were performed on the organic layered compound \aI3 under hydrostatic pressure. The carrier types, densities and mobilities are determined from the magneto-conductance of \aI3 . 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.Comment: 5 pages 5 figure

Croissance de matériaux moléculaires monocristallins par électrocristallisation

L\u27électrocristallisation est devenue à ce jour une technique incontournable pour la préparation de cristaux moléculaires d\u27espèces radicalaires, obtenus sur l\u27électrode par oxydation ou réduction électrochimique de précurseurs moléculaires. C’est un outil à fort potentiel car il n\u27est 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\u27un 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\u27insertion 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

Weaving Nanoscale Cloth through Electrostatic Templating

Here we disclose a simple route to nanoscopic 2D woven structures reminiscent of the methods used to produce macroscopic textiles. We find that the same principles used in macroscopic weaving can be applied on the nanoscale to create two-dimensional molecular cloth from polymeric strands, a molecular thread. The molecular thread is composed of Co6Se8(PEt3)4L2 superatoms that are bridged with L = benzene bis-1,4-isonitrile to form polymer strands. As the superatoms that make up the polymer chain are electrochemically oxidized, they are electrostatically templated by a nanoscale anion, the tetragonal Lindqvist polyoxometalate Mo6O192–. The tetragonal symmetry of the dianionic template creates a nanoscale version of the box weave. The crossing points in the weave feature π-stacking of the bridging linker. By examining the steps in the weaving process with single crystal X-ray diffraction, we find that the degree of polymerization at the crossing points is crucial in the cloth formation. 2D nanoscale cloth will provide access to a new generation of smart, multifunctional materials, coatings, and surfaces

Functional materials based on TTF amino-acids/peptides

We report the synthesis and crystal chemistry of a series of TTF derivatives bearing simple amino acids such as the achiral Glycine or the chiral Alanine or Valine. The amino acids are linked to the TTF cores via the amino group and the acid functionality is further deprotonated to yield a TTF-carboxylate anion. The latter acts as both a pi-donor and electrolyte in the electrocristallisation experiments which deliver unprecedented zwitterionic (neutral) radicals. Their X-ray structures is analyzed and discussed in relation with their electronic and magnetic properties. This work is further extended to engage simple oligopeptides that can easily be linked to the TTF moiety. The preparation and the X-ray structures of both TTF-peptides and/or their zwitterionic radicals prepared by chemical or electrochemical methods will also be reported with an eye on how self-assembly via peptidic intermolecular interactions may be rationalized to direct the construction of novel pi-functional peptidic architectures

Photoluminescence properties of 4,5-dimethyl-4′,5′-di(methylamido) tetrathiafulvalene thin film grown by thermal evaporation

In this paper, a temperature dependence study of photoluminescence spectra of vacuum-deposited organic donor tetrathiafulvalene: 4,5-dimethyl-4′,5′-di(methylamido) tetrathiafulvalene thin layers is presented. The investigated layers were deposited in a high vacuum (2 × 10−6 Torr) using molecular beam deposition (MBD) technique on n-doped (1 1 1) oriented silicon substrates. The photoluminescence studies were carried out in the temperatures range [13 K–325 K]. Under a 325 nm wavelength light excitation and at low-temperature a broad luminescence emission peak was observed in the UV–Visible and 2 peaks in the near infrared region. The photoluminescence spectra exhibit temperature dependence with a maximum emission at 180 K. Furthermore, an enhancement of the photoluminescence signal under a continuous excitation was observed at room temperature

Frustration-induced one-dimensionality in the isosceles triangular antiferromagnetic lattice of δ-(EDT-TTF-CONMe2)2AsF6

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

Role of the antisymmetric exchange in quantum spin liquids

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

Disentangling the conductivity spectra of two-dimensional organic conductors

The optical spectrum of a κ -phase organic conductor is thoroughly analyzed for the example of κ -(BEDT-TTF) 2 Cu [ N(CN) 2 ] Br 0.85 Cl 0.15 in order to identify its various contributions. It is shown how the complex spectra can be decomposed using different approaches; the intradimer and interdimer contributions are discussed. In particular the fingerprints of electronic correlations in these spectra are considered

Radical cation salts of TTF donors with XF6 (X = Re,Ta) anions

Electrocrystallization of the dianionic Re(IV)F6 species with different organic π electron donors was carried out. Depending on the first oxidation potential of the TTF derivatives this crystallization technique gave rise to various radical cations salts involving Re(IV) or Re(V) anions. With tetramethyltetrathiafulvalene (TMTTF) the (TMTTF)2Re(IV)F6  salt was obtained. However, with tetramethyltetraselenafulvalene (TMTSF) we obtained very small needles of the (TMTSeF)2Re(V)F6 system, analogue to the so called “Bechgaard salts” [1]. We present some characteristics of this new metallic phase. We compare to the diamagnetic (TMTSeF)2Ta(V)F6 obtained by the same strategy using TBATaF6 prepared according to the Browstein’s method [2] and explore electrocrystallization of the tantalum based anions [3], [4]. References: [1] K. Bechgaard, C.S. Jacobsen, K. Mortensen, H.J. Pedersen, N. Thorup, Solid State Commun. 1980, 33, 1119-1125. [2] S. Brownstein, Inorg. Chem. 1973, 12, N°3, 584-589. [3] C. Lenoir, K. Boubekeur, P. Batail, E. Canadell, P. Auban, O. Traetteberg, D. Jérome, Synth. Met. 1991, 42, 1939-1942. [4] F. Iwase, K. Sugiura, K. Furukawa, T. Nakamura, J. Phys. Soc. Jpn. 2009, 78, N°10, 104717:1-104717:7