Stéphane Méry

Micron-sized main-chain liquid crystalline elastomer actuators with ultralarge amplitude contractions.

Responsive surfaces composed of cylindrical or square micrometer-sized thermoresponsive pillars made of thiol-ene nematic main-chain liquid crystalline elastomers (LCEs) are produced by replica molding. The individual pillars behave as microactuators, showing ultralarge and reversible contractions of around 300-400% at the nematic to isotropic phase transition. The nematic main-chain LCE microactuators described here present contractions as large as the best macroscopic systems reported in the literature. Moreover, the contraction observed for this new system outperforms the best values already reported for other LCE microsystems.

Perylenediimide-based donor-acceptor dyads and triads: impact of molecular architecture on self-assembling properties.

Perylenediimide-based donor-acceptor co-oligomers are particularly attractive in plastic electronics because of their unique electro-active properties that can be tuned by proper chemical engineering. Herein, a new class of co-oligomers has been synthesized with a dyad structure (AD) or a triad structure (DAD and ADA) in order to understand the correlations between the co-oligomer molecular architecture and the structures formed by self-assembly in thin films. The acceptor block A is a perylene tetracarboxyl diimide (PDI), whereas the donor block D is made of a combination of thiophene, fluorene, and 2,1,3-benzothiadiazole derivatives. D and A blocks are linked by a short and flexible ethylene spacer to ease self-assembling in thin films. Structural studies using small and wide X-ray diffraction and transmission electron microscopy demonstrate that AD and ADA lamellae are made of a double layer of co-oligomers with overlapping and strongly π-stacked PDI units because the sectional area of the PDI is about half that of the donor block. These structural models allow rationalizing the absence of organization for the DAD co-oligomer and therefore to draw general rules for the design of PDI-based dyads and triads with proper self-assembling properties of use in organic electronics.

High net gain at 514 nm in a photorefractive polymer doped with a chalcone derivative

We report on the photorefractive properties of a low Tg composite consisting of functionalized polysiloxane doped with a chalcone derivative. The high transparency of this doping molecule enabled the observation of high net gain at 514 nm. Orientational and Pockels contributions to the total refractive index variations were measured by frequency-dependent ellipsometry experiments. Finally, the field dependence of the gain coefficient is described using Kukhtarev’s model for the space charge field with an effective trap density as a single fitting parameter.

Liquid crystals containing a 2,6-disubstituted anthracene core—mesomorphism, charge transport and photochemical properties

The synthesis of 2-(4-phenyl)-6-anthracenes and 4,4′-bisphenyl-2,6-anthracenes, disubstituted by saturated (decyloxy) or unsaturated ((Z)-dec-4-enyloxy) chains, is reported. All the materials are liquid crystals and exhibit smectic A and/or C phases. As compared to the saturated chains, the unsaturated ones provide a significant decrease of the transition temperatures. The presence of the central “lath-like” anthracene core in the rigid aromatic moiety is found to induce some molecular π-stackings, at short range, in the mesophases. This molecular peculiarity is thought to be in a large part responsible for the high charge-carrier mobility values measured (i.e. 2 × 10−3 cm2 V−1 s−2), despite the disordered character of the mesophases. Preliminary examination of photodimerisation revealed that the formation of photoadducts was very poor in the smectic phases as compared to the same experiment run in solution. This result was attributed to the instability of the anthracene photodimers at the too high temperatures of the mesophases.

Direct comparison of mechanical and electro-optic responses of a low Tg photorefractive doped polymer

The temperature dependence of the electro-optic responses in a low glass transition temperature (Tg) photorefractive polymer was investigated using an ellipsometric technique. The sample was composed of a carbazole functionalized polysiloxane doped with a push–pull chalcone derivative. The results provide information on the orientational dynamics of the chromophores doping the polymer host. For this purpose, the electro-optic response is directly compared, for different temperatures above Tg, to dynamic shear compliance measurements characterizing the mechanical macroscopic behavior of the material. We demonstrate here that these orientational processes are entirely ruled by the mechanical properties of the material.

Thiazole-based scaffolding for high performance solar cells

An interesting way of decreasing both HOMO and LUMO energy levels simultaneously while keeping the band-gap constant in soluble electron-donor small molecules for photovoltaic applications is presented. This consists in the replacement of thiophene rings by thiazole units in small molecules based on the alternation of electron-rich and electron-deficient moieties. A new diketopyrrolopyrrole-based dumbbell-shaped electron-donor soluble molecule for organic photovoltaic applications has been synthesized and characterized. It includes thiazole units as linkers between the bis-lactam core and the triazatruxene moieties used as π-stacking platforms. A power conversion efficiency of 6.3% has been attained with this thiazole derivative and in particular with an increase of the open-circuit voltage of 0.15 V with respect to the thiophene-based organic semiconducting counterpart. This open-circuit voltage increase is due to the lowering of the HOMO level of the thiazole derivative while its LUMO level has also been stabilized as highlighted by the similar band-gap measured for the thiazole and thiophene derivatives.

Synclinic-anticlinic phase transition in tilted organosiloxane liquid crystals

In this paper, we considered the case of low molecular weight bimesogenic liquid crystals containing a siloxane moiety as the central part of their molecular architecture. For some of these compounds, both ferro- and antiferroelectric mesophases are present. Two distinct smectic structures can develop as a function of temperature, the first one at high temperature corresponding to a synclinic molecular arrangement with elongated molecules, and the second one at lower temperature corresponding to an anticlinic organisation with V-shaped molecules. Numerical calculations of the energy of different conformations of these bimesogenic molecules presented here indicate that there is no difference in energy between V-shaped and linear conformations regardless of the number of silicon atoms in the siloxane moiety. Thus a microscopic model of the synclinic–anticlinic phase transition is developed where the driving force is indeed a free energy difference between the two phases, and not a difference of energy between the V-shaped and linear conformations. The model explains why the anticlinic SmCA phase is more stable than the synclinic SmC one, why the synclinic SmC phase is generally the higher temperature one, and why in some organosiloxane materials the anticlinic SmCA phase is not present.

Molecular Packing Determines Charge Separation in a Liquid Crystalline Bisthiophene–Perylene Diimide Donor–Acceptor Material

Combined electronic structure and quantum dynamical calculations are employed to investigate charge separation in a novel class of covalently bound bisthiophene-perylene diimide type donor-acceptor (DA) co-oligomer aggregates. In an earlier spectroscopic study of this DA system in a smectic liquid crystalline (LC) film, efficient and ultrafast (subpicosecond) initial charge separation was found to be followed by rapid recombination. By comparison, the same DA system in solution exhibits ultrafast resonant energy transfer followed by slower (picosecond scale) charge separation. The present first-principles study explains these contrasting observations, highlighting the role of an efficient intermolecular charge-transfer pathway that results from the molecular packing in the LC phase. Despite the efficiency of this primary charge-transfer step, long-range charge separation is impeded by a comparatively high Coulomb barrier in conjunction with small electron- and hole-transfer integrals. Quantum dynamical calculations are carried out for a fragment-based model Hamiltonian, parametrized by ab initio second-order Algebraic Diagrammatic Construction (ADC(2)) and Time-Dependent Density Functional Theory (TDDFT) electronic structure calculations. Simulations of coherent vibronic quantum dynamics for up to 156 electronic states and 48 modes are performed using the Multi-Layer Multi-Configuration Time-Dependent Hartree (ML-MCTDH) method. Excellent agreement with experimentally determined charge separation time scales is obtained, and the spatially coherent nature of the dynamics is analyzed.

Ultrafast broadband laser spectroscopy reveals energy and charge transfer in novel donor-acceptor triads for photovoltaic applications

Triggered by the quest for new organic materials and micro-structures for photovoltaic applications, a novel class of donor-acceptor-donor (DAD) triads extended with siloxane chains has been synthesized in our labs. Because of the siloxane chains, the molecules self-organize into a smectic liquid crystal phase, resulting in a stacking of the DAD cores.We report here a preliminary study of the ultrafast dynamics of energy and charge transfer studied by femtosecond broadband transient absorption experiments on isolated triads in chloroform.

Rational Engineering of BODIPY-Bridged Trisindole Derivatives for Solar Cell Applications

Boron dipyrromethene (BODIPY) and its derivatives are known to be efficient photon-harvesting chromophores. However, their study as active materials in bulk heterojunction (BHJ) solar cells is still scarce. In this study, the development of new synthetic ways to design original BODIPY-based dumbbell-shape molecules, including a first 2,3,5,6-tetravinyl aromatic BODIPY molecule, is reported. High fill factors can be obtained in BHJ solar cells when blended with a fullerene derivative, leading to a new record BODIPY-based power conversion efficiency of 5.8 %.