Stéphane Suárez

Sublimation Not an Innocent Technique : A Case of Bis-Cyclometalated Iridium Emitter for OLED

Isomerization of a neutral bis-cyclometalated iridium(III) complex has been observed for the first time during the preparation of vacuum-processed organic light-emitting devices (OLEDs) and reproduced in solution. Isolation of the isomer revealed a cis organization of the two pyridine rings of the cyclometalating ligands. Photophysical studies show very similar emission properties of the two isomers. However, due to in situ isomerization, it is only possible to prepare vacuum-processed OLED devices having a mixture of isomers.

Luminescence-detected phase transitions in lanthanide-containing liquid crystals

Complexes between lanthanide nitrates and a pro-mesogenic 18-membered diaza-substituted coronand are luminescent both as powders and liquid crystals (between 87 and 195 degrees C), and the phase transitions are detected by monitoring luminescence intensity and lifetime.

Lanthanide luminescent mesomorphic complexes with macrocycles derived from diaza-18-crown-6

Four tetracatenar (L1–L4) and one hexacatenar (L5) ligands, derived from the diaza-18-crown-6 framework, are synthesized and characterized. In these ligands, the amine functions are fitted with benzoyloxybenzyl linker groups, attached either with a carbonyl function (L1) or a methylene bridge (L2–L5) and bearing alkoxy chains, R, of various lengths: R = OCH3 for L2, OC10H21 for L3 and L5, OC12H25 for L1, and OC16H33 for L4. The non-mesomorphic ligands L1 and L3–L5 react with various lanthanide salts to give complexes forming thermotropic hexagonal columnar phases, as ascertained by thermal, optical and small-angle X-ray diffraction methods. The length of the alkoxy chains (L3 and L4) does not much influence the mesogenic behaviour, irrespective of the linker function, the number of alkoxy chains, the counterion or the lanthanide ion. The best systems proved to be the nitrato lanthanide complexes with L3, which present a Colh phase over 100 °C (up to 147 °C for La) with melting transition temperatures between 58 (La) and 86 (Tb) °C. In the case of [Eu(NO3)3L3], chosen as a representative example of all the complexes in this analysis, the inter-column separation of 29.2 A agrees well with the packing of cylindrical columns resulting from an alternated stacking of the molecules, in which the two mesogenic arms extend on the same side, i.e. stacking the molecules in a bent conformation. The liquid crystalline phases containing Eu and Tb display metal-centred emission, meaning that these complexes are interesting building blocks for the design of luminescent liquid crystalline materials.

Organic thin-film transistors: the passivation of the dielectric-pentacene interface by dipolar self-assembled monolayers

In organic thin-film transistors (OTFTs), the conducting channel is located near the interface between the organic semiconductor and the oxide dielectric; this interface is crucial for transistor performance. Self-assembled monolayers (SAMs) on the interface reduce the negative influences of the oxide dielectric surface by decreasing the coupling of the carriers at the gate and the role of the active surface defects on transfer. In this paper, we show that SAMs carrying a dipole moment determine the OTFT performance by controlling the charge transfer between the oxide dielectric and the semiconductor. The charges introduced into the semiconductor by this transfer (i.e., residual carriers) lead to a threshold shift to positive values, as well as a decrease in the contact resistance and an increase in the apparent mobility. In this study, other effects of the SAMs, such as the gate potential shift in the channel or a direct reaction between semiconductor and SAM molecules, can be excluded as dominant processes.

An ester-substituted iridium complex for efficient vacuum-processed organic light-emitting diodes

An orange-red-emitting iridium complex (N958) was prepared, and its photophysical and device-based characteristics were investigated. Despite N958 displaying quite poor photophysical properties in solution (acetonitrile), organic light-emitting diode (OLED) devices based on the complex exhibit an efficiency close to 10%.

Solubility and Crystallizability: Facile Access to Functionalized π‐Conjugated Compounds with Chlorendylimide Protecting Groups

Functional π-conjugated molecules are relevant for the preparation of new organic electronic materials with improved performance. However, their synthesis is often rendered difficult by their inherently low solubility, and the permanent attachment of solubilizing groups may change the properties of the material. Here, we introduced the chlorendylimidyl moiety as a new temporary protecting group for the straightforward large-scale synthesis of protected quarter-, sexi-, octathiophene, and perylene bisimide diamine and dicarboxylic acid derivatives. The obtained chlorendylimides and chlorendylimidyl active esters were highly soluble in organic solvents, and optical spectroscopy confirmed the low tendency of the compounds to aggregate in solution. At the same time, they could be conveniently purified by recrystallization or precipitation. Single-crystal X-ray structures obtained for most compounds showed supramolecular motifs highlighting the role of the rigid, polychlorinated chlorendyl moieties in their crystallization. The obtained protected diamine and dicarboxylic acid derivatives were easily deprotected and converted into various amide-substituted oligothiophenes and perylene bisimides that are of interest as new functional materials for organic electronic thin film or nanowire devices.