Direct Triple Annulations: A Way to Design Large Triazastarphenes with Intertwined Hexagonal Packing.

A new straightforward synthetic strategy has been elaborated to achieve star-shaped triazatrinaphthylene and, for the first time, triazatrianthrylene derivatives. Their solution- and solid-state properties were thoroughly characterized by cyclic voltammetry, UV-vis absorption spectroscopy, X-ray diffraction, and density functional theory calculations. Original hexagonal molecular arrangements were found in the crystal phase, which opens a new pathway for designing materials with improved three-dimensional charge-transport properties.

Exploring the Electronic Properties of Extended Benzofuran-Cyanovinyl Derivatives Obtained from Lignocellulosic and Carbohydrate Platforms Raw Materials.

Two series of linear extended benzofuran derivatives associating cyanovinyl unit and phenyl or furan moieties obtained from benzaldehyde-lignocellulosic (Be series) or furaldehyde -saccharide (Fu series) platforms were prepared in order to investigate their emission and electrochemical properties. For the fluorescence in solution and solid states, contrasting results between the two series were demonstrated. For Be series a net aggregation induced emission effect was observed with high fluorescence quantum yield for the solid state. A [2+2] cycloaddition under irradiation at 350 nm was also revealed for one derivative of Be series. In contrast, for Fu series the fluorescence in solution is higher than in the solid state. The X-ray crystallography studies for the compounds reveal the formation of strong π-π stacking for the derivatives without emissive property in the solid state and the presence of essentially lateral contacts for emissive compounds. Taking advantage of the propensity to develop 2D π-stacking mode for the more extended derivative with a central furan cycle, organic field effect transistors presenting hole mobility have been made.

Low Band Gap Donor-Acceptor Conjugated Systems Based on 3-Alkoxy or 3-Pyrrolidino-4-cyanothiophene and Benzothiadiazole Units.

3-Hexyloxy-4-cyanothiophene, 3-pyrrolidil-4-cyanothiophene, and 3,4-ethylenedioxythiophene (EDOT) units are used with benzothiadiazole as building blocks for the development of three new conjugated donor-acceptor-donor (DAD) derivatives. The DAD molecules have the central acceptor part, which is formed by combining electron-withdrawing cyano groups and the benzothiadiazole moiety, in common. Theoretical calculations and UV/Vis and electrochemical data reveal the key role of the end-capped donor to tune the electronic properties of the derivatives. A study of the electropolymerization process of the three derivatives shows the strong influence of the donor parts on both the reactivity of the precursors and the electronic properties of the resulting polymers. Derivatives end-capped with pyrrolidinocyano thiophene or EDOT units lead to films of polymers presenting low band gaps of around 0.9-1.4 eV. Upon oxidation, the two polymers present different behavior. In the presence of the pyrrolidinocyano thiophene moieties, oxidation leads to a blueshift of the absorption bands, whereas with EDOT units a classical redshift, giving high absorption in the near-IR region, is observed for the oxidized states.

Unprecedented Demonstration of Regioselective SE Ar Reaction giving Unsymmetrical Regioregular Oligothiophenes.

Aromatization of 4-cyano-3-oxotetrahydrothiophene by sulfuryl chloride gives the new building block 4-cyano-3-pyrrolidylthiophene, which forms unsymmetrical regioregular oligothiophenes with a strict alternation of the donor and acceptor groups along the conjugated system. The self-coupling reactions that form the oligomers are shown to proceed by a regioselective electrophilic aromatic substitution mechanism involving a stabilized Wheland intermediate.

Rational Topological Design for Fluorescence Enhancement upon Aggregation of Distyrylfuran Derivatives.

A series of 2,5-distyrylfuran derivatives bearing pentafluorophenyl- and cyanovinyl units have been synthesized for aggregation-induced emission (AIE). The effect of the type and extent of the supramolecular connections on the AIE of the furan derivatives were examined and correlated with their X-ray crystal structures. It was found that the simultaneous presence of cyano and perfluorophenyl units strongly enhances the fluorescence upon aggregation. Single-crystal X-ray diffraction analysis confirmed that CH⋅⋅⋅F, F⋅⋅⋅F, CH⋅⋅⋅nitrile, Ar⋅⋅⋅ArF (Ar=aryl, ArF =fluoroaryl), and nitrile⋅⋅⋅ArF intra- and intermolecular interactions drive the topology of the molecule and that solid-state supramolecular contacts favor AIE of the furan derivatives.