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.

Synthesis and electronic properties of D-A-D triads based on 3-alkoxy-4-cyanothiophene and benzothienothiophene blocks.

3-Alkoxy-4-cyanothiophene units are used as building block for the synthesis of conjugated donor-acceptor-donor (D-A-D) triads. The donor part consists of benzothienothiophene end groups associated with the alkoxy groups of the 3-alkoxy-4-cyanothiophene, while the central acceptor part is formed by combining the electron-withdrawing cyano group with thiophene or benzothiadiazole units.

Facile synthesis of 3-alkoxy-4-cyanothiophenes as new building blocks for donor-acceptor conjugated systems.

3-Alkoxy-4-cyanothiophenes are efficiently synthesized in two steps from the readily available 4-cyano-3-oxotetrahydrothiophene. Regioisomers of bithiophene derivatives are easily synthesized by playing on the strong electronic dissymmetry of the thiophene ring induced by the alkoxy and cyano groups.