Poly[(arylene ethynylene)-alt-(arylene vinylene)]s Based on Anthanthrone and Its Derivatives: Synthesis and Photophysical, Electrochemical, Electroluminescent, and Photovoltaic Properties.

Anthanthrone and its derivatives are large polycyclic aromatic compounds (PACs) that pose a number of challenges for incorporation into the structure of soluble conjugated polymers. For the first time, this group of PACs was employed as the building blocks for the synthesis of copolymers (P1-P5) based on poly[(arylene ethynylene)-alt-(arylene vinylene)]s backbone (-Ph-C≡C-Anth-C≡C-Ph-CH=CH-Ph-CH=CH-) n . During the synthesis of P1-P5, different alkyloxy side chains were incorporated in order to tune the properties of the polymers. Of the copolymer series only P1 (containing anthanthrone and branched 2-ethylhexyloxy side chains on phenylenes), P2 and P3 (for which the anthanthrones containing carbonyl groups were converted to anthanthrene containing alkyloxy substituents) were soluble. The photophysical, electrochemical, electroluminescent and photovoltaic properties of P1-P3 are reported, compared and discussed with respect to the effects of side chains.

Superextended Tetrathiafulvalene: Synthesis, Optoelectronic Properties, Fullerenes Complexation, and Photooxidation Study.

Superextended tetrathiafulvalene compounds were prepared by the substitution of gem-dichlorovinylene with 1,2-benzenedithiol. This strategy allowed for the efficient synthesis of a highly π-extended 9,10-bis(benzo-1,3-dithiol-2-ylidene)-9,10-dihydroanthracene (sExTTF) moiety, which exhibits an intense light absorption in the visible spectrum and a reversible oxidation process. A macrocyclic host for fullerenes containing two sExTTF units was synthesized. Complexation studies revealed that fullerenes promote the photooxidation of the 1,3-dithiolylidene bond. This grants new insights into the nature of the low-energy band that appeared in several reports on fullerene complexation with hosts containing the 1,3-dithiolylidene moiety.

Cruciform alkynylated anthanthrene derivatives: a structure-properties relationship case study.

An efficient and versatile synthetic strategy toward cruciform anthanthrene compounds using Sonogashira couplings steps was developed. Acetylenic linkers were used to effectively extend the π-conjugation of polycyclic anthanthrone and anthanthrene compounds and tune their optoelectronic properties. Structure-property relationships supported by DFT calculations indicated more effective π-conjugation along the 6,12 axis than along the 4,10 axis. These molecules displayed strong J-aggregation both in solution and in the solid state and proved to be highly photostable with reversible redox processes, which are properties of interest in materials sciences.

Synthesis and optoelectronic properties of 6,12-bis(amino)anthanthrene derivatives.

A series of 6,12-bis(amino) anthanthrene-based conjugated molecules were prepared and characterized using UV-vis and fluorescence spectroscopy and cyclic voltammetry. The absorption spectra and redox potentials of these molecules can be modulated by changing the conjugated moieties linked at the 4 and 10 positions. Moreover, the optoelectronic properties of these derivatives strongly depend on the moieties attached to the nitrogen atoms at the 6 and 12 positions.

4,10-Dibromoanthanthrone as a new building block for p-type, n-type, and ambipolar π-conjugated materials.

New p-type, n-type, and ambipolar molecules were synthesized from commercially available 4,10-dibromoanthanthrone dye. Substitution at the 4,10- and 6,12-positions with different electron-rich and electron-poor units allowed the modulation of the optoelectronic properties of the molecules. A bis(dicyanovinylene)-functionalized compound was also prepared with a reduction potential as low as -50 mV versus Ag(+) with a crystalline two-dimensional lamellar packing arrangement. These characteristics are important prerequisites for air-stable n-type organic field-effect transistor applications.

New strapped porphyrins as hosts for fullerenes: synthesis and complexation study.

New strapped porphyrin-based hosts with different π-conjugated moieties and linkers have been prepared and their ability to bind with fullerenes was studied in dilute solution. We found that the ability of these hosts to bind with fullerenes strongly depends on their chemical nature and more precisely on the substitution pattern of the porphyrin deck. As expected, the more electron-rich hosts containing either an exTTF or a porphyrin unit as the strap bind fullerenes more efficiently with association constants of up to 3.9 × 10(5) M(-1). The results clearly demonstrate the potential of such hosts as a supramolecular scaffold for surface immobilization of pristine fullerenes.