New Benzotriazole and Benzodithiophene-Based Conjugated Terpolymer Bearing a Fluorescein Derivative as Side-Group: In-Ternal Förster Resonance Energy Transfer to Improve Organic Solar Cells.

A new benzodithiophene and benzotriazole-based terpolymer bearing a fluorescein derivative as a side group was synthesized and studied for organic solar cell (OSC) applications. This side group was covalently bounded to the backbone through an n-hexyl chain to induce the intramolecular Förster Resonance Energy Transfer (FRET) process and thus improve the photovoltaic performance of the polymeric material. The polymer exhibited good solubility in common organic chlorinated solvents as well as thermal stability (TDT10% > 360 °C). Photophysical measurements demonstrated the occurrence of the FRET phenomenon between the lateral group and the terpolymer. The terpolymer exhibited an absorption band centered at 501 nm, an optical bandgap of 2.02 eV, and HOMO and LUMO energy levels of −5.30 eV and −3.28 eV, respectively. A preliminary study on terpolymer-based OSC devices showed a low power-conversion efficiency (PCE) but a higher performance than devices based on an analogous polymer without the fluorescein derivative. These results mean that the design presented here is a promising strategy to improve the performance of polymers used in OSCs.

Synthesis and Characterization of a 2,3-Dialkoxynaphthalene-Based Conjugated Copolymer via Direct Arylation Polymerization (DAP) for Organic Electronics.

Poly[(5,5'-(2,3-bis(2-ethylhexyloxy)naphthalene-1,4-diyl)bis(thiophene-2,2'-diyl))-alt-(2,1,3-benzothiadiazole-4,7-diyl)] (PEHONDTBT) was synthesized for the first time and through direct arylation polymerization (DAP) for use as p-donor material in organic solar cells. Optimized reaction protocol leads to a donor-acceptor conjugated polymer in good yield, with less structural defects than its analog obtained from Suzuki polycondensation, and with similar or even higher molecular weight than other previously reported polymers based on the 2,3-dialkoxynaphthalene monomer. The batch-to-batch repeatability of the optimized DAP conditions for the synthesis of PEHONDTBT was proved, showing the robustness of the synthetic strategy. The structure of PEHONDTBT was corroborated by NMR, exhibiting good solubility in common organic solvents, good film-forming ability, and thermal stability. PEHONDTBT film presented an absorption band centered at 498 nm, a band gap of 2.15 eV, and HOMO and LUMO energy levels of -5.31 eV and -3.17 eV, respectively. Theoretical calculations were performed to understand the regioselectivity in the synthesis of PEHONDTBT and to rationalize its optoelectronic properties. Bilayer heterojunction organic photovoltaic devices with PEHONDTBT as the donor layer were fabricated to test their photovoltaic performance, affording low power-conversion efficiency in the preliminary studies.

Conjugated Polymer Nanoparticles as Unique Coinitiator-Free, Water-Soluble, Visible-Light Photoinitiators of Vinyl Polymerization.

The use of conjugated polymer nanoparticles (CP NPs) of poly(9,9-dioctylfluorene-alt-benzothiadiazole) and poly(9,9-di-n-octylfluorenyl-2,7-diyl) as efficient photoinitiator systems (PIS) of vinyl polymerization in water is reported herein. CP NPs are biocompatible, excitable with blue commercial LEDs and, unlike visible light Type II PIS, do not need co-initiators to trigger a monomer chain reaction. CP NPs photoinitiate polymerization of a variety of acrylic monomers with initiation rates comparable to those observed for well-known Type II PIS. Given the extraordinarily large molar absorption coefficients of CP NPs (≈108 m-1 cm-1 ) very low particle concentration is required for effective polymerization. Additionally, CP NPs behave as conventional macrophotoinitiators significantly reducing contamination risks due to leaching of low molecular weight byproducts. These combined features make CP NPs PIS suitable to synthesize polymeric materials for many healthcare and biomedical applications including drug delivery, tissue engineering, prosthetic implants, and food/medicine packaging. These CP NPs PIS are also used to synthesize nano-hydrogels with a relatively narrow and controlled size distribution in the absence of surfactants. It is proposed that polymerization is initiated at the CP NPs surface by photogenerated free polarons, in close analogy to the mechanism previously described for PIS based on inorganic semiconductor NPs.

Electron-Transfer Ionization of Nanoparticles, Polymers, Porphyrins, and Fullerenes Using Synthetically Tunable α-Cyanophenylenevinylenes as UV MALDI-MS Matrices.

Electron-transfer ionization in matrix-assisted laser desorption/ionization (ET-MALDI) is widely used for the analysis of functional materials that are labile, unstable, and reactive in nature. However, conventional ET matrices (e.g., trans-2-[3-(4- tert-butylphenyl)-2-methyl-2-propenylidene] malononitrile (DCTB)) still lack in performance due to cluster formation, reactivity with analytes, and vacuum instability. In this contribution, we report the use of α-cyanophenylenevinylene derivatives as UV MALDI matrices for the analysis, by ET ionization, of nanoparticles, polymers, porphyrins, and fullerenes. The synthetic versatility of the phenylenevinylene (PV) core allowed us to modulate physicochemical properties, fundamental for efficient formation of primary ions in the gas phase under MALDI conditions, such as planarity, ionization potentials, molar absorptivity, and laser thresholds. For instance, introduction of -CN groups in vinyl positions of the PV core induced structural disruption in planarity in the new α-CNPV derivatives, shifting their maximum molar absorptivity to UV wavelengths and increasing their ionization energy values above 8.0 eV. UV MALDI-relevant photophysical properties in solution and solid state are reported (λmax and ε355nm). LDI spectra of α-CNPVs exhibit predominant signals due to M+• and [M + H]+ species, whereas the standard matrix DCTB shows peaks associated with clusters and nondesirable products. The mass spectrometry (MS) performance of six α-CNPV derivatives was assessed for the ionization of a standard compound, with α-CNPV-CH3 and α-CNPV-OCH3 exhibiting better analytical figures of merit than those of a standard matrix (DCTB). These new matrices display high vacuum stability (79%) for up to 240 min of residence in the ionization source, in contrast with DCTB with 13%. Vacuum stability is vital, particularly for applications such as high-throughput analysis and imaging MS. In addition, when a mixture of 20 analytes (PAHs, porphyrins, and triphenylamine dyes) ranging from m/z 300 to 1700 was analyzed via ET-MALDI, we observed analyte coverage of 90% with the α-CNPV-CH3 derivative, whereas DCTB afforded only 70%. Finally, α-CNPV-CH3 was tested and compared with DCTB, as ET-MALDI matrix for petroporphyrins, conjugated polymers, gold nanoparticles, and fullerene derivatives analysis, outperforming in most cases the standard matrix.

PANI Branches onto Donor-Acceptor Copolymers: Synthesis, Characterization and Electroluminescent Properties of New 2D-Materials.

A new series of two-dimensional statistical conjugated polymers based on aniline and 9,9-dihexylfluorene as donor units and benzo- or naphtho-quinoxaline/thiadiazole derivatives as acceptor moieties, possessing PANI segments as side chains, were designed and synthesized. To investigate the effects of the perpendicular PANI branches on the properties of the main chain, the optical, electrochemical, morphological and electroluminescence properties were studied. The 2D materials tend to possess lower molecular weights and to absorb and to emit light red-shifted compared to the trunk 1D-polymers, in the yellow-red region of the visible spectrum. The 1D- and 2D-conjugated polymers present optical band gaps ranging from 2.15⁻2.55 eV, HOMO energy levels between -5.37 and -5.60 eV and LUMO energy levels between -3.02 and -3.29 eV. OLED devices based on these copolymers were fabricated. Although the performances were far from optimal due to the high turn-on voltages for which electroluminescence phenomena occur, a maximum luminescence of 55,100 cd/m² together with a current density of 65 mA/cm² at 18.5 V were recorded for a 2D-copolymer, PAFC6TBQ-PANI.

Combined UMC- DFT prediction of electron-hole coupling in unit cells of pentacene crystals.

Pentacene is an organic semiconductor that draws special attention from the scientific community due to the high mobility of its charge carriers. As electron-hole interactions are important aspects in the regard of such property, a computationally inexpensive method to predict the coupling between these quasi-particles is highly desired. In this work, we propose a hybrid methodology of combining Uncoupled Monte Carlo Simulations (UMC) and Density functional Theory (DFT) methodologies to obtain a good compromise between computational feasibility and accuracy. As a first step in considering a Pentacene crystal, we describe its unit cell: the Pentacene Dimer. Because many conformations can be encountered for the dimer and considering the complexity of the system, we make use of UMC in order to find the most probable structures and relative orientations for the Pentacene-Pentacene complex. Following, we carry out electronic structure calculations in the scope of DFT with the goal of describing the electron-hole coupling on the most probable configurations obtained by UMC. The comparison of our results with previously reported data on the literature suggests that the methodology is well suited for describing transfer integrals of organic semiconductors. The observed accuracy together with the smaller computational cost required by our approach allows us to conclude that such methodology might be an important tool towards the description of systems with higher complexity.

Electron-phonon coupling effects on intrachain polaron recombination in conjugated polymers.

Based on a one-dimensional Su-Schrieffer-Heeger (SSH) model with electron correlation considered within the extended Hubbard model (EHM), we investigate the role played by electron-phonon coupling constant on intrachain polaron recombination in conjugated polymers. Our results suggest that a competition between external electric field and electron-phonon coupling on defining the behavior of the charge distribution of the system takes place. Whereas increasing electric field plays the role of destabilizing the charge carriers, an increase of the electron-phonon coupling has the opposite effect. Therefore, a suitable balance of these properties can give rise to the correct description of charge carrier dynamics in conducting polymers.

Removal of 4-Ethylphenol and 4-Ethylguaiacol with Polyaniline-Based Compounds in Wine-Like Model Solutions and Red Wine.

Volatile phenols, such as 4-ethyphenol (4-EP) and 4-ethylguaiacol (4-EG), are responsible for the "Brett character" found in wines contaminated with Brettanomyces yeast (i.e., barnyard, animal, spicy and smoky aromas). In these trials, we explore the effectiveness of polyaniline-based compounds (polyaniline emeraldin salt (PANI-ES) and polyanaline emeraldin base (PANI-EB)), for the removal of 4-EP and 4-EG from acidic model solutions and red wine. First, a screening study, performed in an acidified 12% ethanol solution, was used to optimize parameters such as contact time and the amount of polymers required to remove 4-EP and 4-EG. Then, the trapping ability of PANI agents towards 4-EP and 4-EG was evaluated in a model solution containing other wine phenolics that could potentially be trapped by PANI (i.e., gallic acid and 4-methylcatechol). The results of this trial showed that both PANI compounds were capable of removing 4-EP, 4-EG, regardless of the presence of other phenolic compounds present at a much higher concentration. Finally, the capturing ability of PANI was evaluated in a red wine sample containing 5 mg·L-1 of 4-EP, 5 mg·L-1 of 4-EG and 2.03 ± 0.02 g·L-1 of total phenolics. The results showed that PANI-EB removed significantly more 4-EP and 4-EG than PANI-ES. For instance, a treatment with 10 mg·mL-1 of PANI-EB produced a 67.8% reduction of 4-EP, 50% reduction of 4-EG and 41.38% decrease in total phenols.

The binding of 4-ethylguaiacol with polyaniline-based materials in wines.

4-ethylguaiacol (4-EG) is one of the important compounds responsible for the "Brett character" (i.e. spicy and smoky aromas) found in wines contaminated with Brettanomyces yeast. In this trial, the ability of polyaniline-based materials (PANI-EB and PANI-ES) was tested as a potential fining agent for the removal of 4-EG in wine. First, a screening study was developed in order to determine the binding capacity of 4-EG by PANI materials in 12% ethanol solution. Then, the capturing ability of PANI against 4-EG was evaluated with a solution containing gallic acid (GA), 4-methyl-catechol (4-MC), in which the concentration of the phenolic compounds were maintained as in the real wine. The results obtained showed that the retention percentage varied between 0 to 100% (4-EG), 13.81% to 72.32% (GA), and 0 to 17.39% (4-MC), depending on the interaction time and amount of the PANI used. Finally, the capturing capacity of PANI-EB and PANI-ES against 4-EG was evaluated in a real wine sample containing originally 3.10±0.13 mg L(-1) of 4-EG and 2.55±0.10 g L(-1) of other total phenolic compounds. The analyses performed indicated that PANI-EB is more effective in removing 4-EG than PANI-ES, with retention percentages varying between 36 and 50%.