Efficient Film Fabrication and Characterization of Poly(3,4-ethylenedioxythiophene):Poly(styrenesulfonate) (PEDOT:PSS)-Metalloporphine Nanocomposite and Its Application as Semiconductor Material

The use of composite films with semiconductor behavior is an alternative to enhance the efficiency of optoelectronic devices. Composite films of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and metalloporphines (MPs; M = Co, Cu, Pd) have been prepared by spin-coating. The PEDOT:PSS-MP films were treated with isopropanol (IPA) vapor to modify the polymer structure from benzoid to quinoid. The quinoid structure promotes improvements in the optical and electrical behavior of films. The composite films’ morphology and structure were characterized using infrared and Raman spectroscopy, scanning electron microscopy (SEM), and atomic force microscopy (AFM). Composite films were analyzed for their optical behavior by ultraviolet-visible spectroscopy: at λ < 450 nm, the films become transparent, indicating the capacity to be used as transparent electrodes in optoelectronic devices. At λ ≥ 450 nm, the absorbance in the films increased significantly. The CoP showed an 8 times larger current density compared to the CuP. A light induced change in the J-V curves was observed, and it is larger for the CoP. The conductivity values yielded between 1.23 × 102 and 1.92 × 103 Scm−1 and were higher in forward bias.

Detecting and Quantifying Polyhaloaromatic Environmental Pollutants by Chemiluminescence-Based Analytical Method

Polyhaloaromatic compounds (XAr) are ubiquitous and recalcitrant in the environment. They are potentially carcinogenic to organisms and may induce serious risks to the ecosystem, raising increasing public concern. Therefore, it is important to detect and quantify these ubiquitous XAr in the environment, and to monitor their degradation kinetics during the treatment of these recalcitrant pollutants. We have previously found that unprecedented intrinsic chemiluminescence (CL) can be produced by a haloquinones/H2O2 system, a newly-found ●OH-generating system different from the classic Fenton system. Recently, we found that the degradation of priority pollutant pentachlorophenol by the classic Fe(II)-Fenton system could produce intrinsic CL, which was mainly dependent on the generation of chloroquinone intermediates. Analogous effects were observed for all nineteen chlorophenols, other halophenols and several classes of XAr, and a novel, rapid and sensitive CL-based analytical method was developed to detect these XAr and monitor their degradation kinetics. Interestingly, for those XAr with halohydroxyl quinoid structure, a Co(II)-mediated Fenton-like system could induce a stronger CL emission and higher degradation, probably due to site-specific generation of highly-effective ●OH. These findings may have broad chemical and environmental implications for future studies, which would be helpful for developing new analytical methods and technologies to investigate those ubiquitous XAr.

On the Reaction of 2,5-Dihydroxy-[1,4]-benzoquinone with Diamines – Strain-induced Reactivity Effects

: The regioselectivity of the reaction of 2,5-dihydroxy-[1,4]-benzoquinone (DHBQ) with diamines could not be explained satisfactorily so far. In general, the reaction products can be derived from the tautomeric ortho-quinoid structure of a hypothetical 4,5-dihydroxy-[1,2]-benzoquinone. However, both aromatic and aliphatic 1,2-diamines form in some cases phenazines, formally by diimine formation on the quinoid carbonyl groups, and in other cases the corresponding 1,2- diamino-[1,2]-benzoquinones, by nucleophilic substitution of the OH groups, the regioselectivity apparently not following any discernible pattern. The reactivity was now explained by an adapted theory of strain-induced bond localization (SIBL). Here, the preservation of the "natural" geometry of the two quinoid C–C double bonds (C3=C4 and C5=C6) as well as the N–N distance of the co-reacting diamine are crucial. A decrease of the annulation angle sum (N–C4–C5 + C4–C5–N) is tolerated well and the 4,5-diamino-ortho-quinones, having relatively short N–N spacings are formed. An increase in the angular sum is energetically unfavorable, so that diamines with a larger N–N distance afford the corresponding ortho-quinone imines. Thus, for the reaction of DHBQ with diamines, exact predictions of the regioselectivity, and the resulting product structure, can be made on the basis of simple computations of bond spacings and product geometries.

The short wave near-infrared fluorescence properties of two p-azaquinodimethane (p-AQM)-based conjugated polymers

The absorption, scattering, and autofluorescence of biological tissues in short-wave infrared region (SWIR, 900–1700[Formula: see text]nm) are relatively low, so SWIR fluorescence usually has deeper penetration into living tissues, and can show a higher signal-to-noise ratio when used for imaging in vivo. However, there are few types of organic SWIR fluorescent materials currently. In this work, [Formula: see text]-azaquinodimethane ([Formula: see text]-AQM) with a quinoid structure is used as the acceptor unit, and carbazole or fluorene with sp3 hybridization are used as the donor units, two conjugated polymers were synthesized. The quinone structure is conducive to the redshift of absorption and fluorescence spectra, and the sp3 hybridization structure is conducive to weakening the aggregation quenching of polymer fluorescence. PF and PCz exhibited absorption peaks of 492[Formula: see text]nm and 508[Formula: see text]nm, respectively. The emission peaks of the two polymers are 920[Formula: see text]nm and 950[Formula: see text]nm, respectively, both in the short-wave near infrared region. The quantum yield (QY) of PF and PCz is 0.4% and 0.3%, respectively.

The contraction of PEDOT films formed on a macromolecular liquid-like surface

Vapour phase polymerized PEDOT on the oxidizer layer adopts a neutral benzenoid structure. After solvent rinsing, the polymer chain is deprotonated and rearranged, giving rise to doped quinoid structure and partly contributing to the contraction of the film.

A conjugated polymer with high planarity and extended π-electron delocalization via a quinoid structure prepared by short synthetic steps

A quinoidal polymer,PQuBTV, with high planarity and extended π-electron delocalization was synthesized by short synthetic steps. The polymerPQuBTVshowed balanced ambipolar and high charge carrier mobilities.