Fluoranthene-Based Molecules as Electron Transport and Blue Fluorescent Materials for Organic Light-Emitting Diodes

Herein we report the synthesis, characterization, and potential application of his (4- (7,9,10-triphenylfluoranthen-8-yl)pheny)sulfone (TPFDPSO2) and 2,8-bis (7,9,10-triphenylfluoranthen-8-yl) dibenzo b, d]-thiophene 5,5-dioxide (TPFDBTO2) as electron transport as well as light-emitting materials. These fluoranthene derivatives were synthesized by oxidation of their corresponding parent sulfide compounds, which were prepared via Diels-Alder reaction. These materials exhibit deep blue fluorescence emission in both solution and thin film, high photoluminescence quantum yield (PLQY), thermal and electrochemical stability over a wide potential range. Hole- and electron-only devices were fabricated to study the charge transport characteristics, and predominant electron transport property comparable with that of a well-known electron transport material, Alq(3), was observed. Furthermore, bilayer electroluminescent devices were fabricated utilizing these fluoranthene derivatives as electron transport as well as emitting layer, and device performance was compared with that of their parent sulfide molecules. The electroluminescence (EL) devices fabricated with these molecules displayed bright sky blue color emission and 5-fold improvement in external quantum efficiency (EQE) with respect to their parent compounds.

Solution structural features of N-acyl homoserine lactones

Here we demonstrate that in interbacterial quorum signal moderators, N-acylhomoserine lactones (AHLs), the stabilization of bioactive pharmacophore lactone against lysis is through the e(-) withdrawing N-acyl motif which reduces lactone carbonyl polarization. This lysis is assisted by weak (<0.05 kcal mol(-1)) contacts between N-acyl O and lactone C'. The interactions that preclude this weak contact, in the free and receptor-bound AHLs, improve lactone halflife and hence are key to the design of the antibacterial AHL analogues. (C) 2015 Elsevier Ltd. All rights reserved.

Fluoranthene derivatives as blue fluorescent materials for non-doped organic light-emitting diodes

In this study, we report synthesis of symmetrically and non-symmetrically functionalized fluoranthene-based blue fluorescent molecular materials for non-doped electroluminescent devices. The solid state structure of these fluorophores has been established by single crystal X-ray diffraction analysis. Furthermore, a detailed experimental and theoretical study has been performed to understand the effect of substitution of symmetric and non-symmetric functional groups on optical, thermal and electrochemical properties of fluoranthene. These materials exhibit a deep blue emission and high PLQY in solution and solid state. The vacuum deposited, non-doped electroluminescent devices with the device structure ITO/NPD (15 nm)/CBP (15 nm)/EML (40 nm)/TPBI (30 nm)/LiF (1 nm)/Al were fabricated and characterized. A systematic shift in the peak position of EL emission was observed from sky blue to bluish-green with EL maxima from 477 nm to 490 nm due to different functional groups on the periphery of fluoranthene. In addition, a high luminance of >= 2000 cd m(-2) and encouraging external quantum efficiency (EQE) of 1.1-1.4% were achieved. A correlation of the molecular structure with device performance has been established.

Stimuli and shape responsive `boron-containing' luminescent organic materials

Recent advancements of material science and its applications have been immensely influenced by the modern development of organic luminescent materials. Among all organic luminogens, boron containing compounds have already established their stature as one of the indispensable classes of luminescent dyes. Boron, in its various forms e. g. triarylboranes, borate dyes and boron clusters, has attracted considerable attention owing to its several unique and excellent photophysical features. In very recent times, beyond the realms of solution-state studies, luminescent boron-containing compounds have emerged as a large and versatile class of stimuli responsive materials. Based on several fundamental concepts of chemistry, researchers have come up with an admirable variety of boron-containing materials with AIE (aggregation-induced emission), mechano-responsive luminescence, thermoresponsive-luminescence as well as a number of purely organic phosphorescent materials and other standalone examples. The unique chemical as well as physical properties of boron-containing compounds are largely responsible for the development of such materials. In this review these new findings are brought together.

A comparative study of plasma-enhanced chemical vapor gate dielectrics for solution-processed polymer thin-film transistor circuit integration

This paper considers plasma-enhanced chemical vapor deposited (PECVD) silicon nitride (SiNx) and silicon oxide (SiOx) as gate dielectrics for organic thin-film transistors (OTFTs), with solution-processed poly[5, 5′ -bis(3-dodecyl-2-thienyl)-2, 2′ -bithiophene] (PQT-12) as the active semiconductor layer. We examine transistors with SiNx films of varying composition deposited at 300 °C as well as 150 °C for plastic compatibility. The transistors show over 100% (two times) improvement in field-effect mobility as the silicon content in SiNx increases, with mobility (μFE) up to 0.14 cm2 /V s and on/off current ratio (ION / IOFF) of 108. With PECVD SiOx gate dielectric, preliminary devices exhibit a μFE of 0.4 cm2 /V s and ION / IOFF of 108. PQT-12 OTFTs with PECVD SiNx and SiOx gate dielectrics on flexible plastic substrates are also presented. These results demonstrate the viability of using PECVD SiN x and SiOx as gate dielectrics for OTFT circuit integration, where the low temperature and large area deposition capabilities of PECVD films are highly amenable to integration of OTFT circuits targeted for flexible and lightweight applications. © 2008 American Institute of Physics.

Synthesis and characterization of high-spin organic materials: prototypes for the polaronic ferromagnet

The design, synthesis and magnetic characterization of thiophene-based models for the polaronic ferromagnet are described. Synthetic strategies employing Wittig and Suzuki coupling were employed to produce polymers with extended π-systems. Oxidative doping using AsF_5 or I_2 produces radical cations (polarons) that are stable at room temperature. Magnetic characterization of the doped polymers, using SQUID-based magnetometry, indicates that in several instances ferromagnetic coupling of polarons occurs along the polymer chain. An investigation of the influence of polaron stability and delocalization on the magnitude of ferromagnetic coupling is pursued. A lower limit for mild, solution phase I_2 doping is established. A comparison of the variable temperature data of various polymers reveals that deleterious antiferromagnetic interactions are relatively insensitive to spin concentration, doping protocols or spin state. Comparison of the various polymers reveals useful design principles and suggests new directions for the development of magnetic organic materials. Novel strategies for solubilizing neutral polymeric materials in polar solvents are investigated.

The incorporation of stable bipyridinium spin-containing units into a polymeric high-spin array is explored. Preliminary results suggest that substituted diquat derivatives may serve as stable spin-containing units for the polaronic ferromagnet and are amenable to electrochemical doping. Synthetic efforts to prepare high-spin polymeric materials using viologens as a spin source have been unsuccessful.

Crystal Coulomb energies: I. Organic donor-acceptor complexes--a review. II. Classical Ewald calculations of the Coulomb binding energy of four donor-acceptor crystals and Wurster's blue perchlorate. III. A rapid-convergence quantum-mechanical formalism for crystal electronic energies

Chapter I

Theories for organic donor-acceptor (DA) complexes in solution and in the solid state are reviewed, and compared with the available experimental data. As shown by McConnell et al. (Proc. Natl. Acad. Sci. U.S., 53, 46-50 (1965)), the DA crystals fall into two classes, the holoionic class with a fully or almost fully ionic ground state, and the nonionic class with little or no ionic character. If the total lattice binding energy 2ε₁ (per DA pair) gained in ionizing a DA lattice exceeds the cost 2ε_o of ionizing each DA pair, ε₁ + ε_o less than 0, then the lattice is holoionic. The charge-transfer (CT) band in crystals and in solution can be explained, following Mulliken, by a second-order mixing of states, or by any theory that makes the CT transition strongly allowed, and yet due to a small change in the ground state of the non-interacting components D and A (or D⁺ and A^-). The magnetic properties of the DA crystals are discussed.

Chapter II

A computer program, EWALD, was written to calculate by the Ewald fast-convergence method the crystal Coulomb binding energy E_C due to classical monopole-monopole interactions for crystals of any symmetry. The precision of E_C values obtained is high: the uncertainties, estimated by the effect on E_C of changing the Ewald convergence parameter η, ranged from ± 0.00002 eV to ± 0.01 eV in the worst case. The charge distribution for organic ions was idealized as fractional point charges localized at the crystallographic atomic positions: these charges were chosen from available theoretical and experimental estimates. The uncertainty in E_C due to different charge distribution models is typically ± 0.1 eV (± 3%): thus, even the simple Hückel model can give decent results.

E_C for Wurster's Blue Perchl orate is -4.1 eV/molecule: the crystal is stable under the binding provided by direct Coulomb interactions. E_C for N-Methylphenazinium Tetracyanoquino- dimethanide is 0.1 eV: exchange Coulomb interactions, which cannot be estimated classically, must provide the necessary binding.

EWALD was also used to test the McConnell classification of DA crystals. For the holoionic (1:1)-(N,N,N',N'-Tetramethyl-para- phenylenediamine: 7,7,8,8-Tetracyanoquinodimethan) E_C = -4.0 eV while 2ε_o = 4.6₅ eV: clearly, exchange forces must provide the balance. For the holoionic (1:1)-(N,N,N',N'-Tetramethyl-para- phenylenediamine:para-Chloranil) E_C = -4.4 eV, while 2ε_o = 5.0 eV: again EC falls short of 2ε₁. As a Gedankenexperiment, two nonionic crystals were assumed to be ionized: for (1:1)-(Hexamethyl- benzene:para-Chloranil) E_C = -4.5 eV, 2ε_o = 6.6 eV; for (1:1)- (Napthalene:Tetracyanoethylene) E_C = -4.3 eV, 2ε_o = 6.5 eV. Thus, exchange energies in these nonionic crystals must not exceed 1 eV.

Chapter III

A rapid-convergence quantum-mechanical formalism is derived to calculate the electronic energy of an arbitrary molecular (or molecular-ion) crystal: this provides estimates of crystal binding energies which include the exchange Coulomb inter- actions. Previously obtained LCAO-MO wavefunctions for the isolated molecule(s) ("unit cell spin-orbitals") provide the starting-point. Bloch's theorem is used to construct "crystal spin-orbitals". Overlap between the unit cell orbitals localized in different unit cells is neglected, or is eliminated by Löwdin orthogonalization. Then simple formulas for the total kinetic energy Q^(XT)_λ, nuclear attraction [λ/λ]^XT, direct Coulomb [λλ/λ'λ']^XT and exchange Coulomb [λλ'/λ'λ]^XT integrals are obtained, and direct-space brute-force expansions in atomic wavefunctions are given. Fourier series are obtained for [λ/λ]^XT, [λλ/λ'λ']^XT, and [λλ/λ'λ]^XT with the help of the convolution theorem; the Fourier coefficients require the evaluation of Silverstone's two-center Fourier transform integrals. If the short-range interactions are calculated by brute-force integrations in direct space, and the long-range effects are summed in Fourier space, then rapid convergence is possible for [λ/λ]^XT, [λλ/λ'λ']^XT and [λλ'/λ'λ]^XT. This is achieved, as in the Ewald method, by modifying each atomic wavefunction by a "Gaussian convergence acceleration factor", and evaluating separately in direct and in Fourier space appropriate portions of [λ/λ]^XT, etc., where some of the portions contain the Gaussian factor.

Systematic Studies on 3d- and 4f-Metal Containing Polyoxometalates Suitable for Organic Derivatization

232 p.

Fabrication of an organic field effect transistor using nano imprinting of Ag inks and semiconducting polymers

A simple and cheap procedure for flexible electronics fabrication was demonstrated by imprinting metallic nanoparticles (NPs) on flexible substrates. Silver NPs with an average diameter of 10 nm were prepared via an improved chemical approach and Ag Np ink was produced in α-terpineol with a concentration up to 15%. Silver micro/nanostructures with a dimension varying from nanometres to microns were produced on a flexible substrate (polyimide) by imprinting the as-prepared silver ink. The fine fluidic properties of an Ag NP/α-terpineol solution and low melting temperatures of silver nanoparticles render a low pressure and low temperature procedure, which is well suited for flexible electronics fabrication. The effects of sintering and mechanical bending on the conductivity of imprinted silver contacts were also investigated. Large area organic field effect transistors (OFET) on flexible substrates were fabricated using an imprinted silver electrode and semiconducting polymer. The OFET with silver electrodes imprinted from our prepared oleic acid stabilized Ag nanoparticle ink show an ideal ohmic contact; therefore, the OFET exhibit high performance (Ion/Ioff ratio: 1 × 103; mobility: 0.071 cm2 V-1 s-1). © 2010 IOP Publishing Ltd.

One step self-aligned multilayer patterning process for the fabrication of organic complementary circuits in combination with inkjet printing

Recent development of solution processable organic semiconductors delineates the emergence of a new generation of air-stable, high performance p- and n-type materials. This makes it indeed possible for printed organic complementary circuits (CMOS) to be used in real applications. The main technical bottleneck for organic CMOS to be adopted as the next generation organic integrated circuit is how to deposit and pattern both p- and n-type semiconductor materials with high resolutions at the same time. It represents a significant technical challenge, especially if it can be done for multiple layers without mask alignment. In this paper, we propose a one-step self-aligned fabrication process which allows the deposition and high resolution patterning of functional layers for both p- and n-channel thin film transistors (TFTs) simultaneously. All the dimensional information of the device components is featured on a single imprinting stamp, and the TFT-channel geometry, electrodes with different work functions, p- and n-type semiconductors and effective gate dimensions can all be accurately defined by one-step imprinting and the subsequent pattern transfer process. As an example, we have demonstrated an organic complementary inverter fabricated by 3D imprinting in combination with inkjet printing and the measured electrical characteristics have validated the feasibility of the novel technique. © 2012 Elsevier B.V. All rights reserved.

Sorptive interaction between goethite and strongly reducing organic substances from anaerobic decomposition of green manures

Strongly reducing organic substances (SROS) and iron oxides exist widely in soils and sediments and have been implicated in many soil and sediment processes. In the present work, the sorptive interaction between goethite and SROS derived from anaerobic decomposition of green manures was investigated by differential pulse voltammetry (DPV). Both green manures, Astragaltus sinicus (Astragalus) and Vicia varia (Vicia) were chosen to be anaerobically decomposed by the mixed microorganisms isolated from paddy soils for 30 d to prepare different SROS. Goethite used in experiments was synthesized in laboratory. The anaerobic incubation solutions from green manures at different incubation time were arranged to react with goethite, in which SROS concentration and Fe(II) species were analyzed. The anaerobic decomposition of Astragalus generally produced SROS more in amount but weaker in reducibility than that of Vicia in the same incubation time. The available SROS from Astragalus that could interact with goethite was 0.69 +/- 0.04, 0.84 +/- 0.04 and 1.09 +/- 0.03 cmol kg(-1) as incubated for 10, 15 and 30 d, respectively, for Vicia, it was 0.12 +/- 0.03, 0.46 +/- 0.02 and 0.70 +/- 0.02 cmol kg(-1). One of the fates of SROS as they interacted with goethite was oxidation. The amounts of oxidizable SROS from Astragalus decreased over increasing incubation time from 0.51 +/- 0.05 cmol kg(-1) at day 10 to 0.39 +/- 0.04 cmol kg(-1) at day 30, but for Vicia, it increased with the highest reaching to 0.58 +/- 0.04 cmol kg(-1) at day 30. Another fate of these substances was sorption by goethite. The SROS from Astragalus were sorbed more readily than those from Vicia, and closely depended upon the incubation time, whereas for those from Vicia, the corresponding values were remarkably less and apparently unchangeable with incubation time. The extent of goethite dissolution induced by the anaerobic solution from Vicia was greater than that from Astragalus, showing its higher reactivity. (c) 2008 Published by Elsevier Ltd.

Graphene nanoribbon blends with P3HT for organic electronics.

In organic field-effect transistors (OFETs) the electrical characteristics of polymeric semiconducting materials suffer from the presence of structural/morphological defects and grain boundaries as well as amorphous domains within the film, hindering an efficient transport of charges. To improve the percolation of charges we blend a regioregular poly(3-hexylthiophene) (P3HT) with newly designed N = 18 armchair graphene nanoribbons (GNRs). The latter, prepared by a bottom-up solution synthesis, are expected to form solid aggregates which cannot be easily interfaced with metallic electrodes, limiting charge injection at metal-semiconductor interfaces, and are characterized by a finite size, thus by grain boundaries, which negatively affect the charge transport within the film. Both P3HT and GNRs are soluble/dispersible in organic solvents, enabling the use of a single step co-deposition process. The resulting OFETs show a three-fold increase in the charge carrier mobilities in blend films, when compared to pure P3HT devices. This behavior can be ascribed to GNRs, and aggregates thereof, facilitating the transport of the charges within the conduction channel by connecting the domains of the semiconductor film. The electronic characteristics of the devices such as the Ion/Ioff ratio are not affected by the addition of GNRs at different loads. Studies of the electrical characteristics under illumination for potential use of our blend films as organic phototransistors (OPTs) reveal a tunable photoresponse. Therefore, our strategy offers a new method towards the enhancement of the performance of OFETs, and holds potential for technological applications in (opto)electronics.

Degradation of 17 alpha-ethinylestradiol in aqueous solution by ozonation

This study investigates the ozonation of 17 alpha-ethinylestradiol (EE2) in aqueous solution. The affecting factors on the degradation of EE2 were studied and described in details, such as initial EE2 concentration, initial pH value and ozone concentration. In addition, some parameters such as pH. electrical conductivity, mineralization efficiency and degradation products were monitored during the process. The mineralization efficiency of EE2 could reach 53.9%. During the ozonation process the rapid decrease of pH and the sharp increase of electrical conductivity indicated the fort-nation of acidic by-products, small fragments and ions which were confirmed by high performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GUMS) analysis. Results showed that there were intermediate products of smaller molecule with higher polarity produced during the course of EE2 degradation. Then a possible reaction pathway for EE2 degradation involving all intermediates detected is proposed. During the ozonation process EE2 was first oxidized into hydroxyl-semiquinone isomers which were subsequently degraded into low molecular weight compounds such as oxalic acid, malonate, glutarate, and so on. Furthermore. these organic acids are easily oxidized by ozone into carbon dioxide (CO2). This work shows that ozonation process is promising for the removal of EE2. The results can provide some useful information for the potential treatment of EE2 by ozonation in aqueous solution. (c) 2005 Elsevier B.V. All rights reserved.

Optimization of RP-HPLC analysis of low molecular weight organic acids in soil

RP-HPLC analysis for low molecular weight organic acids in soil solution has been optimized. An Atlantis (TM) C-18 column was used for the analyses. An optimal determination for eleven organic acids in soil solution was found at room temperature (25 degrees C) and 220 nm detection wavelength, with a mobile phase of 10 mM KH2PO4 -CH3OH (955, pH 2.7), a flow rate of 0.8 mL/min and 10 mu L sample size. The detection limits ranged 3.2-619 ng/mL, the coefficients of variation ranged 1.3-4.6%, and the recoveries ranged 95.6-106.3% for soil solution with standard addition on the optimal conditions proposed.

Preliminary study on the photoproduction of hydroxyl radicals in aqueous solution with Aldrich humic acid, algae and Fe(III) under high-pressure mercury lamp irradiation

Under a high-pressure mercury lamp (HPML) and using an exposure time of 4 h, the photoproduction of hydroxyl radicals ((OH)-O-.) could be induced in an aqueous solution containing humic acid (HA). Hydroxyl radicals were determined by high-performance liquid chromatography using benzene as a probe. The results showed that (OH)-O-. photoproduction increased from 1.80 to 2.74 muM by increasing the HA concentration from 10 to 40 mg L-1 at an exposure time of 4 h (pH 6.5). Hydroxyl radical photoproduction in aqueous solutions of HA containing algae was greater than that in the aqueous solutions of HA without algae. The photoproduction of (OH)-O-. in the HA solution with Fe(111) was greater than that of the solution without Fe(III) at pH ranging from 4.0 to 8.0. The photoproduction of (OH)-O-. in HA solution with algae with or without Fe(111) under a 250 W HPML was greater than that under a 125 W HPML. The photoproduction of (OH)-O-. in irradiated samples was influenced by the pH. The results showed that HPML exposure for 4 h in the 4-8 pH range led to the highest (OH)-O-. photoproduction at pH 4.0.