Hydrazone-Linked Donor-Acceptor Covalent Organic Polymer as a Heterogeneous Photocatalyst for C-S Bond Formation.

In the realm of solar energy utilization, there is a growing focus on designing and implementing effective photocatalytic systems, for the conversion of solar energy into valuable chemical fuels. The potential of Covalent Organic Polymers (COPs) as photocatalysts for visible-light-driven organic transformation has been widely investigated, positioning them as promising candidates in this field. In the design of COPs, introducing a donor-acceptor arrangement facilitates the transfer of electrons from the donor to the acceptor, creating a charge transfer complex and leading to enhanced conductivity and improved charge separation. Here we present a novel hydrazone-linked covalent organic polymer ETBC-PyHz containing TPE donor and pyridine acceptor. Utilizing this, an efficient method has been developed for an oxidative cross-coupling reaction involving C-S bond formation. This process involves arylhydrazines and arenethiols, and results in the production of unsymmetrical diaryl sulfides via the formation of aryl and thioarene radicals. This conversion holds significant importance because the byproducts produced during the process are nitrogen and water, making it environmentally benign.

Generation and Application of Aryl Radicals Under Photoinduced Conditions.

Photoinduced aryl radical generation is a powerful strategy in organic synthesis that facilitates the formation of diverse carbon-carbon and carbon-heteroatom bonds. The synthetic applications of photoinduced aryl radical formation in the synthesis of complex organic compounds, including natural products, physiologically significant molecules, and functional materials, have received immense attention. An overview of current developments in photoinduced aryl radical production methods and their uses in organic synthesis is given in this article. A generalized idea of how to choose the reagents and approach for the generation of aryl radicals is described, along with photoinduced techniques and associated mechanistic insights. Overall, this article offers a critical assessment of the mechanistic results as well as the selection of reaction parameters for specific reagents in the context of radical cascades, cross-coupling reactions, aryl radical functionalization, and selective C-H functionalization of aryl substrates.

Donor-Acceptor Covalent Organic Frameworks as a Heterogeneous Photoredox Catalyst for Scissoring Alkenes to Carbonyl Constituents.

The conversion of alkenes to carbonyl constituents via the cleavage of the C═C bond is unique due to its biological and pharmacological significance. Though a number of oxidative C═C cleavage protocols have been demonstrated for terminal and electron-rich alkene systems, none of them were optimized for electron-deficient and conjugated alkenes. In this work, a covalent organic framework containing triphenylamine and triazine units was revealed to cleave the C═C bond of alkenes under very mild conditions involving visible light irradiation due to its photoredox property. The alkenes can be conveniently broken across the double bond to their constituent carbonyl derivatives on light irradiation in the presence of air and the covalent organic framework photocatalyst. This protocol is applicable for a wide range of alkenes in an aqueous acetonitrile medium with high functional group tolerance and regioselectivity. Though the electron-deficient alkenes required tetramethylethylene diamine as a sacrificial donor, the electron-rich alkenes do not demand any additives.

Tuning Selectivity in the Visible-Light-Promoted Coupling of Thiols with Alkenes by EDA vs TOCO Complex Formation.

The visible-light-promoted catalyst-free condition has been demonstrated for self- and cross-coupling reactions of thiols in an ambient atmosphere. Further, synthesis of ß-hydroxysulfides is accomplished under very mild conditions involving the formation of an electron donor-acceptor (EDA) complex between a disulfide and an alkene. However, the direct reaction of thiol with alkene via the formation of a thiol-oxygen co-oxidation (TOCO) complex failed to produce the desired compounds in high yields. The protocol was successful with several aryl and alkyl thiols for the formation of disulfides. However, the formation of ß-hydroxysulfides required an aromatic unit on the disulfide fragment, which supports the formation of the EDA complex during the course of the reaction. The approaches presented in this paper for the coupling reaction of thiols and the synthesis of ß-hydroxysulfides are unique and do not require toxic organic or metal catalysts.

Experimental and DFT studies of gadolinium decorated graphene oxide materials for their redox properties and as a corrosion inhibition barrier layer on Mg AZ13 alloy in a 3.5% NaCl environment.

Magnesium alloys are broadly used worldwide in various applications; however, the serious disadvantage of these alloys are subject to corrosion and in aggressive/corrosive environments. A coating containing gadolinium-based composite materials can increase the alloy protection by strong electron transfer between the host alloy and the lanthanide-containing protective layer. This investigation aims to develop a Gd nanorod functionalised graphene oxide material as a corrosion inhibition barrier on the Mg alloy surface. The obtained functional materials were characterised by various spectroscopy techniques. The corrosion inhibition and composite material stability were studied by the electrochemical methods. The electrochemical stability was shown to increase with the applied current. The hydrogen evolution constantly increased and the corrosion inhibition significantly improved. Also, the computational studies of the material were performed, and their results support the experimental findings. Overall, the resultant composite material's corrosion resistance and cyclic stability are improved, and it could be used as a sodium-ion battery cathode material due to its high reversibility.

Experimental and DFT studies of porous carbon covalently functionalized by polyaniline as a corrosion inhibition barrier on nickel-based alloys in acidic media.

In acidic medium, nickel alloys severely suffer from long term corrosion problems as a result of the breakdown of their passivating oxide. The present study considers polyaniline functionalized fish-scale graphitic carbon as an anticorrosion coating on the nickel alloy surface. The fish-scale porous carbon materials are characterized by XRD, ATR-FITR, UV, Raman, TGA, SS NMR, FESEM, and TEM methods. The surface of the alloy is covalently bound with a polyaniline long chain protonated polymer so that the polyaniline functionalized honeycomb fish-scale carbon structure can exchange electrons with the metal surface. The corrosion inhibition efficiency has been investigated in different acid media like sulfuric acid and hydrochloric acid by electrochemical methods. Polyaniline functionalized porous carbon showed in 1 M H2SO4 inhibition efficiency around 64% and in 1 M HCl inhibition efficiency was around 74%. The inhibition efficiency was higher in HCl because chloride ions were not able to penetrate the graphitic sheet. The novelty of this coating is in the fact that the polyaniline functionalized porous carbon has high conductivity and is electrochemically stable in acidic medium. It is able to donate electrons to the polarized metal surface.

Experimental and DFT studies on the ultrasonic energy-assisted extraction of the phytochemicals of Catharanthus roseus as green corrosion inhibitors for mild steel in NaCl medium.

Catharanthus roseus (Apocynaceae family) extract is rich in organic phytochemicals such as alkaloids, polyphenolic compounds, and flavonoids. It contains several functional entities such as fused heterocycles, and hydroxyl and carbonyl groups, which could be useful for corrosion inhibition of mild steel in NaCl environments. In the present work, ultrasonic energy was used to obtain the ethanolic extracts of root and stem which were then tested as corrosion inhibitors for mild steel in the presence of 3.5% NaCl. The corrosion inhibition process was studied by UV-visible spectroscopy, Fourier transform infrared spectroscopy, atomic force microscopy, weight loss, and electrochemical methods. After immersing in the corrosive medium, the microstructures of mild steel were investigated by scanning electron microscopy, X-ray diffraction, and ellipsometry. The extract of C. roseus showed excellent adsorption on mild steel surface as confirmed by DFT calculations. The results indicate that the extract of C. roseus acts as a mixed type corrosion inhibitor, where the stem extract is the most efficient inhibitor in 3.5% NaCl solution possibly due to the higher active area of stem phytochemicals.

Experimental and computational studies of a graphene oxide barrier layer covalently functionalized with amino acids on Mg AZ13 alloy in salt medium.

Magnesium alloys are promising materials for the biomedical and automobile industries. The Mg alloy's light-weight property leads to numerous industrial applications. However, the magnesium alloy oxide layers are not stable in salt environments. Organic inhibitors and epoxy coatings fail as long term barriers in such media. Recently, carbon based functionalized materials, graphene oxides, were shown to be promising materials for improving corrosion resistance in acid and salt environments. Our research considered graphene oxide covalently functionalized with the amino acid leucine to form anticorrosion coating materials. The functionalized materials were characterized by XRD, Raman, FESEM, HRTEM, FTIR, and AFM methods. The corrosion inhibition efficiency was monitored by electrochemical methods. The novelty of the functionalized graphene oxide materials is that they are water impermeable, and thus could enhance the anticorrosion resistance in salt environments.

Experimental and DFT studies of carbon nanotubes covalently functionalized with an imidazole derivative for electrochemical stability and green corrosion inhibition as a barrier layer on the nickel alloy surface in a sulphuric acidic medium.

Nickel-based alloys are used for various applications such as in automobiles, superalloys and ship making. Their stability in acidic environments, however, is often not sufficient due to their native oxide films not withstanding harsh conditions. Carbon-based materials, in contrast, have shown high stability in acidic environments. In the present work, 4,5-diphenyl-imidazole-functionalized carbon nanotubes were investigated as a corrosion-inhibiting barrier layer on nickel alloy surfaces. We studied the corrosion inhibition efficiency of the imidazole-functionalized carbon nanotubes coated on nickel alloys. The materials were characterized using microscopy and spectroscopy methods. DFT studies were performed as well. The corrosion inhibition was evaluated using electrochemical methods. The imidazole-functionalized CNTs were shown to be crystalline and to have tubular structures. They displayed excellent corrosion inhibition on the nickel alloy surface.

Tuning the Photophysical and Electroluminescence Properties in Asymmetrically Tetrasubstituted Bipolar Carbazoles by Functional Group Disposition.

Carbazoles decorated with both donor and acceptor fragments offer a classical way to optimize bipolar functional properties. In this work, a series of carbazoles featuring triphenylamine donors and cyano acceptors are synthesized and their structure-property relationship is studied. The effects of connectivity and the chromophore number density on photophysical and electroluminescence properties are investigated. The position of the triphenylamine donor on the 3,6-dicyanocarbazole nucleus significantly affected the photophysical and electroluminescence properties. The dye possessing triphenylamine on C2 and C7 displayed a red shift in absorption when compared with the structural analogue with triphenylamine tethered to C1 and C8. The emission wavelength of the dyes are tunable from blue to green, by altering the position of triphenylamine and cyano substituents. All of the dyes exhibited positive solvatochromism in emission, attributable to the photoinduced intramolecular charge transfer from the triphenylamine donor to the cyano acceptor. However, the extent of charge transfer and hybridization of local and charge-transfer-excited states is highly dependent on the position of triphenylamine and cyano groups on the carbazole nucleus. Dyes containing cyano substituents at C2 and C7 showed a prolonged excited state lifetime, broad emission, and large Stokes shifts, indicating the presence of a higher charge transfer component in the excited state. The dyes displayed exceptional thermal stability with the onset decomposition temperature (10% weight loss) > 350 °C. Electrochemical measurements revealed low oxidation potential for dyes containing triphenylamine at C3 and/or C6. Addition of a cyano acceptor on carbazole led to the stabilization of lowest unoccupied molecular orbital. Furthermore, the materials were tested as emitting dopants in solution-processable multilayer organic light emitting diodes and found to display deep-blue/sky-blue electroluminescence with external quantum efficiency as high as 6.5% for a deep-blue emitter (CIE y ∼ 0.06).

Vinyl-Linked Cyanocarbazole-Based Emitters: Effect of Conjugation and Terminal Chromophores on the Photophysical and Electroluminescent Properties.

A series of carbazole-based dyes functionalized with different auxochromes via vinyl linker have been synthesized and characterized. A progressive shift in the absorption maximum is observed as the conjugation and electron-donating nature of chromophore increases. Dyes containing electron-releasing terminal groups such as triphenylamine and carbazole exhibited positive emission solvatochromism attributable to an induced intramolecular charge transfer from triphenylamine/carbazole donor to cyano acceptor. The superior electroluminescence performance of disubstituted dyes demonstrates the role of an additional cyanocarbazole in achieving balanced charge transport compared to monosubstituted analogues. In addition, the electroluminescence performance of the dyes exhibited trends attributable to the electron richness of the linker/terminal chromophore. Thus, the carbazole-based derivatives displayed better electroluminescence efficiency than the analogous fluorene derivatives. Similarly, 2,7-substituted carbazole derivative exhibited better performance than the 3,6-substituted carbazole derivative. A doped electroluminescent device containing 3 wt % tricarbazole derivative showed blue emission with a high external quantum efficiency of 5.3% at a practical brightness of 1000 cd/m2.

Fine-Tuning of Photophysical and Electroluminescence Properties of Benzothiadiazole-Based Emitters by Methyl Substitution.

New benzothiadiazole-based materials containing methyl substitution are prepared and characterized as promising green/yellowish green emitters for electroluminescent applications. The dyes exhibited shorter wavelength absorption and emission when compared to nonmethylated dyes. A dye containing methyl group on the donor side exhibited blue shift in absorption and emission when compared to the analogous dye containing methyl group away from donor. The steric effect exerted by the methyl group is responsible for the nonplanar arrangement of donor and acceptor, which inhibited the intramolecular charge transfer. All the dyes displayed solvatochromism in the emission spectra characteristic of hybridization of local and charge transfer excited states. Due to the benefit of methyl group, the dyes restrained the formation of aggregates in the solid state. Solution processed multilayered OLED device were fabricated employing these compounds either as host emitters or dopant emitters in suitable host matrix and exhibited green/yellowish green electroluminescence with external quantum efficiency as high as 4.6% (15.7 cd A-1).

A new molecular design based on hybridized local and charge transfer fluorescence for highly efficient (>6%) deep-blue organic light emitting diodes.

A deep-blue emitter was developed by modifying carbazole nuclear positions C2 & C7 with a triphenylamine donor and C3 & C6 with a cyano acceptor. The molecular design features cross-conjugated localized and charge transfer chromophores which results in a hybridized local charge transfer (HLCT) excited state. An organic light emitting diode (OLED) using this material exhibited high external quantum efficiency (6.5%) with excellent color saturation (CIEy ∼ 0.06) and small full-width at half maximum (48 nm).

Photophysics, Electrochemistry, Morphology, and Bioimaging Applications of New 1,8-Naphthalimide Derivatives Containing Different Chromophores.

A series of 1,8-naphthalimide-based fluorophores containing different chromophores with varying conjugation and electron richness at the imidic nitrogen atom are synthesized and characterized. These amine-functionalized naphthalimides are bipolar in nature and exhibit interesting optical and morphological variations attributable to the nature of the N substituents. Despite the fact that the dyes are structurally different owing to variation of the substituent on the imidic nitrogen atom, their electronic characteristics are similar and originate from the 4-aminonaphthalimide segment. Nevertheless, they exhibit variations in morphology in the microscopic domain, and this is attributable to structural differences. Further, these fluorescent dyes display biocompatibility and are used in the bioimaging of cells.

Bi-anchoring Organic Dyes that Contain Benzimidazole Branches for Dye-Sensitized Solar Cells: Effects of π†Spacer and Peripheral Donor Groups.

Benzimidazole-branched bi-anchoring organic dyes that contained triphenylamine/phenothiazine donors, 2-cyanoacrylic acid acceptors, and various π linkers were synthesized and examined as sensitizers for dye-sensitized solar cells. The structure-activity relationships in these dyes were systematically investigated by using absorption spectroscopy, cyclic voltammetry, and density functional theory calculations. The wavelength of the absorption peak was more-heavily influenced by the nature of the π linker than by the nature of the donor. For a given donor, the absorption maximum (λmax ) was red-shifted on changing the π linker from phenyl to 2,2'-bithiophene, whilst the dyes that contained triphenylamine units displayed higher molar extinction coefficients (ϵ) than their analogous phenothiazine-based triphenylamine dyes, which led to good light-harvesting properties in the triphenylamine-based dyes. Electrochemical data for the dyes indicated that the triphenylamine-based dyes possessed relatively low-lying HOMOs, which could be beneficial for suppressing back electron transfer from the conduction band of TiO2 to the oxidized dyes, owing to facile regeneration of the oxidized dye by the electrolyte. The best performance in the DSSCs was observed for a dye that possessed a triphenylamine donor and 2,2'-bithiophene π linkers. Electron impedance spectroscopy (EIS) studies revealed that the use of triphenylamine as the donor and phenyl or 2,2'-bithiophene as the π linkers was beneficial for disrupting the dark current and charge-recombination kinetics, which led to a long electron lifetime of the injected electrons in the conduction band of TiO2 .

Benzimidazole-Branched Isomeric Dyes: Effect of Molecular Constitution on Photophysical, Electrochemical, and Photovoltaic Properties.

Three benzimidazole-based isomeric organic dyes possessing two triphenylamine donors and a cyanoacrylic acid acceptor are prepared by stoichiometrically controlled Stille or Suzuki-Miyaura coupling reaction which predominantly occurs on the N-butyl side of benzimidazole due to electronic preferences. Combined with the steric effect of the N-butyl substituent, placement of the acceptor segment at various nuclear positions of benzimidazole such as C2, C4, and C7 led to remarkable variations in intramolecular charge transfer absorption, electron injection efficiency, and charge recombination kinetics. The substitution of acceptor on the C4 led to red-shifted absorption, while that on C7 retarded the charge transfer due to twisting in the structure caused by the butyl group. Because of the cross-conjugation nature and poor electronic interaction between the donor and acceptor, the dye containing triphenylamine units on C4 and C7 and the acceptor unit on C2 showed the low oxidation potential. Thus, this dye possesses favorable HOMO and LUMO energy levels to render efficient sensitizing action in solar cells. Consequently, it results in high power conversion efficiency (5.01%) in the series with high photocurrent density and open circuit voltage. The high photocurrent generation by this dye is reasoned to it exceptional charge collection efficiency as determined from the electron impedance spectroscopy.

Phenothiazine decorated carbazoles: effect of substitution pattern on the optical and electroluminescent characteristics.

A series of thienylphenothiazine decorated carbazoles were synthesized and characterized by optical, electrochemical, thermal, and theoretical investigations. Absorption spectra of the compounds are influenced by the substitution pattern and chromophore number density. Compounds containing 2,7-substitution exhibited red-shifted absorption, while the chromophore loading on the other positions led to the increment in molar extinction coefficients due to the increase in the chromophore density. Multiple substitutions resulted in twisting of chromophores and affected the conjugative delocalization of the π-electrons, which produced shorter wavelength absorption for the 2,3,6,7-tetrasubstituted derivative. Interestingly, the compounds exhibited excited-state solvatochromism attributable to the structural reorganization-induced electronic perturbations. The solvatochromic data are supportive of a general solvent effect, which is further confirmed by Lippert-Mataga correlation. End-capping with butterfly shaped phenothiazine restrained the formation of molecular aggregates in the solid state. All of the compounds displayed exceptional thermal stability attributable to the rigid carbazole building block. Solution processed OLED fabricated using the new materials as emitting dopants in 4,4'-bis(9H-carbazol-9-yl)biphenyl host exhibited bluish green electroluminescence.

Fluorene-based sensitizers with a phenothiazine donor: effect of mode of donor tethering on the performance of dye-sensitized solar cells.

Two types of fluorene-based organic dyes featuring T-shape/rod-shape molecular configuration with phenothiazine donor and cyanoacrylic acid acceptor have been synthesized and characterized as sensitizers for dye-sensitized solar cells. Phenothiazine is functionalized at either nitrogen (N10) or carbon (C3) to obtain T-shape and rod-like organic dyes, respectively. The effect of structural alternation on the optical, electrochemical, and the photovoltaic properties is investigated. The crystal structure determination of the dye containing phenyl linker revealed cofacial slip-stack columnar packing of the molecules. The trends in the optical properties of the dyes are interpreted using time-dependent density functional theory (TDDFT) computations. The rod-shaped dyes exhibited longer wavelength absorption and low oxidation potentials when compared to the corresponding T-shaped dyes attributable to the favorable electronic overlap between the phenothiazine unit and the rest of the molecule in the former dyes. However, the T-shaped dyes showed better photovoltaic properties due to the lowest unoccupied molecular orbital (LUMO) energy level favorable for electron injection into the conduction band of TiO2 and appropriate orientation of the phenothiazine unit rendering effective surface blocking to suppress the recombination of electrons between the electrolyte I3(-) and TiO2. The electrochemical impedance spectroscopy investigations provide further support for the variations in the electron injection and transfer kinetics due to the structural modifications.

Plant Growth Absorption Spectrum Mimicking Light Sources.

Plant factories have attracted increasing attention because they can produce fresh fruits and vegetables free from pesticides in all weather. However, the emission spectra from current light sources significantly mismatch the spectra absorbed by plants. We demonstrate a concept of using multiple broad-band as well as narrow-band solid-state lighting technologies to design plant-growth light sources. Take an organic light-emitting diode (OLED), for example; the resulting light source shows an 84% resemblance with the photosynthetic action spectrum as a twin-peak blue dye and a diffused mono-peak red dye are employed. This OLED can also show a greater than 90% resemblance as an additional deeper red emitter is added. For a typical LED, the resemblance can be improved to 91% if two additional blue and red LEDs are incorporated. The approach may facilitate either an ideal use of the energy applied for plant growth and/or the design of better light sources for growing different plants.

Organic dyes containing fluorene decorated with imidazole units for dye-sensitized solar cells.

New organic dyes containing fluorene functionalized with two imidazole chromophores as donors and cyanoacrylic acid acceptors have been synthesized and successfully demonstrated as sensitizers in nanocrystalline TiO2-based dye-sensitized solar cells (DSSCs). The monoimidazole analogues were also synthesized for comparison. The Sommelet reaction of bromomethylated 2-bromo-9,9-diethyl-9H-fluorene produced the key precursor 7-bromo-9,9-diethyl-9H-fluorene-2,4-dicarbaldehyde required for the preparation of imidazole-functionalized fluorenes. Since the dyes possess weak donor segment, the electron-richness of the conjugation pathway dictated the optical, electrochemical, and photovoltaic properties of the dyes. The dyes served as sensitizers in DSSC and exhibited moderate efficiency up to 3.44%. The additional imidazole present on the fluorene has been found to retard the electron recombination due to the bulkier hydrophobic environment and led to high open-circuit voltage in the devices.