Quinoid Form Research Articles

Innovative Application of Salophen Derivatives in Organic Electronics as a Composite Film with a Poly(3,4-Ethylenedioxythiophene)-poly(styrenesulfonate) Matrix.

In this work, we present the innovative synthesis of salophen (acetaminosalol) derivatives in a solvent-free environment by high-speed ball milling, using a non-conventional activation method, which allowed obtaining compounds in a shorter time and with a better yield. Furthermore, for the first time, the salophen derivatives were deposited as composite films, using a matrix of poly 3,4-ethylene dioxythiophene:polystyrene sulfonate (PEDOT:PSS) polymer. Significant findings include the transformation from the benzoid to the quinoid form of PEDOT post-IPA treatment, as evidenced by Raman spectroscopy. SEM analysis revealed the formation of homogeneous films, and AFM provided insights into the changes in surface roughness and morphology post-IPA treatment, which may be crucial for understanding potential applications in electronics. The optical bandgap ranges between 2.86 and 3.2 eV for PEDOT:PSS-salophen films, placing them as organic semiconductors. The electrical behavior of the PEDOT:PSS-salophen films undergoes a transformation with the increase in voltage, from ohmic to space charge-limited conduction, and subsequently to constant current, with a maximum of 20 mA. These results suggest the possible use of composite films in organic electronics.

Structural and computational exploration of zwitterionic and quinoidal forms in Schiff base compound

The stable NH-form of the Schiff base compound, (Z)-6-(((4-chlorobenzyl) amino) methylene)-2-hydroxycyclohexa-2,4-dienone was synthesized and characterized by FTIR, SEM, EDAX anlysis and X-ray crystallographic analysis. Structural analysis was carried out to examine the NH-form of the halogen-based Schiff base compound. Additionally, an analysis of bond lengths, based on previously reported NH-forms of other Schiff bases, was conducted to distinguish between the zwitterion and quinoid structures. Further, Hirshfeld surface analysis was performed to visualize and quantify intermolecular interactions, supported by shape index, 2D fingerprint plots, and Enrichment ratio analyzes, highlighting the importance of these interactions. Energy frameworks were established to deepen the understanding of crystal packing through the computation of intermolecular interaction energies. QTAIM analysis was performed to visualize and quantify intramolecular interactions, while Density Functional Theory (DFT) studies elucidated molecular properties such as the HOMO-LUMO energy gap and its derivatives. Evaluation of antibacterial activity against S. aureus was conducted via the disc diffusion assay supplemented by molecular docking studies. This comprehensive approach provides valuable structural insights into the NH-form, as well as molecular and biological aspects of (Z)-6-(((4-chlorobenzyl) amino) methylene)-2-hydroxycyclohexa-2,4-dienone.

Thermal Equilibrium Between Quinoid/Biradical Forms Enhancing Electrochemical Amphotericity.

Upon dibenzo annulation on Thiele's hydrocarbon (tetraphenyl-p-quinodimethane), the quinoid form and the biradical form adopt quite different geometries, and thus are no longer resonance structures. When these two forms can interconvert rapidly due to the small energy barrier (ΔG≠), the equilibrated mixture contains both forms in a ratio that is determined by the energy difference (ΔGo) between the two forms. For a series of tetrakis[5-(4-methoxyphenyl)-2-thienyl]-substituted derivatives, the more stable quinoid form and the metastable biradical form coexist in solution as an equilibrated mixture due to small ΔG≠ (<15 kcal mol-1) and ΔGo (1-4 kcal mol-1), in which the proportion of the two forms can be regulated by temperature. Since the biradical form can undergo easy two-electron (2e) oxidation to the corresponding dications as well as easy 2e-reduction to the dianions, it exhibits very high electrochemical amphotericity. This character with a record-small span for not only the first oxidation and reduction potentials but also the second those, [E1 sum≈E2 sum=E2 ox-E2 red=ca. 1.4 V], is attained through thermally enhanced conversion to the biradical form from the corresponding quinoid form, the latter of which is less amphoteric due to higher Eox and lower Ered values.

Near‐Infrared Fluorescence of Novel Pyridinium–Cyclic Enolate Betaine Dyes π‐Expanded by Condensed Cyclic Thiophene Spacers

Herein, we report the synthesis of new near‐infrared (NIR) fluorescent dyes based on the pyridinium–cyclic enolate betaine (PCB) skeleton. The formation of the electron‐donor–π–electron‐acceptor (D–π–A) type dye with the electron‐donating N,N‐diphenylamino group and the electron‐accepting PCB skeleton through a series of π‐spacers allowed us to achieve NIR fluorescence. Particularly, a dye with a thienylisothianaohthene spacer showed NIR fluorescence with a significant intensity (λPL = 822 nm, ΦPL = 0.19 in DMSO). Detailed experimental and theoretical analyses suggested that the structural relaxation to a planar quinoidal form in the S1 state would be critical for intense NIR fluorescence.

Fabrication of mechanically alloyed high entropy alloys (20-Fe-20Cr-20Ni-20Mn-20Ti) modified carbon paste electrode sensor for the cyclic voltammetric determination of methyl orange

We have successfully fabricated high entropy alloys (HEA) of composition 20-Fe-20Cr-20Ni-20Mn-20Ti by ball milling method for 20 h after optimizing the milling parameters. Generally, the HEAs are very popular for their multi-elemental cocktail effect and exhibit excellent high temperature oxidation resistance, high strength, electromagnetic, wear and corrosion resistance properties. But, HEAs also exhibit significant electrocatalytic properties due to their unique morphology, composition, and structure. Therefore, we have used planetary ball milled HEA powders for the electrochemical determination of methyl orange (MO). MO is recalcitrant and very difficult to degrade and can affect the humans as well as the environment. Therefore, we must determine the presence of MO. We have investigated the effect of scan rate, modifier and analyte concentration, and the pH variation on the anodic peak current (Ipa) of MO. The calculated active syrface area of bare carbon paste electrode (BCPE) and HEA-modified carbon paste electrode (HEA-MCPE) were found to be 0.041 cm2 and 0.137 cm2 respectively. We have obtained the maximum oxidation peak current for the 8 mg HEA-MCPE at a pH of 7.2 during the electrochemical oxidation of MO. The increased Ipa in basic medium is due to structural transformation of MO from quinoid form (in acidic medium) to azo structure (in basic medium). We have also calculated the number of electrons and the protons involved in the electrochemical reaction. The calculated values of detection limit (DL) and quantification limit (QL) of 8 mg HEA-MCPE was found to be 0.114 × 10−8 M and 0.38 × 10−8 M respectively.

Photoisomerization of "Partially Embedded Dihydropyridazine" with a Helical Structure.

Herein, we report the synthesis of two "partiallyembedded fused-dihydropyridazine N-aryl aza[5]helicene derivatives" (PDH) and the demonstration of their intrinsic photo-triggered multi-functional properties based on a Kekulé biradical structure. Introducing bulky electron-withdrawing trifluoromethyl or pentafluoroethyl groups into the aza[5]helicene framework (PDH-CF3 and -C2F5) gives PDH axial chirality based on the helicity of the P and M forms, even at room temperature. Upon photo-irradiation of PDH-CF3 in a frozen solution, an ESR signal from the triplet biradical with zero-field splitting values, generated by N-N bond dissociation, was observed. However, when the irradiation was turned off, the ESR signal became silent, indicating the existence of two equilibriums, between the biradical and quinoidal forms based on the Kekulé structure, and between N-N bond cleavage and recombination. The observed photo- and thermally induced behaviors indicate that T-type photochromic molecules are involved in the photoisomerization mechanism involving the two equilibriums. Inspired by the photoisomerization, chirality control of PDH by photoracemization was achieved. Multiple functionalities, such as T-type photochromism, photo-excitation-mediated triplet biradical formation, and photoracemization, which are attributed to the "partiallyembedded dihydropyridazine" structure, are demonstrated.

Chemical and colorimetric study of the influence of grape soluble polysaccharides on the color and stability of malvidin 3-O-glucoside solutions

Red wine color is mainly due to anthocyanins’ flavylium cation. In wine, these pigments are involved in a pH-dependent equilibrium involving other forms, both colored and non-colored. This equilibrium is affected by the presence of other phenolic compounds, the so-called copigments. Moreover, other non-phenolic compounds that can be found in wine, such as polysaccharides, can also affect wine color. In this work, molecular dynamics simulations, tristimulus colorimetry and HPLC-DAD analyses have been performed to assess the effect of soluble polysaccharides (P) on the color and stability of malvidin 3-O-glucoside (Mv) solutions at different pH values, both in presence and absence of other compounds that can establish copigmentation interactions with the pigment. Results showed that P shifts the color of flavylium solutions towards a more intense color with bluer hues, which can be related to a stabilization of the blue quinoidal forms of anthocyanins. This effect is similar to that observed for quercetin 3-β-glucopyranoside (QG), although, in the case of P, it seems to be more relevant. This behavior could be due to the presence of hydrophobic regions in P that allows the interaction with the quinoidal forms, which in the case of the polysaccharide might be related to the type I rhamnogalacturonans.

Dithienoazepine‐Based Near‐Infrared Dyes: Janus‐Faced Effects of a Thiophene‐Fused Structure on Antiaromatic Azepines

AbstractWe here disclose that the incorporation of thiophene rings into a seven‐membered 8π azepine in a fused fashion produces a useful antiaromatic core for near‐infrared (NIR) dyes. In contrast to dibenzazepine derivatives with bent structures, dithieno‐fused derivatives with electron‐accepting groups adopt flat conformations in the ground state. The dithieno‐fused derivatives exhibited broad absorption spectra that cover the visible region as well as sharp emission bands in the NIR region, which are considerably red‐shifted relative to those of the dibenzo‐fused congeners. Theoretical study revealed two contradictory effects of the less‐aromatic thiophene‐fused structure, i.e., the enhancement of the antiaromaticity of the adjacent azepine ring and the relief of the antiaromaticity through the contribution of a quinoidal resonance form. The combination of the dithienoazepine core with cationic electron‐accepting groups produced a NIR fluorescent dye with an emission at 878 nm in solution.

Dithienoazepine-Based Near-Infrared Dyes: Janus-Faced Effects of a Thiophene-Fused Structure on Antiaromatic Azepines.

We here disclose that the incorporation of thiophene rings into a seven-membered 8π azepine in a fused fashion produces a useful antiaromatic core for near-infrared (NIR) dyes. In contrast to dibenzazepine derivatives with bent structures, dithieno-fused derivatives with electron-accepting groups adopt flat conformations in the ground state. The dithieno-fused derivatives exhibited broad absorption spectra that cover the visible region as well as sharp emission bands in the NIR region, which are considerably red-shifted relative to those of the dibenzo-fused congeners. Theoretical study revealed two contradictory effects of the less-aromatic thiophene-fused structure, i.e., the enhancement of the antiaromaticity of the adjacent azepine ring and the relief of the antiaromaticity through the contribution of a quinoidal resonance form. The combination of the dithienoazepine core with cationic electron-accepting groups produced a NIR fluorescent dye with an emission at 878 nm in solution.

Stable Diradical on the Dimethyldihydropyrene Scaffold.

The diradical character in a molecular architecture can be customized primarily in two ways: first, by employing a quinoidal pro-aromatic system with net energy gained by aromatization that compensates for the energy required to generate the diradical species and, second, by employing an antiaromatic system having easily accessible triplet states that impart a diradical character. We have chosen a 14π aromatic framework, Boekelheide's dimethyldihydropyrene, and perturbed its aromaticity through the construction of its quinoidal form. The perturbed aromaticity was evident from the bond alteration in the X-ray diffraction structure, 1H nuclear magnetic resonance chemical shifts, and quantum chemical calculations. The aromaticity was restored as the system underwent a transition to the biradical structure centered on two exocyclic carbons. In addition, upon photoexcitation and without using an external reducing reagent, the diradical could be converted to a radical anion and dianion form easily when dimethylformamide was used as a solvent.

Controlling the Diradical Character of Thiele Like Compounds

Organic diradicals play an important role in many fields of chemistry, biochemistry, and materials science. In this work, by means of high-level theoretical calculations, we have investigated the effect of representative chemical substituents in p-quinodimethane (pQDM) and Thiele's hydrocarbons with respect to the singlet-triplet energy gap, a feature characterizing their diradical character. We show how the nature of the substituents has a very important effect in controlling the singlet-triplet energy gap so that several compounds show diradical features in their ground electronic state. Importantly, steric effects appear to play the most determinant role for pQDM analogues, with minor effects of the substituents in the central ring. For Thiele like compounds, we found that electron-withdrawing groups in the central ring favor the quinoidal form with a low or almost null diradical character, whereas electron-donating group substituents favor the aromatic-diradical form if the electron donation does not exceed 6-π electrons. In this case, if there is an excess of electron donation, the diradical character is reduced. The electronic spectrum of these compounds is also calculated, and we predict that the most intense bands occur in the visible region, although in some cases characteristic electronic transition in the near-IR region may appear.

Polarity-Driven Isomerization of a Hydroxynaphthalimide-Containing Spiropyran at Room Temperature.

Design of spiropyrans showing spontaneous isomerization driven by the polarity of solvents is an important consideration for the synthesis of optical sensory materials. Although some spiropyrans undergo polarity-driven isomerization, they must be heated owing to the high activation energy required for isomerization. In this study, we describe that a spiropyran containing a hydroxynaphthalimide unit (1) exhibits a polarity-driven isomerization at room temperature. It exists as a colorless spirocyclic (SP) form in less polar solvents but is isomerized to a colored merocyanine (MC) form in polar solvents. The equilibrium amount of the MC form increases with an increase in the polarity of solvents. The MC form involves two resonance structures-the quinoidal and zwitterionic forms. In polar media, the zwitterionic form dominates mainly owing to solvation by polar molecules. Solvation stabilizes the negative charge of the zwitterionic form and decreases its ground state energy, thereby enhancing SP → MC isomerization. The SP ⇌ MC isomerization terminates within barely 30 s even at room temperature because the naphthol moiety with high π-electron density lowers the activation energy for the rate-determining rotational step.

Organic-Inorganic Hybrid Pigments Based on Bentonite: Strategies to Stabilize the Quinoidal Base Form of Anthocyanin.

Anthocyanins are one of the natural pigments that humanity has employed the most and can substitute synthetic food dyes, which are considered toxic. They are responsible for most purple, blue, and red pigment nuances in tubers, fruits, and flowers. However, they have some limitations in light, pH, oxygen, and temperature conditions. Combining biomolecules and inorganic materials such as clay minerals can help to reverse these limitations. The present work aims to produce materials obtained using cetyltrimethylammonium bromide in bentonite clay for incorporation and photostabilization of anthocyanin dye. Characterizations showed that the organic molecules were intercalated between the clay mineral layers, and the dye was successfully incorporated at a different pH. Visible light-driven photostability tests were performed with 200 h of irradiation, confirming that the organic-inorganic matrices were efficient enough to stabilize the quinoidal base form of anthocyanin. The pigment prepared at pH 10 was three-fold more stable than pH 4, showing that the increase in the synthesis pH promotes more stable colors, probably due to the stronger intermolecular interaction obtained under these conditions. Therefore, organobentonite hybrids allow to stabilize the fragile color coming from the quinoidal base form of anthocyanin dyes.

Inclusion Polymerization of Pyrrole and Ethylenedioxythiophene in Assembled Triphenylamine Bis-Urea Macrocycles

Herein, two different monomers, pyrrole (Py) and ethylenedioxythiophene (EDOT), are loaded into a self-assembled bis-urea host 1 and oxidatively polymerized within its nanochannels, dramatically changing the properties of the crystalline complexes. Molecular dynamics (MD) simulation of both monomers within the channel demonstrates that they diffuse through the confinement upon applying thermal energy, which may facilitate the polymerization reaction. The structures of these host–guest complexes are characterized before and after polymerization using solid-state and photophysical measurements. The host maintains its columnar morphology during polymerization at 90 °C using iodine as an oxidizing agent. Intriguingly, upon dissolution of the host and recovery by filtration, the polymers exhibit memory of their nanoreactor environment, displaying unusual order by scanning electron microscopy, powder X-ray diffraction, and small- and wide-angle X-ray analysis. Solid-state 13C cross-polarized magic angle spinning NMR suggests that polypyrrole (PPy) exhibits primarily α,α′ linkages with some contributions from the quinoid form. Similarly, poly(ethylenedioxythiophene) (PEDOT) also exhibits formation of primarily α,α′ linkages with minor quinoid contributions. Both the 1·PPy and 1·PEDOT crystals show a 103-fold increase in conductivity to ∼10–6 S/cm versus host 1 crystals, which are nonconductive ∼10–9 S/cm. Overall, supramolecular polymerization strategies have the potential to readily modulate the properties of nanostructured materials.

Polyimide-based ultraviolet-operated nonvolatile photomemory device

Organic nonvolatile photomemory devices have drawn considerable attention in the field of optical computing. However, most organic nonvolatile photomemory devices use a charge-trap-type architecture that is complex and difficult to miniaturize. This paper proposes a nonvolatile polyimide (PI) resistive photomemory device with a simple metal–PI–metal configuration; its resistance can be altered using pulsed ultraviolet (UV) irradiation and can be maintained at the altered level even after irradiation has ceased. The resistance can also be returned to the initial state by subsequent irradiation with UV light. The memory window is around 7 order of magnitude. Fourier-transform infrared spectroscopy and UV–visible/near-infrared spectroscopy demonstrated that UV irradiation caused a high-energy-gap (Eg) aromatic form of PI to transform into low-Eg quinoid form, prompting the dominant conduction mechanism of the photomemory device to change from hopping conduction to ohmic conduction. A model characterizing the PI-based photomemory device was also developed and is discussed herein.

Experimental and Computational Studies on Bio-Inspired Flavylium Salts as Sensitizers for Dye-Sensitized Solar Cells.

Six new bio-inspired flavylium salts were synthesized and investigated by a combined computational and experimental study for dye-sensitized solar cell applications. The compounds were characterized by FT–IR, UV–Vis, NMR spectroscopy, and LC–MS spectrometry techniques. The pH-dependent photochromic properties of the flavylium dyes were investigated through a UV–Vis spectroscopy study and revealed that they follow the same network of chemical reactions as anthocyanins upon pH changes. The structural and electronic properties of the dyes were investigated using density functional theory (DFT) and time-dependent density functional theory (TD–DFT). Geometry optimization calculation revealed that all dyes, regardless of the specie, flavylium cations or quinoidal bases, present a planar geometry. The photovoltaic performances of the dyes, in both flavylium and quinoidal base forms, were evaluated by the HOMO and LUMO energies and by calculating the light-harvesting efficiencies, the free energy change of electron injection, and the free energy change regeneration. The MO analysis showed that all dyes can inject electrons into the conduction band of the TiO2 upon excitation and that the redox couple can regenerate the oxidized dyes. The results obtained for the free energy change of electron injection suggest that the quinoidal bases should inject electrons into the semiconductor more efficiently than the flavylium cations. The values for the free energy change regeneration showed that the redox electrolyte can easily regenerate all dyes. Dipole moment analysis was also performed. DSSCs based on the dyes, in both flavylium and quinoidal base forms, were assembled, and their photovoltaic performances were evaluated by measuring the open-circuit voltage, the short circuit current density, the fill factor, and the energy conversion efficiency. Results obtained by both experimental and computational studies showed that the overall performances of the DSSCs with the quinoidal forms were better than those obtained with the flavylium cations dyes.

Interaction of cyanidin with a hydroxylated surface (kaolin), modeling the effect of pН

The development of interest in anthocyanins in recent years is associated with an increase in the range of applications of these natural glycosides, contained in plants and berries, the color changes from red to blue with increasing pH. In addition to coloring properties (clay, fabric, hair), the use of anthocyanins – components of red and blue berries (including blueberries) – helps to reduce the risk of cardiovascular disease, Parkinson's disease and more.Most practical studies concern the interaction of anthocyanins with surfaces (clay, tissue, gastrointestinal mucosa, etc.) that have many hydroxyl groups. Therefore, the question of determining the approximate pH range is relevant, in which such an interaction is most likely. The aim of the work was to determine the priority form of the dye (according to the pH of the medium), which can be better fixed on the surface of kaolinSimulation of the interaction of cyanidin with the surface of white clay was performed by the Hartree-Fock-Rutaan method, using the GAMESS software package.The paper presents the results of modeling the interaction of different forms of the anthocyanin model – cyanidin (the content of cyanidin in plants is 50 % of the mass of all types of anthocyanins) in solutions with pH&lt;3 (red – forms of cyanidin), 3&lt;pH&lt;7 (violet) and pH&gt;7 (blue) with a hydroxylated surface of white clay – kaolin, having different types of hydroxyl groups.&#x0D; The aglycone part of the cyanidin molecule artificially was approached at a distance of approximately 2.5 Å to the surface of kaolin.&#x0D; It was shown, that the quinoid form of cyanidin (violet) was the most active of the three forms, mainly in interaction with the silanol groups of the kaolin surface. The form of cyanidin at pH&lt;3 (red) have the lowest energies of interaction with the surface of kaolin

(Invited) Development of Benzene-Annelated Quinoidal Systems for Acceptor Applications

Quinoidal oligothiophenes have attracted great attention as promising electron-transporting semiconductors. However, the use of quinoidal molecules as nonfullerene acceptors (NFAs) in organic solar cells has not been reported so far. We hypothesized that control of diradical characteristics to fine-tune the electronic properties of quinoidal oligothiophenes is important for the application to NFAs. Since the representative approach to increase the contribution of the quinoid character is the utilization of aromatic stabilization in a quinoidal form, we designed and developed new quinoidal oligothiophenes that contain benzene annelation. As a result, we revealed that quinoidal terthiophenes having fully benzene annelation functioned as NFAs. Furthermore, the quinoidal thiophene 5-mer showed acceptor characteristics in NIR organic phototransistors. In this presentation, we also discuss the influence of benzene annelation on the diradical character and physical properties.

Conformational Selectivity of Merocyanine on Nanostructured Silver Films: Surface Enhanced Resonance Raman Scattering (SERRS) and Density Functional Theoretical (DFT) Study.

In this study, detailed structural and vibrational analysis of merocyanine has been investigated using Raman, surface enhanced Raman scattering (SERS) and surface-enhanced resonance Raman scattering (SERRS). The Raman, SERS and SERRS studies aided by density functional theoretical (DFT) calculations clearly established the prevalence of the trans- and cis-conformers of the protonated form of merocyanine (MCH+) in solid and acetonitrile solution. The binding characteristics of merocyanine adsorbed on nanostructured silver-coated films (SCFs) were investigated using excitation-dependent SERS, concentration-dependent SERRS and DFT studies. The conformers of merocyanine involved in the surface adsorption processes were recognized. The prominent marker bands observed at 1538 (ethylenic C=C stretch) and 1133 cm−1 (pyridinium C-N stretch) in the Raman spectrum of merocyanine in acetonitrile shifted to 1540 and 1126 cm−1, respectively on the nanostructured SCFs. The shift in the marker bands is associated with either the preferential binding of selective conformer or change in resonance equilibrium between the benzenoid and quinoid forms. The excitation wavelength dependent SERS spectrum infers that in addition to the major contribution from the electromagnetic enhancement, chemical (resonance) effect leads to the amplification of the 1540 cm−1 band. The concentration-dependent SERRS study showed maximum enhancement for the nanostructured SCFs functionalized with 1 μM concentration of merocyanine, indicative of monolayer coverage. For lower concentrations of merocyanine, the SERRS signal intensity reduced without any alteration in the peak positions. The SERRS study thus, revealed sub-nanomolar (0.1 nM) sensing of merocyanine using nanostructured SCFs with the analytical enhancement factor (AEF) of ∼ 1010 for the 1126 cm−1 and 1540 cm−1 Raman bands for MC concentration of 0.1 nM. In this study, combination of SERRS and DFT have clearly established the predominance of trans-MCH+ on the nanostructured silver surface with minor contribution from cis-MCH+, which remain exclusively bound to the surface via the phenoxyl ring O atom. This conformational surface selectivity of geometrical isomers of merocyanine using nanostructured surfaces can be further explored for energy efficient and economical separation of geometrical isomers.

Poly (O-Aminophenol) Produced by Plasma Polymerization Has IR Spectrum Consistent with a Mixture of Quinoid &amp; Keto Structures

A vibrational analysis of various poly(o-aminophenol) structures has been undertaken using first principles methods. It is shown that a mixture of quinoid and keto forms of poly(o-aminophenol) gives rise to a simulated spectrum that replicates the experimental infrared spectra of plasma-produced poly(o-aminophenol) better than either the quinoid or keto poly(o-aminophenol) spectra alone. An unassigned peak in the spectrum is attributed to hydrogen bonding to the silica substrate.