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Synthesis and photochromic properties of some N-phthalimide azo-azomethine dyes. A DFT quantum mechanical calculations on imine-enamine tautomerism and trans-cis photoisomerization
摘要： This paper presents synthesis, photophysical characterization and quantum mechanical calculations of some N-phthalimide azo-azomethine dyes. The dyes were synthesized via azo coupling reaction between 2,4-substituted aromatic anilines and salicylic aldehyde followed by condensation reactions between azo dyes and N-aminophtalimide. Quantum chemical calculations to optimise the molecular geometry and to determine the electron densities of the trans (E) imine ? enamine and the cis (Z) imine ? enamine isomers and their vibrational frequencies have been computed by using DFT at B3LYP/6–31 + G(d,p) level of theory in vacuo. The effect of the used DMF solvent on the molecular structure and bond energies has been determined by using the IEFPCM model. Thermodynamic parameters such as total electronic energy E(RB3LYP), enthalpy H298 (sum of electronic and thermal enthalpies), free Gibbs energy G298 (sum of electronic and thermal free Gibbs energies) and dipole moment μ were computed in order to estimate the ΔE, Δμ, ΔH, ΔG and ΔS values. The NBO analysis was performed in order to understand the intramolecular charge transfer and the energy of resonance stabilization. After molecular geometry optimization, the electronic spectra were obtained by TD-DFT calculations at the above mentioned basis set using the IEFPCM model of DMF as a solvent. The solvatochromic effect of the dyes in four solvents with different polarity has been studied by UV–VIS spectroscopy and compared with the theoretically predicted. The coincidence between measured and calculated spectra is satisfactory. The dynamic photoisomerization experiments were performed in DMF under irradiation with UV light at λ = 365 nm (mostly E → Z) and with VIS light at λ = 400–800 nm (mostly Z → E). The spectra were recorded in the spectral region from 300 to 800 nm at identical sample concentrations of the three dyes and illumination times in order to investigate the photodynamical E → Z → E conversion of the\N_N\chromophore group of the dyes as well as the imine ? enamine tautomerization.
关键词： Tautomerism,DFT calculations,Schiff bases,Azo-azomethine dyes,Photochromism,Trans-cis photoisomerization
更新于2025-09-23 15:21:01
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Near-Infrared Photoluminescence and Electrochemiluminescence from a Remarkably Simple Boron Difluoride Formazanate Dye
摘要： Electrochemiluminescence involves the generation of light via electrochemical reactions and has recently shown utility for single-cell imaging. To further develop this novel imaging platform, it is necessary to produce readily available dyes that photoluminesce and electrochemiluminesce in the near-infrared region to limit absorption by biological tissue. To address this need, we prepared a boron difluoride formazanate dye that exhibits near-infrared photoluminescence in two straightforward synthetic steps. Examination of its solid-state structure suggests that the N-aryl substituents have significant quinoidal character, which narrows the S1-S0 energy gap and leads to near-infrared absorption and photoluminescence. Electrochemical properties were probed using cyclic voltammetry and revealed four electrochemically reversible waves. Electrochemiluminescence properties were examined in the presence of tri-n-propylamine, leading to maximum intensity at 910 nm, at least 85 nm (1132 cm?1) red-shifted compared to all other organic dyes. This work sets the stage for the development of future generations of dyes for emerging applications, including single-cell imaging, that require near-infrared photoluminescence and electrochemiluminescence.
关键词： NIR electrochemiluminescence,Electrochemistry,Formazanate ligands,Organic dyes,NIR photoluminescence
更新于2025-09-23 15:21:01
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First theoretical probe for efficient enhancement of nonlinear optical properties of quinacridone based compounds through various modifications
摘要： In this study, first attempt has been made for theoretical designing of quinacridone (QA) dye and new QA-based compounds (QA-1 to QA-9) were proposed by installing auxiliary donors (dimethylvinyl, methoxy, and N,N-dimethylamine), donor (diphenylamine) and acceptors (cyanoacrylic acid, CN and NO2) segments into fixed π-bridge QA. DFT and TDDFT calculations with B3LYP/6-31G(d,p) and CAM-B3LYP/6-31G(d,p) functional were used to shed light on the promising structure, charge transport and NLO properties. Introduction of auxiliary donors/donor and acceptor successfully modified the structure which led to superior NLO properties. An eye-catching NLO response was observed in all designed compounds. Interestingly, QA-9 exhibits appealingly large enhancement in NLO properties through ICT process with < α > and βtot computed to be 716.02 (a.u) and 128082.15 (a.u) respectively. UV–Vis results indicates the QA-9 most red shifted among all studied compounds with λmax = 489.02 nm. QA-1 to QA-9 showed narrow HOMO-LUMO energy gap as compared to QA which results in enhanced NLO response. NBO analysis confirms the formation of charge separation state in QA-1 to QA-9 due to successful migration of electrons from auxiliary donors/donor to acceptors via π-bridge. The present research evokes the scientific interest regarding the development of QA based tempting NLO compounds that can be beneficial in modern hi-tech applications.
关键词： Density functional theory,Molecular modeling,Quinacridone-based dyes,Donor and acceptor units,NLO properties,Two-state model
更新于2025-09-23 15:21:01
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Redox-Switchable Cyan Fluorescence of a BODIPY Analog Inspired by Propentdyopent Pigments
摘要： The combination of reversible redox chemistry and bright redox-responsive emission properties is key to the development of electrofluorochromic switches for applications in bioimaging and optoelectronics. Herein, the redox-active dipyrrin-1,9-dione fragment, which is characteristic of the propentdyopent family of heme metabolites and urinary pigments, is employed for the synthesis of a BODIPY analog. This boron difluoride complex exhibits bright fluorescence in organic solvents and a significant ipsochromic shift to the cyan region when compared to typical green BODIPY dyes. Electrochemical and spectroscopic measurements show that the dipyrrindione ligand acts as an electron reservoir by hosting an unpaired spin upon one-electron reduction. This ligand-based redox event reversibly abolishes the fluorescence emission, thus switching off the novel electrofluorochromic system.
关键词： Redox chemistry,Switches,BODIPY,Fluorescence,Dyes/Pigments
更新于2025-09-23 15:21:01
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A Blue Photosensitizer Realizing Efficient and Stable Green Solar Cells via Color Tuning by the Electrolyte
摘要： Semitransparent dye-sensitized solar cells (DSCs) are appealing as aesthetically pleasing and colorful see-through photovoltaics. Green semitransparent DSCs have been presented, but the best ones rely on green zinc porphyrin photosensitizers and high volatile electrolytes. For potential outdoor applications, the zinc porphyrin DSCs employing ionic liquid electrolytes merely reached a power conversion efficiency (PCE) of 6.3% even with opaque mesoporous TiO2 films. Herein, the new green DSC is realized by using a blue organic photosensitizer in conjunction with an orange ionic-liquid-based electrolyte, presenting a simple and an effective path for color tuning of photovoltaics. The new approach allows for broadly modulating the color from spring green to cyan by tuning the contributions of the light absorption by the dye-sensitized TiO2 film and the electrolyte layer. The new semitransparent DSCs with spring green to cyan colors have PCEs ranging from 6.7% to 8.1% and show stability for 1000 h under accelerated ageing test at 80 °C, superior to the zinc porphyrin DSCs. The findings pave a new way to achieve efficient and stable colorful solar cells.
关键词： semitransparent solar cells,blue dyes,porphyrin dyes,dye-sensitized solar cells,ionic liquid electrolytes
更新于2025-09-23 15:19:57
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Acid(g)/base(g)-controlled reversible ????1/2 of absorption spectrum of a functional dye film
摘要： UV–Vis absorption full width at half maximum (FWHM) plays a significant role not only in describing spectral shapes but also in determining the use of organic dyes for a particular application. For example, organic dyes with a relatively wide absorption FWHM are beneficial with respect to enhancing photon absorption efficiency of solar cells, whereas, for improving color purity in optical filters, narrow FWHM is desirable. Despite such a critical role, studies examining the modulation of absorption FWHM from an organic dye in the solid state are relatively lacking. In this work, we suggest rapid, simple, and effective method to control the absorption FWHM of a squarylium-based dye (SQ) film using an organic solvent vapor. Alternative treatments of base/acid gas to the SQ film (2.0 s for each gas) resulted in reversible absorption FWHM (D FWHM: 121 nm). From the systematic optical and morphology characterizations, it was revealed that changes in FWHM originated from reversible molecular arrangements between monomer-type and H-aggregate-type of SQ by efficient base/acid vapor diffusion into the SQ film. Moreover, the modulation exhibited high fatigue resistance against repeated gas treatments, which secures its practical applications. These results suggest that the proposed simple gas-treatment process in this work is beneficial for the efficient modulation of absorption FWHM of various organic dyes.
关键词： gas treatment,aggregation,organic dyes,full width at half maximum,monomer,absorption spectrum
更新于2025-09-23 15:19:57
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Dye Engineered Perovskite Solar Cells under Accelerated Thermal Stress and Prolonged Light Exposure
摘要： Herein, the thermal and light stability enhancement of planar perovskite solar cells (PSCs) based on the approach of dye-sensitization of the titania compact layer with the triphenylamine-based metal-free organic (E)-3-(5-(4-(bis(2’,4’-dibutoxy-[1,1’-biphenyl]-4-yl) amino) phenyl) thiophen-2-yl)-2-cyanoacrylic acid (D35) dye is reported. The D35 molecule is chemically adsorbed via a bidentate anchor group upon the TiO2 underlayer. This enhances the power conversion efficiency of PSCs due to its well-established versatile role, offering facilitation of electron charge transfer to the anode while favoring the growth of robust and homogenous perovskite layers. However, its influence in the PSC performance seems to expand further. The stability experiments showed an enhanced endurance for the devices after the insertion of D35, not only in shelf-shield conditions but also after accelerated thermal tests and prolonged light exposure. This study confirms the plethoric role of dye sensitization strategy and its advantages to interfacial engineering via organic chromophores towards efficient and stable PSCs.
关键词： dyes/pigments,perovskite solar cells,titanium dioxide,perovskite phases,stability enhancement
更新于2025-09-23 15:19:57
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Influence of the meso-substituents of zinc porphyrins in dye-sensitized solar cell efficiency with improved performance under short periods of white light illumination
摘要： The sensitization activity of four zinc metalloporphyrin dyes: meso-tetrakis(4-pyridyl)porphyrinato Zn(II) (a), meso-triphenyl-(4-carboxyphenyl)porphyrinato Zn(II) (b), meso-tetrakis(4-carboxyphenyl)porphyrinato Zn(II) (c) and meso-tripyridyl(4-carboxyphenyl)porphyrinato Zn(II) (d) is reported here, in terms of current-potential curve, open-circuit potential, fill factor, and overall solar energy conversion efficiency which have been evaluated under 100 mW/cm2 light intensity and their performances compared to the benchmark N719 (di-tetrabutylammonium cis-bis(isothiocyanato)bis(2,2′-bipyridyl-4,4′-dicarboxylato) ruthenium(II). This work focus the structural aspects of dyes with anchoring groups using TiO2-based Dye Sensitized Solar Cells (DSSCs), which includes pyridyl and carboxyphenyl acid groups and argue how the combination of both anchoring groups, in the same structure, may allow relevant optimization of DSSCs performance in the near future. Also, a noticeable improvement in the photovoltaic performance of all dyes, reaching a maximum increase from 25% to 69% in the overall DSSC efficiency under short periods of white light illumination is discussed.
关键词： Dye sensitized solar cells (DSSCs),Macrocycles,Carboxylic acid anchoring group,Dyes,Photoconversion efficiency,TiO2,Metalloporphyrin
更新于2025-09-23 15:19:57
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Photovoltaic cells with various azo dyes as components of the active layer
摘要： The photovoltaic response of six cells with an active layer of heterocyclic azo dyes is presented for the first time. The active azo layers differed in the type of substituent (i.e. electron-donating: CH3, OCH3 and electron withdrawing: Br). We showed that by changing the substituent in the heterocyclic azo dye we change the power efficiency of the device. It should be mentioned that all presented data showed high potential of heterocyclic azo dyes for effective photovoltaic output. The studied heterocyclic azo dyes have higher photovoltaic parameters than those obtained for photovoltaic cell with 4-Diethoxyphenylsilylazobenzene.
关键词： Theoretical DFT calculations,Photovoltaic cell,Thin films,Heterocyclic azo dyes,Current density-voltage characteristics
更新于2025-09-23 15:19:57
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Dual-Activatable Cell Tracker for Controlled and Prolonged Single-Cell Labeling
摘要： Cell trackers are fluorescent chemical tools that facilitate imaging and tracking cells within live organisms. Despite their versatility, these dyes lack specificity, tend to leak outside of the cell and stain neighboring cells. Here, we report a dual activatable cell tracker for increased spatial and temporal staining control, especially for single-cell tracking. This probe overcomes the typical problems of current cell trackers: off-target staining, high background signal, and leakage from the intracellular medium. Staining with this dye is not cytotoxic and it can be used in sensitive primary cells. Moreover, this dye is resistant to harsh fixation and permeabilization conditions and allows for multi-wavelength studies with confocal microscopy and fluorescence-activated cell sorting. Using this cell tracker, we performed in vivo homing experiments in mice with primary splenocytes and tracked a single cell in a heterogenous, multicellular culture environment for over 20 h. These experiments, in addition to comparative proliferation studies with other cell trackers, demonstrated that the signal from this dye is retained in cells for over 72 h after photoactivation. We envision that this type of probes will facilitate the analysis of single-cell behavior and migration in cell culture and in vivo experiments.
关键词： fluorescent dyes,photoactivation,single-cell tracking,cell trackers,intracellular labeling
更新于2025-09-23 15:19:57