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Structure, Reactivity, Nonlinear Optical Properties and Vibrational Study of 5-Thioxo-1,4-thiazaolidin-3-one and 5-thioxo-1,4,2-thiazasilolidin-3-one (Silicon vs. Carbon). A DFT Study
摘要： The structures and nonlinear optical properties (NLO) of 5-thioxo-1,4-thiazaolidin-3-one(Rhodanine) and 5-thioxo-1,4,2-thiazasilolidin-3-one (silarhodanine) tautomers were studied in gas phase and in solutions using the B3LYP density functional theory and composite CBS-QB3 method. The global minimum at the B3LYP/6-31++G(d,p) and CBS-QB3 levels of theory is tautomer 5 in the gas phase and in solvents for rhodanine, and simiarly, tautomer 13 is the global minimum for silarhodanine. The interconversion among the tautomers is proceeded by an intramolecular proton transfer reaction. An identical solvent effects can be noted for rhodanine and silarhodanine tautomers. The activation barrier towards ring-opening processes (1→2, 9→10) decreases with the increasing dielectric constant of the solvent; on the other hand, the barrier of the ring-closure processes (2→3, 10→11) increases with the increasing dielectric constant. The tautomers are predicted to show significant NLO properties. Also, a number of correlations between the dipole moment and electron densities in bond critical points of the S3-C4 bond and interaction energy as well as vibrational frequencies at the transition states (TS2–3,TS10–11) were examined under different solvents. Finally, the investigation of the heavy atom substitution effects on the properties of silarhodanine is proven to be very weak under these conditions.
关键词： Vibrational assignments,Silarhodanine,Reactivity,Rhodanine,NLO,Ring-opening,Solvent effects
更新于2025-09-23 15:23:52
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A Simple Rhodanine-Based Fluorescent Sensor for Mercury and Copper: The recognition of Hg2+ in aqueous solution, and Hg2+/Cu2+ in organic solvent
摘要： Detection of copper and mercury attracts important in most environmental and biological systems. In this study, the simple probe 2-OxI-Rh containing rhodanine core was synthesized by a green approach and sensing properties were studied using colorimetric and fluorometric detection. The research indicated that the specific ion affinity for Hg2+ ions in aqua systems and the multi-ion affinity for Hg2+ and Cu2+ in organic solvent results in drastic color and spectral changes. According to the data obtained, while the peak intensity increases at 390 nm, the peak intensity decreased at 272 nm in the absorption spectrum of 2-OxI-Rh and an increase in fluorescence intensity of 2-OxI-Rh were observed in the presence of Hg2+ and Cu2+ ions. The binding ratio of 2-OxI-Rh to Hg2+ and Cu2+ were found to be 1:1 according to Job's plot experiments. The binding constants were calculated using the Benesi-Hildebrand equation and found to be 2.15×104 M?1 for Hg2+ and 1.21×104 M?1 for Cu2+. Based on these concentration dependent fluorescence changes, the limit of detection (LOD) values were also calculated and found to be 3.36 μM for Hg2+ and 2.31 μM for Cu2+, which is the range of copper that should be in the blood (11.8–23.6 μM). As a result of all these studies, we can understand that prove 2-OxI-Rh, which is non-toxic, is a good selective candidate turn-on sensor that can be used for Hg2+ and Cu2+ detection in different solvent systems.
关键词： oxindole,Rhodanine,colorimetric,turn-on sensor.,mercury,chemosensor,copper
更新于2025-09-23 15:23:52
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Enhancement in Photovoltaic Properties of <i>N</i> , <i>N</i> a??diethylaniline based Donor Materials by Bridging Core Modifications for Efficient Solar Cells
摘要： The increasing demand of energy expedited the development of efficient photovoltaic materials.Herein, five push-pull donor materials (D1-D5) having N,N-diethylaniline as donor moiety and rhodanine-3-acetic as acceptor group are designed to be used as donor molecules in organic solar cells (OSCs). The bridging core modification of recently synthesized MR3 molecule (reference R) has been made with different π-spacers namely thiazole (B1), thieno[3,2-b]thiophene (B2), thiazolo[5,4-d] thiazole (B3), 2-(thiophen-2-yl)thiophene (B4) and 5-(thiazol-5yl)thiazole (B5). The structure–property relationship is studied and influence of bridging core modifications on photovoltaic, photophysical and electronic properties of D1-D5 are calculated and compared with reference R.The DFT and TDDFT calculations have been performed for the estimation of frontier molecular orbital (FMO) analysis, density of states (DOS) graphs, reorganization energies of electron and hole, open circuit voltage, photophysical characteristics, transition density matrix (TDM) surfaces and charge transfer analysis.Designed molecules exhibit better and comparable optoelectronic properties than synthesized reference molecules. Among all investigated molecules, D5 is proven as best candidate for OSCs application due to its promising photovoltaic properties including lowest band gap (2.24 eV), small electron mobility (λe = 0.0056 eV), small hole mobility (λh = 0.0046 eV), low binding energy (Eb = 0.21 eV), highest λmax values 610.76 nm (in gas) 670.22 nm (in acetonitrile) and high open circuit voltage (Voc = 1.17 V) with respect to HOMOdonor–LUMOPC61BM. This theoretical framework demonstrates that bridging core modification is a simple and effective alternative strategy to achieve the desirable optoelectronic properties. Furthermore, conceptualized molecules are superior and thus are recommended to experimentalist for out-looking future developments of highly efficient solar cells.
关键词： Rhodanine-3-acetic acid,Solar cells,Photovoltaic properties,Bridging core modifications,Density functional theory (DFT),N,N-diethylaniline
更新于2025-09-23 15:21:01
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Design, Synthesis and Application of Imidazole-Based Organic Dyes in Dye Sensitized Solar Cells
摘要： Metal-free D–D–p–A type dyes (i.e., Car-Cy, Car-Rh, Dpa-Cy, and Dpa-Rh) were designed and synthesized for dye-sensitized solar cells (DSSCs). In the structure of the sensitized dyes, an imidazole ring is connected to a carbazole or diphenylamine moiety as a donor while cyanoacetic acid or rhodanine-3-acetic acid was introduced as an acceptor/anchor. The molecular structures of D–D–p–A type dyes were characterized using IR, NMR and MS spectral data. The optical, electrochemical, theoretical, light harvesting property, HOMO/LUMO levels, redox behavior, and photovoltaic properties of the synthesized dyes were evaluated. Among the fabricated photovoltaic devices based on the prepared dye, Dpa-Cy dye containing diphenylamine as a donor and cyanoacetic acid as an acceptor exhibited a high-power conversion efficiency of 1.70% with a short-circuit current density (JSC) of 4.48 mA cm?2, an open-circuit photovoltage (VOC) of 0.53 V and a fill factor of 72% under AM1.5 illumination (85 mW cm?2) in comparison with other dyes. Plane-wave calculations indicate that the dye binds reasonably strongly to the TiO2 surface, and the generated DOS picture shows an overlap of the molecular orbitals of the dye and the TiO2 bands. We conclude that the dyes have a promising role as sensitizers in DSSCs.
关键词： rhodanine-3-acetic acid,cyanoacetic acid,carbazole,DSSCs,diphenylamine
更新于2025-09-23 15:21:01
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Molecular Engineering of a New Organic Chromophore with D-π-A Architecture for Dye-Sensitized Solar Cells
摘要： Herein, we report design and synthesis of a new metal-free organic dye N1 derived from (Z)-3-(9-hexyl-9H-carbazol-3-yl)-2-(thiophen-2-yl) acrylonitrile scaffold. In this design, the electron rich carbazole unit is connected to rhodanine-3-acetic acid via cyano vinyl thiophene as π-spacer. Its molecular structure was confirmed by FTIR, NMR, Mass spectral and elemental analyses. The dye was subjected to optical and electrochemical studies in order to investigate their absorption/emission behaviour as well as HOMO/LUMO energies. The DFT studies were performed using Turbomole 7.1V software and the results indicated the existence of proper charge separation between its HOMO and LUMO energy levels.
关键词： DFT,Rhodanine-3-acetic acid,DSSC,FMO level,Carbazole
更新于2025-09-16 10:30:52
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Fabrication of rhodanine self-assembled monolayer thin films on copper: Solvent optimization and corrosion inhibition studies
摘要： Rhodanine self-assembled monolayer (Rh-SAM) films were prepared on copper specimens in different solvents. The assembled films were characterized using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FT-IR) and contact angle measurements. The inhibition efficiency of the films against copper corrosion in 3.5% NaCl solution was studied using electrochemical impedance spectroscopy (EIS), potantodynamic polarization (PP) and linear polarization resistance (LPR) techniques. It was found that very well-ordered and almost homogenously distributed Rh-SAM films were assembled on the copper surface. The appearance, electrochemical and physical properties of the films were depending on preparation conditions. The SAM films reduce greatly the corrosion rate of copper in 3.5% NaCl solution. Their protection ability depends on the type of solvent. The best film for this aim was obtained in 10 mM Rh after 24 h film formation time when methanol was used as solvent. The high corrosion protection ability of the films was assigned to the formation of a compact and protective structure over the copper surface. Assembling SAM films of this healthy compound and their application for corrosion protection has not been reported yet and is very original.
关键词： Copper,Rhodanine,Self-assembled monolayers,Corrosion inhibition
更新于2025-09-10 09:29:36