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Visible Light Driven Hydrogen Evolution by Molecular Nickel Catalysts with Time-Resolved Spectroscopic and DFT Insights
摘要： Hydrogen (H2) is a clean fuel that can potentially be a future solution for the storage of intermittent renewable energy. However, current H2 production is mainly dominated by the energy intensive steam reforming reaction, which consumes a fossil fuel, methane, and emits copious amounts of carbon dioxide as one of the byproducts. To address this challenge, we report a molecular catalyst that produces H2 from aqueous solutions, is composed of affordable, earth-abundant elements such as nickel, and has been incorporated into a system driven by visible light. Under optimized conditions, we observe a turnover number of 3880, among the best for photocatalytic H2 evolution with nickel complexes from water?methanol solutions. Through nanosecond transient absorption, electron paramagnetic resonance, and UV?vis spectroscopic measurements, and supported by density functional theory calculations, we report a detailed study of this photocatalytic H2 evolution cycle. We demonstrate that a one-electron reduced, predominantly ligand-centered, reactive Ni intermediate can be accessed under visible light irradiation using triethylamine as the sacrificial electron donor and reductive quencher of the initial photosensitizer excited state. In addition, the computational calculations suggest that the second coordination sphere ether arms can enhance the catalytic activity by promoting proton relay, similar to the mechanism among [FeFe] hydrogenases in nature. Our study can form the basis for future development of H2 evolution molecular catalysts that incorporate both ligand redox noninnocence and alternative second coordination sphere effects in artificial photosynthetic systems driven by visible light.
关键词： Proton relay,Second coordination sphere,DFT calculations,Time-resolved spectroscopy,Visible light photocatalysis,Hydrogen evolution,Molecular nickel catalysts
更新于2025-09-23 15:23:52
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A new non-centrosymmetric Chlorobismuthate(III) hybrid material: Crystal structure, optical properties and antibacterial study
摘要： As part of our interest in organic-inorganic metallate complexes, we had prepared a novel non-centrosymmetric chlorobismuthate (III) compound with the chemical formula (C6H7NCl)3 [BiCl6]$H2O, by slow evaporation method at room temperature. It was characterized by single crystal X-ray diffraction (SCXRD), X-ray powder diffraction (PXRD), spectroscopic measurements, thermal study, Hirshfeld surface analysis, DFT investigation, and antimicrobial activity. A preliminary SCXRD structural analysis revealed that the compound crystallizes in the Orthorhombic system (P212121 space group) with the following unit cell parameters a ? 7.3432 (1) ?, b ? 13.8257 (2) ? and c ? 28.2140 (5) ? with Z ? 4 and V ? 2864.42 (8) ?3. The examination of the structure shows that its atomic arrangement can be described as inorganic [BiCl6]3- units isolated from each other by the organic cations and the co-crystallized water molecules. The cohesion between these entities is performed via the NeH/Cl, NeH/O, CeH/O, CeH/Cl, and OeH/Cl hydrogen bonding interactions between the 4-dichloroanilinium cations, the [BiCl6]3- anions and water molecules forming a 3D network. The Hirshfeld surface calculation was conducted to investigate: intermolecular interactions, associated 2D ?ngerprint plots, and enrichment ratio, indicating the relative contribution of these interactions in the crystal structure quantitatively. Thermal analysis reveals the decomposition of the compound at 180 (cid:2)C. The quantum mechanical calculations such as geometry optimization, vibrational frequencies, simulated UVeVisible spectrum, FMOs analysis were made together with the experimental studies. Furthermore, the new synthesized compound was screened for its antibacterial activity. Results revealed that it has the most effective activity against all the tested bacteria compared to the amine alone and to the BiOCl.
关键词： Hirshfeld surface analysis,Hybrid material,DFT calculations,Hexachlorobismuthate(III),X-ray diffraction,Antimicrobial activity
更新于2025-09-23 15:23:52
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Bay-Linked Perylenediimides are Two Molecules in One: Insights from Ultrafast Spectroscopy, Temperature Dependence, and Time-Dependent Density Functional Theory Calculations
摘要： Bay-linked di-perylenediimide (di-PDI) molecules are finding increasing use in organic electronics due to their steric hindrance that 'twists' the two monomer units relative to one another, decreasing molecular aggregation. In this paper we explore the electronic spectroscopy and ultrafast dynamics of the singly-linked β-β-S-di-PDI (2,9'-di(undecan-5-yl)-2',9-di(undecan-6-yl)-[5,5'-bianthra[2,1,9-def:6,5,10-d'e'f']diisoquinolin]-1,1',3,3',8,8',10,10'(2H,2'H,9H,9'H)-octaone). Excitation-emission spectroscopy reveals two distinct emitting species, which are further characterized by time-dependent density functional theory (TD-DFT), demonstrating that the bay-linked PDI dimers exist in two geometrical conformations. These conformations are an 'open' geometry, where the two monomer sub-units are oriented nearly at right angles, giving them more J-like coupling, and a 'closed' geometry, in which the two monomer sub-units are nearly π-stacked, resulting in more H-like coupling. Given the extent of through-space and through-bond coupling, however, neither di-PDI conformer can be well-described simply in terms of independently-coupled monomers; instead, a full quantum chemistry description is required to understand the electronic structure of this molecule. Temperature-dependent experiments and the TD-DFT calculations indicate that the 'closed' conformer is ～70 meV more stable than the 'open' conformer, so that both conformers are important to the behavior of the molecule at room temperature and above. We use a combination of steady-state and femtosecond transient absorption and emission spectroscopies to globally fit the multiple electronic transitions underlying the spectra of both the 'closed' and 'open' conformers, which agree well with the TD-DFT calculations. The fact that di-PDI molecules are molecular species that adopt two distinct quasi-independent chemical identities has important ramifications for charge trapping and mobility in the organic electronic devices employing these materials.
关键词： TD-DFT calculations,ultrafast spectroscopy,conformational isomers,organic electronics,Bay-linked perylenediimides
更新于2025-09-23 15:22:29
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Syntheses, X-Ray Crystal Structures, Emission Properties and DFT Calculations of Monoprotonated Polypyridines
摘要： Monoprotonated compounds [(L)HPF6] were prepared by the reaction of (L = bpy, phen, dpphen, bqn and ppy) with concentrated HCl in water. Monoprotonated pyridine rings are hydrogen bonded intramolecularly to the adjacent pyridine ring and intermolecularly to the adjacent PF6- in compounds. These hydrogen bonds restrain the nonradiative decay to produce intense emission. Density functional theory was applied to interpret the planarity in compounds. The attachment of one proton to the nitrogen in [(dpphen)HPF6] and [(bqn)HPF6] leads to the strong emission in acetonitrile (Φ = 0.046 and 0.097, respectively). In particular, the attachment of one proton to the ppy nitrogen results in exhibiting a strong emission with a large quantum yield (Φ = 0.264).
关键词： crystal structure,DFT calculations,blue emission,monoprotonated polypyridine
更新于2025-09-23 15:22:29
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<i>l</i> -Stercobilin-HCl and <i>d</i> -Urobilin-HCl. Analysis of Their Chiroptical and Conformational Properties by VCD, ECD, CPL Experiments and MD, DFT Calculations
摘要： Vibrational circular dichroism (VCD) and IR spectra of dichloromethane solutions of l-stercobilin and d-urobilin hydrochlorides have been recorded in the mid-IR region. The spectra are best interpreted by combining molecular dynamics (MD) calculations and DFT calculations within the QM/MM ONIOM-type framework, and the combined predicted results are better and more informative than the more standard analysis provided by DFT calculations. The same approach also sheds light on the Cotton effect sign inversion of room temperature versus low temperature electronic CD (ECD) spectra of the same compounds in methanol-glycerol solution. Finally, circularly polarized luminescence (CPL) spectra for l-stercobilin in chloroform solution provide information on the excited state geometry of this molecule.
关键词： Vibrational circular dichroism,electronic CD,molecular dynamics,IR spectra,QM/MM ONIOM-type framework,Cotton effect,circularly polarized luminescence,DFT calculations
更新于2025-09-23 15:21:21
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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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Crystal structure, vibrational spectra, optical properties and density functional theory approach of a picrate salt based on substituted triphenylphosphinium
摘要： A new organic crystal, [BzTPP][PIC](1) ([BzTPP]+ = benzyl triphenylphosphinium, [PIC]- = picrate), has been grown by slow evaporation solution growth technique. Single crystal XRD reveals that it belongs to monoclinic system with P21/c. The two neighboring [BzTPP]+ cations from a dimer through C-H···π interaction while anions stack into a columnar structure through N···O, O···O and π···π interaction. The anions and cations form a column structure alternately in ···AC-AC-AC-AC··· sequence through C-H···O hydrogen bonds. The experimental vibrational bands (IR and Raman) have been discussed and assigned based on DFT calculations. The HOMO-LUMO energy gap explains the charge transfer interactions in the molecule. The thermal stability of the hybrid crystal was analyzed by TG-TDA-MS technique and revealed that the title crystal was stable up to 290 °C. The fluorescence spectra reveal three main emission peaks at 295, 388 and 543 nm upon excitation at 250 nm in solid state at room temperature. The energy of weak interactions in the molecule and nonlinear optical properties were studies using DFT calculations.
关键词： Substituted benzyl triphenylphosphinium picrate,Optical properties,vibrational spectra,Crystal structure,DFT calculations
更新于2025-09-23 15:21:01
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Thina??Film Morphology Improvement and Density Functional Theorya??Driven Findings for the Photovoltaic Perovskite MAPI/MAPSI
摘要： The morphology of thin films of the mixed MAPI / MAPSI material has been studied, revealing that the addition of toluene in the synthesis stage markedly improves the porosity problem of the manufactured films. The presence of crystalline domains of the two materials is verified, as reported by the X-ray diffraction patterns. The calculated band gap values from the diffuse reflectance measurements using the Tauc plots with the Kubelka-Munk transformation function confirm the presence of the two materials in the mixture. On the other hand, the results of the DFT-based computational calculations give answers to the true geometry that the SCN groups adopt within the MAPSI unit cell. The COHP analysis suggests that the most stable structure has an axial geometry for the SCN groups, which is confirmed by the analysis of non-covalent interactions (NCI), in which it is established that there is a greater number of hydrogen bond interactions for the same axial configuration, and results for Electron Localization Functions were shown (ELF), where it is found that there is indeed electron localization (at the level at which a bonding interaction is expected, ELF > 0.8) both for the SCN groups and the methyl-ammonium cations, in the same way as seen in the results of the NCI analyses.
关键词： hybrid perovskites,solar cells,thin films,SEM,DFT calculations
更新于2025-09-23 15:19:57
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Exploring optical properties of Gd doped zincblende GaN for novel optoelectronic applications (A DFT+U study)
摘要： In current research, we investigate optical properties of Gd doped zincblende GaN using Wien2K code, by employing DFT+U. We consider pure GaN and we dope various Gd concentrations 3.12%, 6.25% and 12.5% into the host GaN lattice while supercell size is kept fixed (1×2×2) for all cases. We elaborate and present a detailed comparison among optical and electronic properties of pure GaN with various Gd concentrations. Interaction of Gd and N atoms and localization of d and f states of dopant are remarked near Fermi level or maxima of valence band. In comparison to pure GaN, absorption spectra for 3.12% Gd concentration shows redshift but for highest Gd concentration (6.25% 12.5%), a blueshift in absorption spectrum is noted. Absorption is pronounced and enhanced in the UV region. Study of optical spectra for various optical properties suggest that Gd:GaN system is mostly suitable for UV optoelectronics. Results for optical properties have great similarity with the existing literature works. Our unprecedented and first ever reported results on optical properties of Gd:GaN system, direct future path of this material for its potential uses in UV optoelectronic, photonic, LEDs, UV sterilization application, photosensors, thermochromic solar cells and biochemical sensing industries.
关键词： optical properties,density of states,DFT calculations,gallium nitride (GaN),Gd doping
更新于2025-09-23 15:19:57
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Computational DFT calculations, photovoltaic properties and synthesis of (2R, 3S)-2, 3, 4-trihydroxybutoxy substituted phthalocyanines
摘要： In this study, 4-((2R, 3S)-2, 3, 4-trihydroxybutoxy) phthalonitrile was synthesized and characterized as starting material. This new starting material reacts with cobalt and copper metal salts to obtain metallophthalocyanine complexes. The electronic absorption of cobalt and copper phthalocyanine compounds in different concentrations of THF was investigated. In addition, the solubility and absorption of the compounds in different solvents were investigated. Density functional theory was also performed to support the relevant experimental results of the synthesized copper and cobalt center atomic compound. The photovoltaic performance of compounds was measured as current density–voltage (J–V).
关键词： DFT calculations,aggregation,photovoltaic,synthesis,Phthalocyanine
更新于2025-09-23 15:19:57