β-Diketonate Coordination: Vibrational Properties, Electronic Structure, Molecular Topology, and Intramolecular Interactions. Beryllium(II), Copper(II), and Lead(II) as Study Cases

The Journal of Physical Chemistry A, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 17, 2025

Nine metal complexes formed by three symmetric β-diketonates (viz., acetylacetonate (acac), 1,1,1,3,3,3-hexafluoro-acetylacetonate (hfac), and 2,2,6,6-tetramethylheptane-3,5-dionate (tmhd)) ions (with different coordination geometries, viz., BeII - tetrahedral, CuII square planar, PbII "swing" pyramidal) were investigated. The study combines structural analyses, vibrational spectroscopic techniques, quantum chemical calculations with the aim of bridging crystal structure, electronic molecular topology, far-infrared (FIR) characteristics. effect intramolecular interactions on structural, electronic, features is center this study. structure Be(tmhd)2 also reported discussed for first time. A complete review experimental IR spectra offered; discrepancies in assignments some peaks are revealed among published works. Anharmonic effects considered acac complexes; however, they negligible FIR modes. systematic comparison between computed experimentally measured data allowed us to design an inexpensive, yet efficient computational protocol investigate large polynuclear complexes.

Language: Английский

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Synthesis of Nonadentate Ligand Diethylene Glycol-Bis(3-Aminopropyl Ether)-N,N,N′,N′-Tetraacetic Acid DEGTA and Its Complexation Behavior toward Trivalent Lanthanides and Actinides

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 28, 2025

A new nonadentate ligand, DEGTA (diethylene glycol-bis(3-aminopropyl ether)-N,N,N′,N′-tetraacetic acid), from the polyaminopolycarboxylate family, was synthesized in a two-step reaction. The ligand's pH-dependent behavior (structure and pKa values) determined by nuclear magnetic resonance (NMR) spectroscopy. complexation ability of ligand toward trivalent lanthanides actinides studied time-resolved laser-induced fluorescence spectroscopy (TRLFS) using Eu(III) Cm(III) as representatives. For Eu(III), two species occurring at different pH values were observed corroborated concentration- pD-dependent NMR-titration series, viz. [EuH2(DEGTA)]+ [Eu(DEGTA)]−. latter is shown to be nine-coordinate, forming isostructural complexes with Sm(III) inferred TRLFS 2D NMR experiments, respectively. Since can seen consecutive derivative EDTA EGTA an elongated backbone, structures their calculated density functional theory (DFT) same aminoacetate binding motif proven Fourier-transform infrared (FT-IR) Upon comparison structure–property relationships (denticity chain length vs coordination geometry complex stability) one draw conclusions on DEGTA's particular, some generalizable trends properties within complexone series are discussed. Looking further ahead, this knowledge will help developing decontamination, decommissioning, decorporation strategies.

Language: Английский

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Assessment of the potential and application of Be12O12 nanocage for removal of ciprofloxacin from water employing density functional theory

Scientific Reports, Journal Year: 2025, Volume and Issue: 15(1)

Published: Jan. 6, 2025

The modern world is facing the issue of emerging pollutants for its sustainable development. We report a detailed study on abatement ciprofloxacin (CIP) by Be12O12 nanocage. Five different geometries nanocage with CIP i.e., Com-A, Com-B, Com-C, Com-D and Com-E are optimized. All complexes show chemisorption highest adsorption energies (Eads) − 39.86 kcal/mol followed Com-C without any structural change. O F atoms interacts strongly Be respectively. Charge transfer from to reveals strong interaction in all optimized complexes, maximum charge -0.199 e smallest bond lengths 1.52 Å 1.63 Å. decrease bandgap witnesses increase sensing ability adsorbent demonstrates between adsorbate supporting energies. positive values Hb ∇2ρb electrostatic nature which supported tools DFT. overall suggests an efficient, reusable purification water therefore can be used effectively eliminate antibiotics water.

Language: Английский

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Polarizable force fields for the structural and thermophysical properties of molten actinide chlorides

Journal of Nuclear Materials, Journal Year: 2025, Volume and Issue: unknown, P. 155822 - 155822

Published: April 1, 2025

Language: Английский

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Design of C24 fullerene-based sensors for gamma-butyrolactone detection as advanced tools for biomedical and pharmaceutical applications

Scientific Reports, Journal Year: 2025, Volume and Issue: 15(1)

Published: April 21, 2025

The detection of gamma-butyrolactone (GBL) is crucial in medicinal chemistry due to its role as a precursor gamma-hydroxybutyrate (GHB) and potential for misuse. This study presents sensor GBL based on fullerene C24 beryllium-, calcium-, magnesium-doped derivatives. Using density functional theory (DFT) time-dependent DFT (TD-DFT), we optimized the structures analyzed their electronic, optical, quantum properties. Key parameters such energy gaps, chemical reactivity, dipole moments, adsorption energies were evaluated. Among studied systems, (MgC23) exhibited highest pronounced red shift UV absorption upon complexation, an optimal balance recovery time. These results highlight MgC23 promising candidate sensitive efficient pharmaceutical forensic applications.

Language: Английский

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Systematic Improvement of Redox Potential Calculation of Fe(III)/Fe(II) Complexes Using a Three-Layer Micro-solvation Model

Physical Chemistry Chemical Physics, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Electrochemical transformations of metal ions in aqueous media are challenging to model accurately due the dynamic solvation structure surrounding at different charge states.

Language: Английский

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Discovering XSiGeN4: 2D Janus layers with ultra-high carrier mobility and pathways to future electronics

Surfaces and Interfaces, Journal Year: 2025, Volume and Issue: unknown, P. 106025 - 106025

Published: Feb. 1, 2025

Language: Английский

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Curcumin Electroanalysis at a Disposable Graphite Electrode

Biosensors, Journal Year: 2025, Volume and Issue: 15(3), P. 137 - 137

Published: Feb. 23, 2025

Curcumin (CU, turmeric), a polyphenolic phytochemical that is largely used as food spice, has benefits for human health, which have led to increased interest in its therapeutic applications and analysis from different matrices. The two guaiacol moieties of CU are responsible antioxidant properties allow voltammetric quantification. Cyclic differential pulse voltammetry (DPV) investigations at single-use pencil graphite electrode (PGE) emphasized complex pH-dependent processes, involving an equal number protons electrons. Theoretical calculations predicted folded geometry the β-diketone conformers, interact with PGE surface, exposing electroactive only one aromatic ring. Gibbs energy variations structures involved electro-oxidation theoretical electrochemical potential values were calculated. CU’s DPV cathodic peak intensity recorded HB-type 0.05 mol × L−1 H2SO4 varied linearly range 5.00 10−8–5.00 10−6 CU. method’s detection quantification limits 2.12 10−8 6.42 L−1, respectively. practical applicability developed method, successfully tested by assessment dietary supplements, provided recovery 99.28 ± 2.04%.

Language: Английский

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Analytical First Derivatives of the SCF Energy for the Conductor‐Like Polarizable Continuum Model With Non‐Static Radii

Journal of Computational Chemistry, Journal Year: 2025, Volume and Issue: 46(11)

Published: April 24, 2025

ABSTRACT Within this work, we present the derivation and implementation of analytical gradients for Gaussian‐switching (SwiG) Conductor‐like Polarizable Continuum Model (CPCM) with general nuclear coordinate‐dependent non‐static radii used creation van der Waals‐type cavities. This is done using recently presented dynamic adjustment continuum solvation ( Draco ) scheme. allows efficient geometry optimization reasonable numerical Hessian calculations. The derived gradient implemented in ORCA, therefore easily applicable. validated by comparing testing optimizations on a diverse test set, including small organic compounds, metal‐organic complexes, highly charged species. We additionally continuity potential energy surface an example where very strong changes occur. computational efficiency investigated.

Language: Английский

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Fast and Robust Modeling of Lanthanide and Actinide Complexes, Biomolecules, and Molecular Crystals with the Extended GFN-FF Model

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(41), P. 19364 - 19374

Published: Sept. 28, 2024

Lanthanides (Ln) and actinides (An) have recently become important tools in biomedical materials science. However, the development of computational methods able to describe such elements various environments has not kept up with pace field. Addressing this challenge, work introduces showcases an extension GFN-FF An alongside a reparameterization for Ln. This fills gap fast that are out-of-the-box applicable large f-element-containing systems thousands atoms. We discuss charge model covalent topology setup showcase through applications: Molecular dynamics simulations, optimization Ln-containing biomolecules, optimizations several periodic structures. With presented improvements, is powerful method routinely delivers robust accurate geometries Ln/An

Language: Английский

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