Luminescence properties of lanthanide tetrakis complexes as molecular light emitters

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 502, P. 215590 - 215590

Published: Dec. 21, 2023

Language: Английский

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Exploring Jahn-Teller distortions: a local vibrational mode perspective

Journal of Molecular Modeling, Journal Year: 2024, Volume and Issue: 30(4)

Published: March 13, 2024

Abstract The characterization of normal mode (CNM) procedure coupled with an adiabatic connection scheme (ACS) between local and vibrational modes, both being a part the Local Vibrational Mode theory developed in our group, can identify spectral changes as structural fingerprints that monitor symmetry alterations, such those caused by Jahn-Teller (JT) distortions. Employing PBE0/Def2-TZVP level theory, we investigated this proof-of-concept study hexaaquachromium cation case, $$[\text {Cr}{(\text {OH}_{2})}_{6}]^{3+}$$ [ Cr ( OH 2 ) 6 ] 3 + / {Cr}(\text {OH}_{2})_{6}]^{2+}$$ , commonly known example for JT distortion, followed more difficult ferrous ferric hexacyanide anion {Fe}{(\text {CN})}_{6}]^{4-}$$ Fe CN 4 - {CN})}_{6}]^{3-}$$ . We found cases CNM characteristic modes reflects delocalization consistent high ACS confirms breaking, evidenced separation axial equatorial group frequencies. As underlined Cremer-Kraka criterion covalent bonding, from to {OH}_{2})}_{6}]^{2+}$$ there is increase covalency whereas bonds shift toward electrostatic character. From observed without altering bond nature. Distinct $$\pi $$ π back-donation disparity could be confirmed comparison isolated $$\text {CN}^{-}$$ system. In summary, positions CNM/ACS protocol robust tool investigating less-explored distortions, paving way future applications. Graphical abstract relates breaking giving rise frequencies

Language: Английский

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Drug Property Optimization: Design, Synthesis, and Characterization of Novel Pharmaceutical Salts and Cocrystal-Salt of Lumefantrine

Molecular Pharmaceutics, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 13, 2025

Lumefantrine (LMF) is a low-solubility antimalarial drug that cures acute, uncomplicated malaria. It exerts its pharmacological effects against erythrocytic stages of Plasmodium spp. and prevents malaria pathogens from producing nucleic acid protein, thereby eliminating the parasites. Modifying structure through formation pharmaceutical cocrystal or salt presents an avenue which physicochemical properties can be optimized. In this work, we report design/synthesis solid-state characterization four new salts cocrystal-salt forms LMF; LMF-ADP salt, monoclinic space group P21/n; LMF-FUM cocrystal-salt, P21/c; LMF-TAR solvate LMF-SUC triclinic, P1̅ (ADP, dianion adipic acid; FUM, monoanion fumaric TAR, tartaric SUC, succinic acid). These obtained by solution as well mechanochemical cocrystallization methods. The multicomponent systems gain their stability hydrogen partial ionic bonding interactions (N-H···O, O-H···O, N+-H···O-, O-H+···O-) originating both dibutyl ammonium (N+-H) site alcohol hydroxyl (-OH) LMF toward carboxylate (-C(O-)═O) functional groups coformer anions. SCXRD indicates for LMF-ADP, LMF-TAR, complete transfer all carboxylic protons (H+) nitrogen, while LMF-FUM, one transferred (leaving hydrofumarate monoanion). Using salicylic acetylsalicylic acids coformers yielded coamorphous solids. Solid-state using powder X-ray diffraction (XRD) thermal techniques (DSC TGA) support confirm structures single-crystal XRD. present superior under standard conditions (40 ± 2 °C, 75 5% RH, 3 months) compared to amorphous samples other two salts. showed poor DSC/TGA, XRD patterns substantial change after 3-month test. Finally, calculated equilibrium solubilities indicate increase more than twofold LMF's solubility.

Language: Английский

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Synthesis, Spectroscopic Characterization, Molecular Docking, Quantum Chemical Studies, Topological Analysis (RDG, ELF, LOL), and Evalubation of Antibacterial and Anticancer Activities of Thiomorpholinium 4-Nitrobenzoate Crystalline Salt

Journal of Molecular Structure, Journal Year: 2025, Volume and Issue: unknown, P. 142438 - 142438

Published: April 1, 2025

Language: Английский

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Local vibrational mode theory meets graph theory: Complete and non-redundant local mode sets

Chemical Physics Letters, Journal Year: 2024, Volume and Issue: 849, P. 141416 - 141416

Published: June 12, 2024

This Frontiers Article introduces a unique perspective on the well-established concept of completeness in chemically meaningful set non-redundant local vibrational modes. By utilizing graph theory, we demonstrate how this naturally arises when Euler's theorem is fulfilled molecular graphs tree, cycle, and polyhedral types. significantly advances our understanding topology, leading to new interpretation for deriving such set. A key aspect mode theory decomposition normal modes into contributions, which provides powerful approach analyzing spectra. however requires complete modes, as demonstrated IR spectra both non-zwitterionic zwitterionic forms glycine, cubane perfluorocubane pair, Ar–benzene dimer. The mathematical put test by applying counting formulas sets series organic molecules with increasing complexity.

Language: Английский

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pH-dependent synthesis, characterization, crystal structures, and acetone sensing properties of two new 1D ladder-like cadmium(II) coordination polymers based on 4,4′-bipyridine and benzoate ligands

Polyhedron, Journal Year: 2024, Volume and Issue: 253, P. 116907 - 116907

Published: Feb. 20, 2024

Language: Английский

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Adaptive guided stochastic optimization: A novel approach for fitting the theoretical intensity parameters for lanthanide compounds

Optical Materials X, Journal Year: 2023, Volume and Issue: 20, P. 100275 - 100275

Published: Oct. 18, 2023

In this study, we introduce a state-of-the-art approach to enhance the fitting accuracy of theoretical intensity parameters in lanthanide spectroscopy. Lanthanide-based compounds play pivotal role wide range applications due their distinctive photophysical characteristics. Theoretical understanding and computational descriptions are essential for advancing these applications. The Judd-Ofelt theory stands as fundamental stone, offering insights into luminescence exhibited by compounds. Our methodology addresses procedure charge factors (g Simple Overlap Model) ligand effective polarizabilities (α′ Bond Model), quantities used determination (Ωλ). We propose Adaptive Guided Stochastic Optimization (AGSO), method that employs randomized initial points within predefined bounds each variable. By iteratively updating variable based on population statistics, AGSO systematically minimizes error function with respect experimental data. Extensive tests were conducted comparing well-established simulated annealing (SA) method. Remarkably, consistently outperformed SA, demonstrating its efficacy various Through AGSO, offer robust efficient tool accurate study lanthanide-based compounds, broad implications diverse

Language: Английский

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The Hydrogen‐Bond Continuum in the Salt/Cocrystal Systems of Quinoline and Chloro‐Nitrobenzoic Acids

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(68)

Published: Aug. 23, 2024

Abstract This study investigates the hydrogen‐bond geometry in six two‐component solid systems composed of quinoline and chloro‐nitrobenzoic acids. New X‐ray diffraction studies were conducted using both conventional independent‐atom model more recent Hirshfeld atom‐refinement method, with latter providing precise hydrogen‐atom positions. The can be divided into salts (the hydrogen atom transferred to nitrogen), cocrystals retained by acid), intermediate structures. Solid‐state NMR experiments corroborated diffraction‐derived H−N distances. DFT calculations, five functionals including hybrid B3LYP PBE0, showed varying energy profiles for bonds, notable differences across functionals. These calculations revealed different preferences salt or cocrystal structures, depending on functional used. Path‐integral molecular dynamics simulations incorporating nuclear quantum effects demonstrated significant delocalization, forming a continuum, provided average N−H distances excellent agreement experimental results. comprehensive theoretical approach highlights complexity multicomponent solids. emphasizes that classification is frequently inadequate, as often significantly delocalized bond. insight crucial understanding predicting behavior such pharmaceutical applications.

Language: Английский

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Crystals of Organic Acid–Base Complexes Defy the ΔpK_a Rule Under Compression

The Journal of Physical Chemistry C, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 27, 2024

Language: Английский

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Chemical Bond Overlap Descriptors From Multiconfiguration Wavefunctions

Journal of Computational Chemistry, Journal Year: 2024, Volume and Issue: 46(1)

Published: Nov. 28, 2024

The chemical bond is a fundamental concept in chemistry, and various models descriptors have evolved since the advent of quantum mechanics. This study extends overlap density its topological (OP/TOP) to multiconfigurational wavefunctions. We discuss comparative analysis OP/TOP using CASSCF DCD-CAS(2) wavefunctions for diverse range molecular systems, including X-O bonds X-OH (XH, Li, Na, H

Language: Английский

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