Journal of Molecular Structure最新文献

{"title":"Growth, structural characterization, enhanced NLO and optoelectronic properties of L-valine-based semi-organic crystals doped with CdCl2 and CuCl2","authors":"N. Sheen Kumar ,&nbsp;V. Vijimon Moni ,&nbsp;M. Gerald Arul Selvan ,&nbsp;B. Brailson Mansingh ,&nbsp;J.S. Binoj","doi":"10.1016/j.molstruc.2025.142820","DOIUrl":"10.1016/j.molstruc.2025.142820","url":null,"abstract":"<div><div>Individual crystals of biological and inorganic materials form the basis of modern science and technology, playing essential roles in sectors such as telecommunications and optoelectronics. Their specific structural and optical properties enhance optical modulation and device performance. Exploring these materials yields valuable knowledge for improving their suitability for future technologies. In this work, L-Valine-based semi-organic nonlinear optical (NLO) single crystals of L-Valine Cadmium Chloride (LVCC) and L-Valine Copper Chloride (LVCUC) were synthesized at ambient temperature using a slow evaporation process. Single crystal X-ray diffraction (XRD) investigation indicated that both crystals form in the monoclinic system. The FT-IR spectroscopy indicated coordination connections between L-Valine's amino and carboxyl groups and the metal ions, indicating complex formation. The reverse indentation size effect was more visible in LVCC than in LVCUC, indicating improved mechanical stability. The Kurtz-Perry powder technique confirmed that the second harmonic generation (SHG) efficiency of LVCC and LVCUC crystals was 2.57 and 2.43, respectively, when compared to that of conventional KDP crystals at varied molar ratios of 1:1. These findings suggest that L-Valine-based semi-organic NLO single crystals could be viable options for next-generation nonlinear optical systems and solar thermal devices. Furthermore, UV-Vis spectroscopy, dielectric research, and photoconductivity properties show tremendous promise as an alternate material for optoelectronic and photonic device applications.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1343 ","pages":"Article 142820"},"PeriodicalIF":4.0,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144204618","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A nonporous Cd(II) coordination polymer based on a new triangle imidazole‒carboxylic ligand for iodine adsorption and tetracyclic antibiotic detection","authors":"Xiao-Feng Huang,&nbsp;Jia-Hui Guo,&nbsp;Hui-Qi Xie,&nbsp;Jia-Hui Ni,&nbsp;Song-Liang Cai,&nbsp;Wei-Guang Zhang,&nbsp;Jun Fan,&nbsp;Sheng-Run Zheng","doi":"10.1016/j.molstruc.2025.142809","DOIUrl":"10.1016/j.molstruc.2025.142809","url":null,"abstract":"<div><div>A new Cd(II) coordination polymer (CP) based on (3,3′-(4-(4-(1H-imidazol-1-yl)phenyl)pyridine-2,6-diyl)dibenzoic acid (H₂IPPDA), namely, [Cd(IPPDA)(H₂O)]_n (Cd-IPPDA), was constructed. It exhibits a two-dimensional coordination network with a (4·8²) topology, and the 2D networks are packed into a 3D supramolecular framework via hydrogen bonds. Interestingly, Cd-IPPDA is capable of absorbing iodine molecules with a capacity of 3.4 g/g, although it has no significant pores in the framework. A mechanistic study revealed that the strong interactions between the iodine molecules and the framework cause the transformation from crystalline nonporous to porous amorphous structures. The resulting porous amorphous network, namely, a-Cd-IPPDA, still showed good iodine adsorption performance. It’s capacity was 3.0 g/g but adsorption kinetics significant increased, and could be reused for at least five cycles without a significant capacity decrease. In addition, the luminescence intensity of Cd-IPPDA was quenched by tetracyclines (TCs) in water; thus, this material can be used as a sensor for detecting TCs. The detection limits for OXY, CTE, and GEN are 0.51, 0.93, and 0.42 μmol/L, respectively. Moreover, the detection selectively is also good. The internal filtering effect and fluorescence resonance effect contribute to fluorescence quenching.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1343 ","pages":"Article 142809"},"PeriodicalIF":4.0,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144168125","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis, crystal structure, DNA interaction and anticancer activity of novel organotin cinnamate complexes","authors":"Jingni Wang ,&nbsp;Meifen Wei ,&nbsp;Zhiyu Pan ,&nbsp;Wen Zhong ,&nbsp;Shaofeng Chen ,&nbsp;Shijie Lin ,&nbsp;Wei Tian","doi":"10.1016/j.molstruc.2025.142814","DOIUrl":"10.1016/j.molstruc.2025.142814","url":null,"abstract":"<div><div>Four dibutyltin cinnamate complexes (<strong>1a</strong>∼<strong>4a</strong>) and four tricyclohexyltin cinnamate complexes (<strong>1b</strong>∼<strong>4b</strong>) were successfully synthesized and were characterized by various techniques including Fourier-transform infrared spectroscopy (FT-IR), multinuclear nuclear magnetic resonance (¹H, ¹³C, and ¹¹⁹Sn), and thermogravimetric analysis (TGA). The crystal structures of these eight complexes were thoroughly determined. Among them, the dibutyltin cinnamate complexes (<strong>1a</strong>∼<strong>4a</strong>) exhibited a tetranuclear trapezoidal structure, while the tricyclohexyltin cinnamate complexes (<strong>1b</strong>∼<strong>4b</strong>) displayed a monomeric structure. The supramolecular structures were observed in <strong>1b, 3a, 3b, 4a,</strong> and <strong>4b</strong> All complexes were tested for their inhibitory activity against human cell lines A549, HepG2, and MDA-MB-231. The results showed that the <strong>4a</strong> complex demonstrated the most significant inhibitory effect on HepG2 cells, with an IC₅₀ value of 0.08 ± 0.02 μM. Preliminary studies indicated that complex <strong>4a</strong> induced apoptosis in HepG2 cells, accompanied by G2 phase cell cycle arrest. The DNA binding activity of <strong>4a</strong> was investigated using ultraviolet-visible, fluorescence competition assays, and molecular docking, revealing that <strong>4a</strong> can effectively intercalate the DNA groove.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1343 ","pages":"Article 142814"},"PeriodicalIF":4.0,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144178131","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Modern screen-printed carbon electrodes modified with multilayered double transition metals carbides (MXenes) for Ascorbic Acid Detection in Urine and sweat samples","authors":"Cittrarasu Vetrivel ,&nbsp;Mani Durai ,&nbsp;Daochen Zhu ,&nbsp;Mathivanan Durai ,&nbsp;Shivakumara K N ,&nbsp;Ayman A. Ghfar ,&nbsp;M. Ajithkumar ,&nbsp;B. Subash ,&nbsp;Surya Chinnasamy ,&nbsp;Young Ho Ahn","doi":"10.1016/j.molstruc.2025.142738","DOIUrl":"10.1016/j.molstruc.2025.142738","url":null,"abstract":"<div><div>The detection of ascorbic acid (AA) plays a vital role in biotechnology, food analysis, and clinical diagnosis due to its numerous biological functions and importance as a nutritional marker. Here, a Multi-layered double transition metals carbides (DTMC)(Mo₂TiC₂T<em>_x</em>) MXene modified screen-printed carbon electrode as enzyme mimic electrode for the ascorbic acid detection. The surface-tailored, multi-layered Mo₂TiC₂Tₓ MXene on the exterior surface of a screen-printed carbon electrode (SPCE) significantly enhances the electrode's intrinsic properties, particularly in terms of conductivity and stability. MXenes, a family of 2D transition metal carbides and nitrides, have gained attention due to their remarkable electrochemical properties, and Mo₂TiC₂Tₓ MXene, in particular, exhibits outstanding conductivity, high surface area, and excellent electrocatalytic activity toward ascorbic acid. The multi-layered DTMC-modified SPCE electrode exhibits remarkable electrocatalytic efficiency for ascorbic acid oxidation. Fabricated with a multi-layered Mo₂TiC₂Tₓ MXene/SPCE composite, the electrode displayed exceptional performance, achieving a high sensitivity of 106.71 µA µM⁻¹ cm⁻², a wide linear detection range of 10–300 µM, a minimal detection limit of 0.082 µM, and a rapid response time of 2 s. This innovative electrode showcases excellent precision, selectivity, reproducibility, stability, and sensitivity. Such advancements underscore the potential of the multi-layered DTMC/SPCE system to enhance the accuracy and efficiency of ascorbic acid detection in applications like clinical diagnostics, food safety monitoring, and pharmaceutical analysis, representing a significant leap in sensor development. These features collectively make this electrode highly effective for practical applications in clinical diagnostics, food safety, and biotechnological research. This combination of DTMC /SPCE electrode is highly promising for accurate and efficient ascorbic acid detection in various practical applications.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1342 ","pages":"Article 142738"},"PeriodicalIF":4.0,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144170152","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Biological screening of thiadiazole-thiazolidinone based chalcone derivatives as potential bioactive molecules: An approach toward enzymatic inhibition","authors":"Shoaib Khan ,&nbsp;Rafaqat Hussain ,&nbsp;Tayyiaba Iqbal ,&nbsp;Kasim Sakran Abass ,&nbsp;Azam Hayat ,&nbsp;Waris Raza ,&nbsp;Mohammad Shahidul Islam ,&nbsp;Gaber E. Eldesoky","doi":"10.1016/j.molstruc.2025.142807","DOIUrl":"10.1016/j.molstruc.2025.142807","url":null,"abstract":"<div><div>In the current research work, we have synthesized and studied biological activity of fourteen different analogs of thiadiazole derived thiazolidinone based chalcone derivatives against two enzymes thymidine phosphorylase (TP) and urease. These newly synthesized analogs were structurally confirmed via characterization techniques; ¹H NMR, ¹³C NMR and HRMS. In vitro analysis revealed analogs 4, 5, 7 and 9 as most effective inhibitors of both TP and urease. Analog-5 with IC₅₀ value of 2.40 ± 0.10 <em>µ M</em> against TP and 2.30 ± 0.10 <em>µ M</em> against urease emerged as the lead compound of the series due to the presence of triflouromethyl moiety. 7-Deazaxanthine (IC₅₀ = 4.50 ± 0.10 <em>µ M</em>) and thiourea (IC₅₀ = 4.10 ± 0.10 <em>µ M</em>) were for the comparative analysis. Furthermore, molecular docking was conducted to investigate ligand-protein interactions of potent analogs. Drug-like properties of potent analogs of thiadiazole derived thiazolidinone based chalcone derivatives were also explored by conducting ADMET analysis. The novel compounds have demonstrated significant inhibitory potential against thymidine phosphorylase and urease as all results of comprehensive in vitro and <em>in silico</em> studies highlight their promise as efficient inhibitors of both enzymes.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1343 ","pages":"Article 142807"},"PeriodicalIF":4.0,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144204748","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis, spectroscopic, Hirshfeld surface analysis, electronic and Z-scan analysis of 4-bromobenzylidene picolinohydrazide (4BBPH): experimental and computational study","authors":"S.Arun Prabhu ,&nbsp;M. Saradha ,&nbsp;R. Sathyalakshmi ,&nbsp;M. Suresh ,&nbsp;M. Sathiyaraj","doi":"10.1016/j.molstruc.2025.142810","DOIUrl":"10.1016/j.molstruc.2025.142810","url":null,"abstract":"<div><div>Nonlinear optical (NLO) materials, particularly organic and semi-organic crystals, have garnered significant interest for their promising applications in superionic conductors, polarizers, fiber optic communications, photonics, and electronics. This study focuses on the synthesis, characterization, and NLO properties of 4-bromobenzylidene picolinohydrazide (4BBPH), a promising organic compound. The 4BBPH crystal was grown via slow solvent vaporization, and its structural properties were determined using single-crystal X-ray diffraction (XRD), revealing a monoclinic crystal structure with the space group Pc. The XRD results revealed single crystal lattice parameters such as <em>a</em> = 6.289 Å, <em>b</em> = 20.077 Å, and <em>c</em> = 15.051 Å, α = 90ᵒ, β = 98.33ᵒ, γ = 90ᵒ. The Z-scan method, used to measure third-order NLO characteristics, indicated a nonlinear refractive index of n₂=3.16 × 10⁻⁹ cm²/W and a nonlinear absorption coefficient β=1.12 × 10⁻⁴ cm/W, corresponding to a third-order nonlinear optical susceptibility χ³=4.39 × 10⁻⁶ esu. The DFT calculations are calculated by DFT/ 6-31++G(d,p) basis set. Theoretical studies using Density Functional Theory (DFT) and Time-Dependent DFT (TD-DFT) methods corroborated the experimental findings, providing insights into the molecular geometry, electronic properties, and vibrational modes of the 4BBPH molecule. Furthermore, the molecular electrostatic potential (MEP) and frontier molecular orbitals (FMOs) analysis revealed favorable sites for electrophilic and nucleophilic attack, reinforcing the compound's potential for further NLO optimization. Thermal stability was assessed through TGA-DSC, showing stability up to 245 °C. The findings highlight the promising NLO characteristics of 4BBPH and suggest its potential applications in nonlinear optical systems, particularly for optoelectronics and photonic devices.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1343 ","pages":"Article 142810"},"PeriodicalIF":4.0,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144204752","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis, characterization and geometrical optimization of azo dyes derived from the substituted pyrazole and benzothiazole amines coupled with 3-N, N‑diethyl amino phenol","authors":"RB Shakuntala ,&nbsp;J Keshavayya ,&nbsp;Hareesha Nagarajappa ,&nbsp;Y Surendra Naik ,&nbsp;Itte Pushpavathi","doi":"10.1016/j.molstruc.2025.142802","DOIUrl":"10.1016/j.molstruc.2025.142802","url":null,"abstract":"<div><div>This paper discusses the synthesis and characterization of four different azo compounds (<strong>1A-1D</strong>), which were obtained via diazotization of substituted pyrazole amines and benzothiazole with sodium nitrite, followed by coupling with diethyl amino phenol. The synthesized compounds (<strong>1A-1D</strong>) are characterized by IR, NMR, Mass, and UV–visible spectroscopy. The chemical reactive parameters of the title compounds were resolved by performing the DFT analysis through the B3LYP functional with 6–31 G (d, p) basis set and getting the optimized structures of the prepared azo compounds. Also, the energy gap between the molecular orbitals was calculated, which summarizes the reactivity and stability of the synthesized azo molecules. The electronic absorption spectra of the synthesized azo molecules were studied in various solvents and exhibited the maximum wavelength in the region 450–570 nm. Further, the drug potential of the synthesized azo compounds can be checked by carrying the various biological activities, such as anti-bacterial and <em>in silico</em> molecular docking. Moreover, the antibacterial activity of the synthesized compounds was tested using the agar well diffusion method, with Kanamycin as the standard drug; here, <strong>1A</strong> compound was found to possess moderate activity than the other remaining azo compounds (<strong>1B-1D</strong>). And also, <em>in silico</em> molecular docking was performed on these synthesized azo molecules by docking with specific target protein receptors and getting the binding affinity values for all the azo compounds.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1343 ","pages":"Article 142802"},"PeriodicalIF":4.0,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144184660","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Designing isoquinoline-based orange emissive Ir(III) complexes featuring different auxiliary ligands for solution-processed OLEDs","authors":"Xinru Wang ,&nbsp;Lixiang Li ,&nbsp;Jiangyu Zhu ,&nbsp;Yan Chen ,&nbsp;Jingqi Gong ,&nbsp;Song Guo ,&nbsp;Guohua Xie ,&nbsp;Yuanli Liu","doi":"10.1016/j.molstruc.2025.142812","DOIUrl":"10.1016/j.molstruc.2025.142812","url":null,"abstract":"<div><div>Two novel neutral and ionic phosphorescent iridium(III) complexes (Ir1 and Ir2) were successfully synthesized using 3-(6-methoxynaphthalen-2-yl)isoquinoline as the main ligand and 2-pyridinecarboxylic acid and bipyridine as auxiliary ligands. The two complexes exhibited bright orange and red phosphorescence emissions at 555 and 609 nm, respectively, demonstrating excellent solubility and stable photophysical properties, which is suitable to prepare organic light-emitting diodes (OLEDs) by solution method. Then, they were incorporated into the design and fabrication of OLEDs based on solution method. Only the orange device based on Ir1 showed the optimal electroluminescence performance with maximum brightness, current efficiency (CE), power efficiency (PE), and maximum external quantum efficiency (EQE) of 2330 cd/m², 20.33 cd/A, 3.87 lm/W, and 7.20 %, respectively. The findings highlight that fine-tuning the auxiliary ligands can significantly impact the emission properties, offering new opportunities for the design of highly efficient OLEDs.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1343 ","pages":"Article 142812"},"PeriodicalIF":4.0,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144168127","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemical sensing of nitrite by Cu and Zn based metal-organic frameworks – A green synthesis approach","authors":"Takumi Nagasaka ,&nbsp;Keerthiga Gopalram ,&nbsp;Nagashree K․L․ ,&nbsp;Srinivasadesikan Venkatesan","doi":"10.1016/j.molstruc.2025.142801","DOIUrl":"10.1016/j.molstruc.2025.142801","url":null,"abstract":"<div><div>Electrochemical sensing of nitrite ions is less time-consuming, more easily manageable, and inexpensive, compared to sophisticated instrumental techniques such as fluorescence. In this work, Copper (Cu) and Zinc (Zn) based Metal-organic frameworks (MOFs) were synthesized by ‘Green synthesis’ approach using water as a solvent and without heat treatment for the electrochemical sensing of <span><math><mrow><mi>N</mi><msubsup><mi>O</mi><mn>2</mn><mo>−</mo></msubsup></mrow></math></span> ions. The ‘Green synthesis’ method is advantageous in terms of being manageable, eco-friendly, safe, and inexpensive. The synthesized Cu BTC (BTC - Benzene-tricarboxylate) and ZIF-8 (ZIF- Zeolitic Imidazolate Framework) were investigated by XRD (X-ray diffraction), SEM (Scanning electron microscopy), FT-IR (Fourier transform infrared), and XPS (X-ray photoelectron spectroscopy) techniques. The Cu BTC had a thick bar-like morphology with aggregation while ZIF-8 had a rhombic dodecahedron morphology without aggregation. The Cu BTC and ZIF-8 were investigated for the detection of <span><math><mrow><mi>N</mi><msubsup><mi>O</mi><mn>2</mn><mo>−</mo></msubsup></mrow></math></span> ions by cyclic voltammetry (CV) and chronoamperometry. The limit of detection (LOD) of nitrite ions at the Cu BTC and ZIF-8 were 16.39 and 24.48 µM, respectively, which were superior to the stipulated quantity (65.2 µM) by the World Health Organization (WHO). Detection of <span><math><mrow><mi>N</mi><msubsup><mi>O</mi><mn>2</mn><mo>−</mo></msubsup></mrow></math></span> with the Cu BTC and ZIF-8 was successfully carried out in tap water suggesting their promising utility in real sample analysis. Density functional theory (DFT) studies were performed on Cu BTC, ZIF-8 and their coordinate complexes with nitrite ions, where Cu BTC confirmed the formation of more stable complex with <span><math><mrow><mi>N</mi><msubsup><mi>O</mi><mn>2</mn><mo>−</mo></msubsup></mrow></math></span> ions than ZIF-8.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1343 ","pages":"Article 142801"},"PeriodicalIF":4.0,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144204749","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Charge transfer properties of diarylamine-substituted phenyl osmium(II) compounds","authors":"Xiaofei Yang ,&nbsp;Shanting Liu ,&nbsp;Ya-Ping Ou ,&nbsp;Ming-Xing Zhang ,&nbsp;Sheng Hua Liu","doi":"10.1016/j.molstruc.2025.142702","DOIUrl":"10.1016/j.molstruc.2025.142702","url":null,"abstract":"<div><div>The localization or delocalization of charges and charge transfer characteristics in organometallic complexes, have consistently been significant areas of research. In this study, we investigate the charge distribution and transfer properties of four organometallic complexes containing Os(II) and triarylamine (NAr₃) ligands. These compounds display dual single-electron oxidation waves: the initial oxidation involves the NAr₂ unit and <em>π</em>(C₆H₃) segment, followed by a subsequent process primarily centered on Os(II) and <em>π</em>(C₆H₃). The oxidation potential and reversibility of these compounds within this series are contingent upon the positioning of the NAr₂ acceptor and the Os(II) donor on the benzene ring, along with their mutual interactions. Through ultraviolet-visible-near-infrared (UV–Vis-NIR) absorption spectroscopy, observable charge transfer metal-to-ligand charge transfer (MLCT) absorptions from ClOs to NAr₂⁺ and distinct absorption features of NAr₂^‧+ are identified. Notably, ligand-to-ligand charge transfer (LLCT) band emerges in the para isomer (Cl→NAr₂⁺) and in the metamer (<em>π</em>(PMe₃–ClOs−C₆H₃)→ NAr₂⁺). Furthermore, density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations are in agreement with the results obtained from electrochemical experiments, electronic properties, and optical behavior.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1342 ","pages":"Article 142702"},"PeriodicalIF":4.0,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144134129","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}