Journal of Molecular Structure最新文献

{"title":"Arylformylhydrazone triphenylphosphine Ni(II) complexes: synthesis, crystal structure, and efficient catalysis access to selenophenes","authors":"Penghui Ni ,&nbsp;Jing Tan ,&nbsp;Jiazhao Duan,&nbsp;Yuxing Tan,&nbsp;Wujiu Jiang","doi":"10.1016/j.molstruc.2025.144220","DOIUrl":"10.1016/j.molstruc.2025.144220","url":null,"abstract":"<div><div>Three arylformylhydrazone triphenylphosphine Ni(II) complexes [X-C₆H₄-(O)C=N-N=C(Me)-CH=C(O)-Ph]Ni(PPh₃) (<strong>Ni-1</strong>: X = H; <strong>Ni-2</strong>: X = 4-NO₂; <strong>Ni-3</strong>: X = 4-CH₃) were synthesized by microwave “one-pot” reaction with arylformylhydrazine, benzoylacetone, triphenylphosphine and Ni(II) chloride hexahydrate. These Ni(II) complexes were systematically characterized using IR, NMR, X-ray single-crystal diffraction, and TGA analysis. Structural determination confirmed that the fully deprotonated arylformylhydrazone acts as a dianionic tridentate (ONO) pincer ligand, coordinating to the center Ni(II) through its oxygen and nitrogen donor atoms. The Ni(II) adopts a distorted square planar coordination geometry, with the triphenylphosphine occupying the fourth coordination site. Importantly, these complexes demonstrated significant catalytic potential in the synthesis of selenophene derivatives from readily available terminal alkynes and elemental selenium. Exceptional catalytic efficiency was achieved at a low loading of 5 mol %.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144220"},"PeriodicalIF":4.7,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145269852","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":"Microwave-assisted synthesis of poly aromatic pyrimido[4,5-b]quinoline derivatives: Design, in silico pharmacokinetics, molecular dynamics simulation, molecular docking, POM analysis, and in vitro antimicrobial screening","authors":"Anand W. Mehta ,&nbsp;Ragini C. Patil ,&nbsp;Ajmal R. Bhat ,&nbsp;Mohammad Murwih Alidmat ,&nbsp;Shadid Alotaibi ,&nbsp;Taibi Ben Hadda ,&nbsp;Pranali Vijaykumar Kuthe ,&nbsp;Murugesan Sankaranarayanan ,&nbsp;Sujata Kundan ,&nbsp;Sumeer Ahmed ,&nbsp;Gabriela Tataringa","doi":"10.1016/j.molstruc.2025.144201","DOIUrl":"10.1016/j.molstruc.2025.144201","url":null,"abstract":"<div><div>A series of polyaromatic Pyrimido[4,5-b]quinoline derivatives <strong>4</strong>(<strong>a</strong>–<strong>j</strong>) were synthesized using a rapid and efficient microwave-assisted method. The targeted Compounds <strong>4</strong>(<strong>a</strong>–<strong>j</strong>) showed significant antibacterial and antifungal activity. Structural design was guided by rational drug design principles to enhance antimicrobial potential. The synthesized compounds were subjected to comprehensive in silico pharmacokinetic profiling (ADMET) to predict drug-likeness and bioavailability. Molecular docking studies were performed to assess binding interactions with key microbial targets, followed by molecular dynamics (MD) simulations to evaluate the stability of ligand–target complexes. POM (Petra/Osiris/Molinspiration) analysis further supported the biological relevance of the compounds. In vitro antimicrobial screening against selected bacterial and fungal strains revealed promising activity, with some derivatives demonstrating superior potency compared to standard drugs. The integration of green synthesis, computational modeling, and biological validation highlights these compounds as potential scaffolds for future antimicrobial drug development. Docking studies with S. aureus NDK (PDB ID: 3Q89) revealed strong molecular interactions. ADME, Lipinski, and Veber analyses predicted good bioavailability and safety. Molecular dynamics confirmed stability, highlighting this method's promise in green medicinal chemistry.Structural elucidation of the synthesized compounds was confirmed through FT-IR, ¹H NMR, ¹³C NMR, and ESI mass spectrometry</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144201"},"PeriodicalIF":4.7,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145270276","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":"Supramolecular assemblies in fumarato and succinato based Mn(II) and Ni(II) coordination solids involving pyridine and phenanthroline: Anticancer activities and theoretical studies","authors":"Trishnajyoti Baishya ,&nbsp;Mridul Boro ,&nbsp;Rosa M. Gomila ,&nbsp;Antonio Frontera ,&nbsp;Miquel Barcelo-Oliver ,&nbsp;Akalesh Kumar Verma ,&nbsp;Aminur Rahman ,&nbsp;Manjit K. Bhattacharyya","doi":"10.1016/j.molstruc.2025.144191","DOIUrl":"10.1016/j.molstruc.2025.144191","url":null,"abstract":"<div><div>Two new coordination compounds [Mn(3-Mepy)₂(µ-fum)(H₂O)₂]_n (<strong>1</strong>) and [Ni(phen)(succH_0.5)(H₂O)₃](NO₃)_0.5·2H₂O (<strong>2</strong>) (3-Mepy = 3-Methylpyridine, phen = 1,10-phenanthroline, fum = fumarate, succH = monoanion of succinic acid) were synthesized and characterized by SCXRD technique, electronic, FT-IR spectroscopy and thermogravimetric analysis (TGA). Polymer compound <strong>1</strong> exhibits two distinct polymeric chains with identical coordination environment, slightly differing in bond distances and bond angles surrounding the Mn(II) metal centres. The polymeric chains are interconnected via various hydrogen-bonding and π-stacking interactions forming the 2D supramolecular layered architecture. Crystal structure analysis of <strong>2</strong>, a Ni(II) monomer, reveals the enclathration of dual guest water molecules and nitrate anions in Ni(II) supramolecular host cavities. DFT (Density Functional Theory) was used to analyze the important non-covalent interactions present in the crystal structures of the compounds. Moreover, MEP (Molecular Electrostatic Potential) surface calculations, QTAIM (Quantum Theory of Atoms In Molecules), and NCI (Non-Covalent Interaction) plot analyses were also employed to rationalize and characterize these interactions. Computational studies confirm the strong stabilizing role of the network of H-bonds and π-stacking interactions in extending the polymeric chains into 2D supramolecular architectures in compound <strong>1</strong>. Similarly, for compound <strong>2</strong>, the QTAIM/NCI plot analysis of the H-bonded self-assembled dimer, reveals the contribution of O–H···O and C–H···O H-bonds. The <em>in vitro</em> cytotoxicity of compounds <strong>1</strong> and <strong>2</strong> were evaluated against Dalton’s lymphoma (DL) cancer cell line supported by Trypan blue assay and LDH (Lactate Dehydrogenase) leakage parameters. Apoptosis was investigated through dual fluorochrome staining and mitochondrial membrane potential (MMP) studies. Results demonstrated that both the compounds induced cytotoxicity and apoptosis in DL cells, highlighting their potential as therapeutic agents for further study.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144191"},"PeriodicalIF":4.7,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145270510","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":"Impact of substituents on bromination sites of (E)-1-[5-methyl-1-aryl-1H-1,2,3-triazol-4-yl]-3-arylprop-2-en-1-ones using N-bromosuccinimide: Synthesis and crystal structure elucidation","authors":"Bakr F. Abdel-Wahab ,&nbsp;Hanan A. Mohamed ,&nbsp;Mohamed S. Bekheit ,&nbsp;Benson M. Kariuki ,&nbsp;Gamal A. El-Hiti","doi":"10.1016/j.molstruc.2025.144172","DOIUrl":"10.1016/j.molstruc.2025.144172","url":null,"abstract":"<div><div>The bromination of (<em>E</em>)-1-[1-aryl-5-methyl-1<em>H</em>-1,2,3-triazol-4-yl]-3-arylprop-2-en-1-ones using <em>N</em>-bromosuccinimide (NBS) in polar protic solvents, such as methanol and ethanol, under acidic conditions was investigated. The bromination site was found to depend on the substituents in chalcones and the reaction conditions. Bromination of phenyl, 4-chlorophenyl, and 4-fluorophenyl-1<em>H</em>-1,2,3-triazolyl chalcones using NBS in methanol occurred at the aliphatic carbon-carbon double bond, producing the corresponding α‑methoxy bromide derivatives with a 90–95 % yield. In contrast, bromination of chalcones with a 4-methoxyphenyl group attached to the unsaturated center under similar conditions resulted in bromination on both the aliphatic double bond and <em>ortho</em> to the methoxy group on the aryl ring, producing the corresponding dibrominated triazoles in 85–90 % yields. When chalcones with a phenyl group on the triazole ring and a phenyl or 4-methoxyphenyl group on the unsaturated center were treated with NBS in ethanol, bromination occurred at the aliphatic double bond, yielding α-ethoxy bromide derivatives in 90–92 % yield. The crystal structures of the synthesized compounds have been determined to confirm their molecular structures, and Hirshfeld surfaces have been utilized to analyze intermolecular interactions within the crystals.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1350 ","pages":"Article 144172"},"PeriodicalIF":4.7,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145222503","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":"Exploring density functional theory to gain insight into the enolimine-ketoenamine tautomerism of dihydroxyl Schiff bases derived from 4-(diethylamino)salicylaldehyde and investigating their use as antidiabetes and antioxidant agents","authors":"Segun D. Oladipo ,&nbsp;Robert C. Luckay ,&nbsp;Abosede A. Badeji ,&nbsp;Kolawole A. Olofinsan","doi":"10.1016/j.molstruc.2025.144188","DOIUrl":"10.1016/j.molstruc.2025.144188","url":null,"abstract":"<div><div>Three dihydroxyl Schiff bases namely, 5-chloro-2-((4-(diethylamino)-2-hydroxybenzylidene)amino)phenol (<strong>DAC</strong>), 2-((4-(diethylamino)-2-hydroxybenzylidene)amino)-4-methylphenol (<strong>DAM</strong>) and 5-(diethylamino)-2-(((2-hydroxy-4-nitrophenyl)imino)methyl)phenol (<strong>DAN</strong>) were prepared by the condensation reaction between 4-(diethylamino)salicylaldehyde and amino-phenol derivatives. The compounds were elucidated using spectroscopic and elemental analysis techniques. Attempts to grow the crystal structure of <strong>DAC</strong> and <strong>DAM</strong> (enolimine form) at 60 –70 °C in methanol resulted in the formation of their ketoenamine form and are denoted as <strong>DAC′</strong> and <strong>DAM′</strong>. The molecular conformation of <strong>DAC′</strong> and <strong>DAM′</strong> revealed that the 4-diethylamino and the aminophenol phenyl rings are coplanar with the azomethine functional group as evident by C13—C8—C7—N1 dihedral angles of -178.78º (<strong>DAC′</strong>) and -174.99º (<strong>DAM′</strong>) as well as C1/C3—C6/C4—N1—C7 dihedral angles of 179.16º (<strong>DAC′</strong>) and 174.08º (<strong>DAM′</strong>). The longer bond length observed in C7—N1 as well as slightly shorter bond length observed in C9—O1 of <strong>DAC′</strong> and <strong>DAM′</strong> affirms their tautomeric properties related to <strong>DAC</strong> and <strong>DAM</strong>. We used Density functional theory (DFT) to investigate the structural, electronic, and tautomeric properties of <strong>DAM, DAC</strong>, and <strong>DAN</strong>. Notably, all the compounds exhibit single intramolecular hydrogen bonding that stabilizes its structure and facilitates proton transfer to yield its ketoenamine tautomer. However, the enamine tautomer is more stabilized due to the presence of dual intermolecular hydrogen bonding, hence supporting the crystallization of <strong>DAC′</strong> and <strong>DAM′</strong> over <strong>DAC</strong> and <strong>DAM</strong>. Compound <strong>DAN</strong> with the lowest energy bandgap of 6.158 eV is suggested to be the most reactive and polarizable molecule among the three compounds. Ferric reducing ability power (FRAP), 2,2-diphenyl-1-picrylhydrazyl (DPPH) as well as nitric oxide assays were explored to evaluate the antioxidant potential of the compounds. They exhibited good to moderate antioxidant activities i.e., <strong>DAN</strong> with IC₅₀ value of 0.51 μΜ scavenge nitric oxide radical better than quercetin with an IC₅₀ value of 149.96 μΜ. The evaluation of the antidiabetic potential was carried out using α-glucosidase and α-amylase inhibition assays. For the α-amylase assay, <strong>DAC</strong> with an IC₅₀ value of 0.13 μΜ exhibited almost equivalent capacity as acarbose with IC₅₀ value of 0.11 μΜ.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144188"},"PeriodicalIF":4.7,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145222871","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, structural analysis, and computational investigations of metronidazole and climbazole derivatives","authors":"Ebrar Nur Özkan ,&nbsp;Melek Gökmen Karakaya ,&nbsp;Özlem Gündoğdu Aytaç ,&nbsp;Ertan Şahin ,&nbsp;Abdullah Menzek","doi":"10.1016/j.molstruc.2025.144223","DOIUrl":"10.1016/j.molstruc.2025.144223","url":null,"abstract":"<div><div>This study details the synthesis, characterization, and in silico studies of two new molecules, 4-(3-(2-methyl-5-nitro-1<em>H</em>-imidazol-1-yl)propyl)phthalonitrile (<strong>5</strong>) and 1-(4-chloro-2-nitrophenoxy)-1-(1<em>H</em>-imidazol-1-yl)-3,3-dimethylbutan-2-one (<strong>7</strong>), which are derivatives of metronidazole and climbazole. The structural description of nitro-climbazole (<strong>7</strong>) was confirmed by single crystal X-ray analysis, which revealed the monoclinic crystal system with the space group P2₁/n. Complementary to the experimental findings, computational studies were carried out using Density Functional Theory (DFT) with Gaussian 09 software. These calculations, including geometry optimization and frequency analysis, were performed at the mPW1PW91/6-311G(d,p) level for molecule <strong>5</strong> and at the wb97xd/6-311G(d,p) level for molecule <strong>7</strong>. These analyses yielded important data regarding the stability and electronic structures of the molecules. Hirshfeld surface analysis based on CIF data obtained from the crystal structure <strong>7</strong> revealed intermolecular H∙∙∙H, O∙∙∙H, and Cl∙∙∙H contacts, demonstrating the contribution of these interactions to the stability of the crystal structure. Energy framework analyses elucidated the internal interactions of the structure by visualizing the cohesive forces within the crystal lattice. Frontier Molecular Orbital (FMO) analysis of molecules <strong>5</strong> and <strong>7</strong> revealed the distribution of their HOMO and LUMO orbitals, providing insights into their electronic behavior and reactivity potential. Furthermore, surface Electrostatic Potential (ESP) mapping identified electron-rich and electron-poor regions within the molecules, providing complementary information regarding potential biological interaction sites. Furthermore, their antibacterial and antifungal activities were investigated using in silico methods. This study, which combines experimental and theoretical approaches, comprehensively reveals the structural and electronic properties of the synthesized molecules.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144223"},"PeriodicalIF":4.7,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145270895","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":"Crystallographic, hirshfeld surface, and DFT analyses of a fluorine–bromine schiff base: Insights into structural features and MAO-A binding potential","authors":"Medine Karadag-Alpaslan ,&nbsp;Abdelmadjid Benmohammed ,&nbsp;Emine Berrin Poyraz ,&nbsp;Abdelkader Chouaih ,&nbsp;Necmi Dege ,&nbsp;Rachida Rahmani ,&nbsp;Youcef Megrouss ,&nbsp;Ayada Djafri","doi":"10.1016/j.molstruc.2025.144218","DOIUrl":"10.1016/j.molstruc.2025.144218","url":null,"abstract":"<div><div>In this study, a fluorine–bromine-substituted Schiff base compound, (E)-2-(((2-bromophenyl)imino)methyl)-6-fluorophenol (BFSB), was synthesized and structurally investigated using both experimental and theoretical approaches. The crystal structure, determined by single-crystal X-ray diffraction, revealed an orthorhombic system featuring a stabilizing intramolecular O–H···N hydrogen bond, complemented by halogen and dispersion interactions, as demonstrated through Hirshfeld surface and energy framework analyses. Computational studies employing Density Functional Theory (DFT) provided a reliable match with experimental geometry and offered insight into the molecule’s electronic structure and reactivity. Additionally, ADMET evaluations predicted favorable drug likeness and ease of synthesis despite some pharmacokinetic limitations. Molecular docking simulations were conducted against a range of protein targets to explore potential biological interactions, among which MAO-A showed the strongest affinity. Overall, the results underscore the relevance of combining crystallographic data with computational modeling to characterize multifunctional small molecules.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144218"},"PeriodicalIF":4.7,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145269855","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":"Bio-inspired one-dimensional cadmium halide stabilized by cytosinium: Structural, spectroscopic and theoretical investigations","authors":"Hesna Messalaoui ,&nbsp;Radhwane Takouachet ,&nbsp;Rim Benali-Cherif ,&nbsp;Wahiba Falek ,&nbsp;Lynda Golea ,&nbsp;Amel Marir ,&nbsp;Erwann Jeanneau ,&nbsp;Oumaima Ghodbane ,&nbsp;Nourredine Benali-Cherif","doi":"10.1016/j.molstruc.2025.144216","DOIUrl":"10.1016/j.molstruc.2025.144216","url":null,"abstract":"<div><div>Inspired by biomolecular recognition strategies, hybrid organic–inorganic cadmium halides are emerging as versatile materials for optoelectronic and dielectric applications, owing to their structural diversity and tunable physical properties. In this study, we report the synthesis and comprehensive characterization of a new cadmium chloride hybrid compound incorporating cytosinium cations; Bis(cytosinium) chloride trichlorocadmate hydrate (<strong>1</strong>). Single-crystal X-ray diffraction reveals a monoclinic structure composed of infinite [CdCl₃]⁻ chains interconnected by hydrogen bonding and electrostatic interactions. Spectroscopic analyses (UV–Vis and FTIR) confirm the optical transparency and vibrational features associated with the inorganic framework and organic cations, while SEM images show a well-defined needle-like morphology. Density functional theory calculations, <em>Hirshfeld</em> surface analysis and full interaction maps (FIM) provide further insight into the electronic structure and intermolecular interactions that stabilize the crystal lattice. This work highlights, for the first time, the integration of a nitrogenous nucleobase (cytosine) into a cadmium chloride hybrid system, offering a biomimetic pathway toward multifunctional crystalline materials. These results pave the way for the design of bioinspired halide frameworks with potential optoelectronic and dielectric functionalities.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144216"},"PeriodicalIF":4.7,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145222873","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":"Transition metal-directed architectures constructed from Anderson-type polyoxmatelates with different electrocatalytic hydrogen production performance in alkaline/seawater medium","authors":"Zhifei Zu,&nbsp;Zhihan Chang,&nbsp;Yaling Zhu,&nbsp;Juju Liang,&nbsp;Yuchu Lin,&nbsp;Haining Jiang,&nbsp;Xiuli Wang","doi":"10.1016/j.molstruc.2025.144217","DOIUrl":"10.1016/j.molstruc.2025.144217","url":null,"abstract":"<div><div>In this work, four new Anderson-type polyoxometalate-based metal-organic complexes (MOCs) with different central metals and various architectures, namely, {Cu₃(3-AT)₂[(TeMo₆O₂₄)](H₂O)₈}·6H₂O (<strong>1</strong>), {Co₃(3-AT)₂[(TeMo₆O₂₄)](H₂O)₈}·6H₂O (<strong>2</strong>), {Ni₃(3-AT)₂[(TeMo₆O₂₄)](H₂O)₈}·6H₂O (<strong>3</strong>), {Co₂(3-AT)₂[CrMo₆(OH)₅O₁₉](H₂O)₄}·7H₂O (<strong>4</strong>), were synthesized <em>via</em> hydrothermal or solvothermal methods. Their composition and structure were characterized by single-crystal X-ray diffraction, IR spectroscopy, powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The influence of the central metal ion on the structure was discussed. The electrocatalytic hydrogen evolution (HER) performances of the title complexes <strong>1–4</strong> modified cloth carbon electrodes (<strong>1–4</strong>/CC) in alkaline solution and simulated seawater condition were systematically studied. Notably, <strong>1/</strong>CC exhibited the lowest overpotential of 30.5 mV at the current density of 10 mA cm^-2 for HER in 1 M KOH. Furthermore, in simulated seawater, <strong>1</strong>/CC maintained a low overpotential of 34.8 mV at 10 mA cm^-2 for HER. The central metals and their coordination modes show a significant influence on their electrocatalytic performance. In addition, complex <strong>1</strong> also shows electrocatalytic activity towards the reduction reaction of the CO₂ (CO₂RR).</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144217"},"PeriodicalIF":4.7,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145223611","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, structure, and single-molecule magnet property of a mixed cyanide-oxo-bridged {FeIII2FeII2} complex featuring pentagonal bipyramidal Fe(II) centers","authors":"Fu-Xing Shen ,&nbsp;Kun-Hua Zhang ,&nbsp;Ao-Na Sun ,&nbsp;Jiong Yang ,&nbsp;Dong Shao","doi":"10.1016/j.molstruc.2025.144209","DOIUrl":"10.1016/j.molstruc.2025.144209","url":null,"abstract":"<div><div>The first cyanide-oxo-bridged tetranuclear {Fe^III₂Fe^II₂} complex, {[(Tp*)Fe^III(CN)₃][Fe^II(tdmmb)]O}₂·H₂O·3MeOH (<strong>Fe₄</strong>) (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate, tdmmb = 1,3,10,12-tetramethyl-1,2,11,12-tetra-aza[[3](2,6)pyridino[3](2,9)-1,10-phenanthrolinophan-2,10-diene) was prepared and structurally and magnetically characterized. Structural characterization of the tetranuclear molecule reveals an uncommon structure in which a pentagonal bipyramidal iron(II) sites (<em>S</em> = 2) are connected by one single O^2- bridge and further the Fe(II) dimer are bridged terminally by two tricyanoferrate(III) anions (<em>S</em> = 1/2). Magnetic susceptibility reveals antiferromagnetic coupling between Fe³⁺-CN-Fe²⁺ and Fe²⁺-O-Fe²⁺ centers, with the coupling constants of <em>J</em>_{Fe(III)/Fe(II)} = -4.8 cm⁻¹ and <em>J</em>_{Fe(II)/Fe(II)} = -11.2 cm⁻¹, to give an <em>S</em> = 5 ground state. This <strong>Fe₄</strong> molecule was found to exhibit the single-molecule magnet (SMM) behavior with the effective energy barrier <em>U</em>_eff = 38.2 K. Furthermore, an open magnetic hysteresis loop was observed for the compound. This work provides not only a rare cyanide-oxo mixed bridged complex but also suggest pentagonal bipyramidal Fe(II) building block represents a promising avenue to create high-performance single molecule magnets.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144209"},"PeriodicalIF":4.7,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145270270","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}