Polyhedron最新文献

{"title":"Synthesis, crystal structures and cytotoxic activity of new Cu(II) complexes based on podands with terminal 8-oxyquinolyl groups","authors":"Tamara A. Bazhenova ,&nbsp;Gennadiy V. Shilov ,&nbsp;Denis V. Korchagin ,&nbsp;Galina S. Tsebrikova ,&nbsp;Yulia R. Aleksandrova ,&nbsp;Dmitry V. Baulin ,&nbsp;Natalya S. Nikolaeva ,&nbsp;Mariya A. Lapshina ,&nbsp;Margarita E. Neganova ,&nbsp;Vladimir E. Baulin","doi":"10.1016/j.poly.2025.117607","DOIUrl":"10.1016/j.poly.2025.117607","url":null,"abstract":"<div><div>In this study, we present the synthesis of four novel Cu(II) complexes based on podands with terminal 8-oxyquinolyl groups and evaluation of their potential anticancer activity. The syntheses of ligands were achieved by a unified procedure in which 1,5-bis(8-oxyquinolyl)-3-oxapentane (L¹), 2,6-bis((8-oxyquinolyl)methyl)pyridine (L²), 1,8-bis(8-oxyquinolyl)-3,6-dioxaoctane (L³) were prepared by a one-step reaction of 2 equiv. of 8-hydroxyquinoline sodium salt with diethylene glycol ditosyl, 2,6-bis(tosylatemethyl)pyridine and triethylene glycol ditosyl, respectively, in good yields. The synthesis of copper(II) complexes [Cu₂L¹Br₂(<em>µ</em>-OCH₃)₂] (<strong>1</strong>), [Cu₂L¹Br₂(<em>µ</em>-OH)(<em>µ</em>-Br)] (<strong>2</strong>), [Cu₂L¹Br₂(<em>µ</em>-Br)₂]·CH₃CN (<strong>3</strong>), and [CuL²Br]Br (<strong>4</strong>) was performed through the reaction of CuBr₂ with L¹ and L² ligands under mild conditions. Single crystal X-ray diffraction analysis revealed that complexes <strong>1–3</strong> possessed binuclear structures, while complex <strong>4</strong> exhibited a mononuclear configuration. The <em>in vitro</em> anticancer activities of the four complexes were evaluated against four different cancer cell lines. The complexes exhibited higher activity compared to their respective free ligands, inducing cell growth inhibition and apoptosis in a concentration-dependent manner. Compounds <strong>3</strong> and <strong>4</strong> exhibited the most pronounced cytotoxic effect against the A549 cell line, with IC₅₀ values of 21.43 ± 0.20 and 30.67 ± 2.23 μM, respectively. It is also noteworthy that lower IC₅₀ values were observed for all compounds against Hek-293 cells of normal origin. A selectivity index of 2 was calculated for compound <strong>3</strong>. According to study of the effect on apoptosis, compounds <strong>1</strong> and <strong>4</strong> at the selected concentration after 24 h significantly increased the percentage of the apoptotic population. Confocal microscopy revealed that all the synthesized complexes penetrate into the cells and localize in the perinuclear space. It is suggested that aberrant glycolysis is one of the primary targets of the action of Cu(II) complexes <strong>1</strong>–<strong>4</strong>, and the detected cytotoxic activity appears to be related to the ability of <strong>1</strong>–<strong>4</strong> to alter the pathological mechanism of tumor cell metabolism.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"278 ","pages":"Article 117607"},"PeriodicalIF":2.4,"publicationDate":"2025-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154560","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Templated borates derived copper-based oxygen reduction reaction catalysts for zinc-air batteries","authors":"Xiang-Yu Huang,&nbsp;Chun-Yang Pan","doi":"10.1016/j.poly.2025.117608","DOIUrl":"10.1016/j.poly.2025.117608","url":null,"abstract":"<div><div>Two Cu-based templated borates, [Cu(o-phen)₂OAc]·[B₅O₆(OH)₄]·C₅H₅N (OAc⁻ = CH₃COO^–) (<strong>1</strong>) and [Cu(o-phen)₂Cl]·[B₅O₆(OH)₄]·H₂O (<strong>2</strong>), were synthesized with the o-phenanthroline (o-phen) ligand, and their structures were characterized by single crystal X-ray diffraction, PXRD, and FT-IR. The structural differences between the two compounds result from the distinct interactions between the complex template and the oxoboron cluster through hydrogen bonds (H-Bs). Templated borates were pyrolyzed to obtain high performance oxygen reduction reaction (ORR) catalysts. <strong>1-</strong>based catalyst showed better ORR activity and was used as cathode catalyst in zinc-air batteries (ZABs). Under high-temperature conditions, the metal complexes decompose into metal nanoparticles anchored on the <em>N</em>-doped carbon layer, which provides the primary active site for ORR catalysis. This research provides an innovative approach for the synthesis of high-performance ORR catalysts.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"278 ","pages":"Article 117608"},"PeriodicalIF":2.4,"publicationDate":"2025-05-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144177538","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Valonia aegagropila-shaped manganese oxide with hybrid Battery-Supercapacitor behavior for lithium-ion storage","authors":"Han-Yu Zou ,&nbsp;Huan Yang ,&nbsp;Zhen-Dong Wei ,&nbsp;Qiao-Ming Liang ,&nbsp;Jing-Wen Sun ,&nbsp;Meng-Ting Li","doi":"10.1016/j.poly.2025.117605","DOIUrl":"10.1016/j.poly.2025.117605","url":null,"abstract":"<div><div>Manganese-based oxides exhibit diverse applications and demonstrate exceptional performance in the field of electrochemical energy storage and conversion. However, the utilization of transition metal oxides as anode electrode materials in lithium-ion batteries faces several challenges, including inadequate cycling stability and poor conductivity. To address these issues, a unique nanostructured single-metal oxide, specifically manganese oxide with valonia aegagropila-shaped morphology, was achieved using a uniform thermal decomposition approach. The valonia aegagropila-shaped Mn₂O₃ anode material exhibits remarkable discharge specific capacity at low current densities, with an initial discharge specific capacity reaching up to 1280 mA h g⁻¹ and maintaining a consistent specific capacity of approximately 830 mA h g⁻¹. During this process, reversible oxidation–reduction reactions of Mn³⁺ ions occur, thereby enhancing the stability of Mn₂O₃ anode. Moreover, the valonia aegagropila-shaped Mn₂O₃ anode exhibits a hybrid behavior of battery and supercapacitor according to the electrochemical kinetic analyses. This might open new avenues for the design of manganese-based oxides with various morphologies anode materials to achieve high-performance energy storage.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"278 ","pages":"Article 117605"},"PeriodicalIF":2.4,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144117089","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhancement of degradation of herbicide atrazine through efficient manganese-porphyrins: Mechanistic insights, degradation products, and toxicity assessment","authors":"Iasmin T. Resende ,&nbsp;Larissa P. Bento ,&nbsp;Elaine M. Souza-Fagundes ,&nbsp;Eduardo S. Neves ,&nbsp;Dayse C.S. Martins","doi":"10.1016/j.poly.2025.117588","DOIUrl":"10.1016/j.poly.2025.117588","url":null,"abstract":"<div><div>The herbicide atrazine (ATZ) is widely used in weed control, especially in Brazil. Its persistence and toxicity raise environmental and health concerns and may cause several problems. In this context, manganese porphyrins emerge as promising catalysts for ATZ degradation, mimicking the action of cytochrome P450. This study evaluated the catalytic potential of five manganese porphyrins in the degradation of ATZ under mild conditions. Different oxidants were tested, including Oxone®, H₂O₂, iodosylbenzene, and iodobenzene diacetate. The effect of axial ligands as cocatalysts was also investigated. The best results were obtained for third-generation porphyrins and the iodoarenes oxidants, achieving up to 85% of ATZ degradation, the best result for Mn-porphyrins so far. Axial ligands did not bring improvements to the catalytic systems while assessments with radical inhibitors indicated the participation of reactive species, such as Mn^V-oxo, ·OH, and ¹O₂. Mass spectrometry analysis confirmed the formation of the main ATZ metabolites, mostly desisopropylatrazine, and the formation of 6-acetamidoatrazine which is observed for the first time for manganese porphyrins catalyzed systems.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"278 ","pages":"Article 117588"},"PeriodicalIF":2.4,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144138443","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Influence of copper valence states on antiferromagnetic Behavior: A Comparative study of three Copper-based polyoxomolybdate hybrid compounds","authors":"Jia-Peng Cao ,&nbsp;Qianxiang Xu ,&nbsp;Yuanhang Ren,&nbsp;Hehua Hui,&nbsp;Jining Shang,&nbsp;Bin Yue,&nbsp;Heyong He","doi":"10.1016/j.poly.2025.117604","DOIUrl":"10.1016/j.poly.2025.117604","url":null,"abstract":"<div><div>Three Cu-based polyoxomolybdate coordination polymers, [Cu^I_xCu^II_1-x(mbpy)(H₂O)][Cu^II(mbpy)(H₂O)₂][Na(HPO₄)(H<em>_x</em>PO₄)-Mo₅O₁₅]·5·.5H₂O (<strong>1</strong>), Cu(mbpy)Mo₂O₇ (<strong>2</strong>) and [(Cu^II(mbpy))(Cu^I_yCu^II_1-y(mbpy))(H₂O)(H_yPO₄)]₂[H₃PMo^VI₁₀Mo^V₂O₄₀]·H₂O (<strong>3</strong>) (mbpy = 4,4′-dimethyl-2,2′-dipyridyl, 0 &lt; <em>x</em> &lt; 1, 0 &lt; <em>y</em> &lt; 1), have been hydrothermally synthesized. Single crystal X-ray diffraction analysis of compounds <strong>1</strong>–<strong>3</strong> indicates that three different types of polyoxomolybdate unit, namely Strandberg-type {P₂Mo₅}, dimeric {Mo₂} and Keggin-type {PMo₁₂}, are included, respectively. Compound <strong>1</strong> is constructed by Strandberg-type {P₂Mo₅} and Cu(mbpy) to form a dimeric unit. Compound <strong>2</strong> has a 1D nanorod-like structure connected by the simplest {Mo₂} unit. Compound <strong>3</strong> is an isolated structure consisting of a Keggin-type {PMo₁₂} and a {Cu₄} unit. BVS and XPS studies demonstrate that both Cu⁺ and Cu²⁺ coexist in compounds <strong>1</strong> and <strong>3</strong>, and magnetic measurement indicates the existence of anti-ferromagnetic interactions in compounds <strong>1</strong>–<strong>3</strong>. We proposed three possible magnetic modes, namely {Cu₄}, linear {Cu₂} and {Cu₄-Mo₂}, to explain the complex magnetic behavior and try to use both magnetic study and the structure analysis to probe the Cu(I) centers in the compounds.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"278 ","pages":"Article 117604"},"PeriodicalIF":2.4,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144105741","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Noncovalent intermolecular interactions between pyrazine and thiophene: Harnessing a luminescent ‘binuclear cadmium (II)’ coordination complex for the trace quantity detection of Fe3+ ion and modelling a smart device","authors":"Arka Patra ,&nbsp;Pubali Das ,&nbsp;Gurupada Bairy ,&nbsp;Nayim Sepay ,&nbsp;Suvendu Maity ,&nbsp;Suprava Bhunia ,&nbsp;Partha Pratim Ray ,&nbsp;Chittaranjan Sinha","doi":"10.1016/j.poly.2025.117602","DOIUrl":"10.1016/j.poly.2025.117602","url":null,"abstract":"<div><div>Detection of trace amount of analyte through a dual mode sensing method has an edge over solitary signalling method because of its precision and efficacy. On the other hand, in the modern era of energy crisis, alternate sustainable storage device manufacturing has become a regularity to provide a green platform and to diminish carbon footprints from earth. To learn these model, we have designed a soberly emissive binuclear cadmium (II) complex, <strong>{[Cd₂(tppz)(2,5-TDA)₂(H₂O)₄]₂.(2H₂O)}</strong> (<strong>C1</strong>) (tppz = tetra-2-pyridinylpyrazine; 2,5-TDA²⁻ = 2,5-thiophenedicarboxylate). The Single Crystal X-ray diffraction analysis of <strong>C1</strong> has validated its structural integrity and revealed notable noncovalent intermolecular interactions between the electron-accepting pyridinyl and the electron-donating thiophenyl rings, with a distance of 3.770 Å between two adjacent molecules. Consistent with the experimental data, the fluorogenic technique shows superior sensitivity for Fe³⁺ detection, with a Limit of Detection (LOD) of 84.6 nM, compared to the colorimetric method, which has a LOD of 3.57 µM. The optical band gap (3.57 eV) of the complex predominantly falls within the semiconducting range, making it particularly suitable for the development of a Schottky diode, which can serve as a viable approach to mitigate the energy crisis in the realm of contemporary sustainable research. An electrical conductivity of 2.60 × 10⁻⁴ Sm⁻¹, coupled with the visible remediation of iron (III) ions, underscores the potential application of the complex in the realm of materials.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"278 ","pages":"Article 117602"},"PeriodicalIF":2.4,"publicationDate":"2025-05-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144138445","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"NMR study of paramagnetic chemical shifts of [Dy(DTPA)]2− at various concentrations in solution","authors":"E.N. Zapolotsky ,&nbsp;I.P. Chuikov ,&nbsp;Jinsheng Zhang ,&nbsp;S.P. Babailov","doi":"10.1016/j.poly.2025.117603","DOIUrl":"10.1016/j.poly.2025.117603","url":null,"abstract":"<div><div>The [Dy(H₂O)_n(DTPA)]²⁻ complex was studied in aqueous solution by ¹H NMR at different temperatures and concentrations. It was experimentally found that the longitudinal relaxation rates of signals in the NMR spectra of the [Dy(H₂O)_n(DTPA)]²⁻ complex are sensitive to concentration changes. It was found that the Curie-spin contribution to the lanthanide-induced enhancement in the spin–spin relaxation rate is dominant in the region of high concentrations and low temperatures. The complex can be considered as a promising NMR/MRI probe and reagent for <em>in vitro</em> and in vivo determination of temperature in aqueous media, as well as for temperature control during in situ studies of exothermic or endothermic processes.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"278 ","pages":"Article 117603"},"PeriodicalIF":2.4,"publicationDate":"2025-05-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144105742","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Luminescent [(2-PBO)CuILP] complexes: Synthesis, crystal structures, properties, and TD-DFT calculation","authors":"Xin-Yu Wei ,&nbsp;Li Song ,&nbsp;Yu Chen ,&nbsp;Ying-Ying Zhang ,&nbsp;Yu-Xin Zhang ,&nbsp;Hao-Nan Hu ,&nbsp;Yong Zhang ,&nbsp;Xia-Qun Zeng ,&nbsp;Zhou-Hang Jiang ,&nbsp;Wen-Xiang Chai","doi":"10.1016/j.poly.2025.117601","DOIUrl":"10.1016/j.poly.2025.117601","url":null,"abstract":"<div><div>We report herein a series of new [(2-PBO)CuIL_P] type luminescent complexes <strong>1</strong>–<strong>6</strong> and their application in fluorescent VOCs detection. These CuI complexes (except <strong>1</strong> as CuBr) are constructed by a diimine ligand 2-PBO (2-(2′-pyridyl)-benzoxazole) and five P-containing ligands (L_P) PPh₃ (<strong>1</strong>–<strong>2</strong>), PPh₂Cy (<strong>3</strong>), o-Tol₃P (<strong>4</strong>), TXP24 (<strong>5</strong>), and TXP25 (<strong>6</strong>), where PPh₃ = triphenylphosphine, PPh₂Cy = 4-cyclohexyldiphenylphosphine, o-Tol₃P = 4-tri(o-tolyl)-phosphine, TXP24 = tris(2,4-xylyl)phosphine, and TXP25 = tris(2,5-xylyl)phosphine. All complexes exhibit isolated structures with tetrahedral CuIN₂P coordination. TD-DFT calculations assign their low-energy UV absorption band to a mixed (XL + ML)CT¹ transition from Cu-I fragment to 2-PBO, the similarly assigned (XL + ML)CT excited state is proposed as the source of photoluminescence (PL). The modification of phosphine ligands is found to have minimal impact on the PL properties of these materials. A thin-film sensor based on complex<!--> <strong>2</strong> <!-->was fabricated, achieving VOCs detection through remarkable PL enhancement and vapochromism behavior.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"277 ","pages":"Article 117601"},"PeriodicalIF":2.4,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144070190","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Palladium analogues as complementary of Cis-platin- a mini review","authors":"Arup Mandal","doi":"10.1016/j.poly.2025.117585","DOIUrl":"10.1016/j.poly.2025.117585","url":null,"abstract":"<div><div><em>Cis</em>-platin was the first discovered anticancer drug based on the transition metal complex. It showed its anticancer activities on various types of cancers such as head and neck, testicular, small-cell lung and non-small-cell lung, bladder, cervical and ovarian cancers. But due to some adverse effects, scientists developed some platinum analogues as second and third generation drugs for cancer treatment. Among them, some passed clinical trials and some failed. Then non platinum complexes were also introduced with effective anticancer properties. Lot of research has been done on Iron, Ruthenium, Rhodium analogues. In this review, immense bio-activity of Palladium Complexes has been discussed and tried to demonstrate that Palladium complexes and its derivatives may also function as alternatives of <em>Cis</em>-platin.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"277 ","pages":"Article 117585"},"PeriodicalIF":2.4,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144072383","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Corrigendum to “Exploring the chemistry of divalent P(I) compounds: an insight from theory” [Polyhedron 276 (2025) 117561]","authors":"Bijoy Ghosh ,&nbsp;Sanchaita Rajkhowa ,&nbsp;Bitupon Borthakur","doi":"10.1016/j.poly.2025.117586","DOIUrl":"10.1016/j.poly.2025.117586","url":null,"abstract":"","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"277 ","pages":"Article 117586"},"PeriodicalIF":2.4,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144169461","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}