Transition Metal Chemistry最新文献

{"title":"Recent advances in quinoline-based fluorescent sensors for Zn2⁺ detection in environmental and biological samples (2011–2025)","authors":"Duraisamy Udhayakumari","doi":"10.1007/s11243-026-00794-3","DOIUrl":"10.1007/s11243-026-00794-3","url":null,"abstract":"<div><p>The selective detection of Zn²⁺ is critically important owing to its essential roles in biological regulation, neurological signaling, and environmental systems. Among diverse fluorophoric platforms, quinoline-based scaffolds have attracted considerable attention as efficient Zn²⁺ sensing platforms due to their rigid π-conjugated architecture, strong metal-binding nitrogen site, and excellent photostability. This review critically summarizes research advances from 2011 to 2025 on quinoline-derived fluorescent probes developed for selective Zn²⁺ detection. Key fluorescence response mechanisms, including chelation-enhanced fluorescence, suppression of photoinduced electron transfer, and modulation of intramolecular charge transfer that govern signal transduction upon Zn²⁺ coordination, are discussed. Performance parameters such as detection limits, binding stoichiometry, solvent compatibility, pH responsiveness, and reversibility are systematically compared. Recent developments highlighting water-soluble probes, ratiometric systems, and bioimaging-capable sensors are also addressed, demonstrating the growing relevance of quinoline fluorophores in live-cell imaging and biomedical diagnostics. Finally, current challenges and future perspectives are outlined, focusing on improving in vivo applicability, real-time sensing, and multifunctional probe design.</p></div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":"51 6","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149338288","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Molecular precursor engineering of Cu3 Clusters for Cu(I)-PCN photocatalysts enabling efficient CO2-to-Ethanol Conversion","authors":"Chun-Yu Liu,&nbsp;Bing Zhu,&nbsp;Liang Chen","doi":"10.1007/s11243-026-00793-4","DOIUrl":"10.1007/s11243-026-00793-4","url":null,"abstract":"<div><p>Photocatalytic conversion of CO₂ into multi-carbon products is severely constrained by the inefficient C–C coupling process, which remains a fundamental challenge in artificial photosynthesis. To address this limitation, we propose a molecular precursor engineering strategy based on a well-defined Cu₃ cluster precursor (Cu₃(PyCA)₃, PyCA = pyrazolate-4-carboxaldehyde) to fabricate the Cu₃@PCN photocatalyst, in which Cu species are highly dispersed on the PCN framework. The optimized catalyst exhibits exceptional performance in CO₂-to-C₂H₅OH conversion, achieving a production rate of 8.26 µmol·g^− 1·h^− 1 with 87.8% electron selectivity. Mechanistic investigations combining photoelectrochemical analysis and in situ spectroscopy elucidate that the Cu species derived from the Cu₃ molecular precursor not only as electron reservoirs for efficient charge accumulation but also as catalytic centres for stabilizing critical C₂ intermediates, thereby facilitating C–C coupling and promoting the formation of C₂ products. This work establishes a new paradigm for constructing Cu cluster precursor-derived Cu species and provides profound insights into the molecular-level design of advanced photocatalysts for sustainable CO₂ valorization into value-added multi-carbon products.</p><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div><p> Photocatalytic CO2 conversion to multi-carbon products is severely limited by inefficient C–C coupling, a fundamental challenge in artificial photosynthesis. Here we report a Cu cluster precursor-derived Cu3@PCN photocatalyst that delivers a C2H5OH production rate of 8.26 μmol·g-1·h-1 with 87.8% electron selectivity and outstanding stability, establishing cluster precursor engineering as a design principle for selective CO2 valorization to multi-carbon products.</p></div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":"51 6","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149338289","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A robust magnetically recoverable nickel nanocatalyst for α-olefination of nitriles using primary alcohols","authors":"Effat Vatankhah,&nbsp;Hossein Eshghi,&nbsp;Ali Shiri","doi":"10.1007/s11243-026-00792-5","DOIUrl":"10.1007/s11243-026-00792-5","url":null,"abstract":"<div><p>A novel nickel nanocatalyst with a magnetic core was designed and synthesized through a multi-step procedure. First, an iron oxide core was prepared and then coated with a silica layer (Fe₃O₄@SiO₂). The catalyst support was further functionalized using epichlorohydrin (EP) and ortho-phenylenediamine (OPDA) to form Fe₃O₄@SiO₂/EP/OPDAFinally, nickel was loaded onto the structure to obtain the finished catalyst (Fe₃O₄@SiO₂/EP/OPDA@Ni). Successful fabrication was confirmed by various characterization techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), vibrating-sample magnetometry (VSM), Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), Brunauer–Emmett–Teller (BET) analysis, and inductively coupled plasma optical emission spectrometry (ICP-OES).The nanocatalyst was effectively applied in the α-olefination of nitriles using primary alcohols, demonstrated by the reaction of a benzyl alcohol derivative with a benzyl cyanide derivative in refluxing toluene, using KO<i>t</i>-Bu as the base. The catalyst could be easily separated from the reaction mixture by applying an external magnetic field. It was also reusable, retaining its activity with only a minor loss in catalytic performance over at least five consecutive cycles. This method provides access to α,β-unsaturated nitriles, which are valuable building blocks in pharmaceuticals, polymers, and fine chemicals.</p></div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":"51 6","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149338098","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Anion-dependent synthesis, crystal structures and antibacterial activity of nickel(II) complexes derived from 1-(((2-(pyrrolidin-1-yl)ethyl)imino)methyl)naphthalen-2-ol","authors":"Zhong-Lu You,&nbsp;Zheng-Wei Wu,&nbsp;Yu-Qun Ye,&nbsp;Jin Mu,&nbsp;Ji-Ke Muji","doi":"10.1007/s11243-026-00791-6","DOIUrl":"10.1007/s11243-026-00791-6","url":null,"abstract":"<div><p>Four nickel(II) complexes derived from 1-(((2-(pyrrolidin-1-yl)ethyl)imino)methyl)naphthalen-2-ol (HL) were synthesized from nickel(II) acetate or nickel(II) nitrate in the absence or presence of ammonium thiocyanate or sodium azide, and their crystal structures and antibacterial activities were investigated. Reaction of HL with nickel(II) acetate afforded the centrosymmetric acetate/phenoxo-bridged trinuclear complex [Ni₃(µ₂-η¹:η¹-OAc)₂(µ₂-η²:η¹-OAc)₂L₂] (<b>1</b>), whereas the reactions with nickel(II) acetate/NH₄NCS, nickel(II) nitrate, and nickel(II) nitrate/NaN₃ gave the mononuclear complexes [NiL(NCS)] (<b>2</b>), [Ni(HL)₂](NO₃)₂ (<b>3</b>), and [NiL(N₃)] (<b>4</b>), respectively. Single crystal X-ray diffraction shows that the identity and coordination preference of the anion markedly influence the nuclearity and coordination geometry of the products, although the four syntheses differ in more than one experimental variable. Complexes <b>2</b>–<b>4</b> are square planar, while complex <b>1</b> contains six-coordinate terminal and central nickel centres. Antibacterial assays show strain-dependent activity: <b>3</b> has the lowest MIC against <i>B. subtilis</i> (2.3 µM), <b>1</b> is the most active against <i>S. aureus</i>, <i>E. coli</i> and <i>P. fluorescens</i>, and <b>2</b> and <b>4</b> show MIC values identical to those of HL. These results demonstrate a strong anion-dependent structure-modifying effect and indicate that the antibacterial response is compound- and strain-specific.</p></div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":"51 6","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149338097","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Pyrazole-based tetradentate transition metal complexes (Fe, Zn, Co, Cu): synthesis, characterization, catalytic performance, antimicrobial activity, and molecular docking studies","authors":"Ziloukha Ridal,&nbsp;Zakariae Abbaoui,&nbsp;Imane Oualdi,&nbsp;El Bekkaye Yousfi,&nbsp;Mohamed El KodadI,&nbsp;Chahrazad Belkhiri,&nbsp;Faiza Souna,&nbsp;Ilyesse Rahhou,&nbsp;Hicham Elmsellem,&nbsp;Rachid Touzani,&nbsp;Ismail Ozdemir,&nbsp;Abdelouahed Aouniti,&nbsp;Antar A. Abdelhamid,&nbsp;Ahmed A. Elhenawy,&nbsp;Hany M. Abd El-Lateef","doi":"10.1007/s11243-026-00790-7","DOIUrl":"10.1007/s11243-026-00790-7","url":null,"abstract":"<div><p>Tetradentate pyrazole–biphenyl ligands offer tunable coordination chemistry for catalysis and bioactivity, but cross-domain structure–activity relationships are underexplored. The synthesized tetraethyl 1,1’,1’’,1’’’-(((3,3’-dimethoxy-[1,1’-biphenyl]-4,4’-diyl)bis(azanetriyl)) tetrakis(methylene))tetrakis(5-methyl-1 H-pyrazole-3-carboxylate) (ligand 3; 31.12% yield) and prepared Fe(II), Zn(II), Co(II), and Cu(II) complexes. Compounds were characterized by FT-IR, UV–Vis, NMR, elemental analysis, magnetic susceptibility, molar conductivity. Catecholase-like activity was measured spectrophotometrically and analyzed by Michaelis–Menten kinetics for both in situ (ligand + metal salt) and isolated complexes. Antifungal (<i>Fusarium oxysporum f. sp. albedinis</i>) and antibacterial (<i>Staphylococcus aureus</i>,<i> Listeria monocytogenes</i>,<i> Salmonella sp.</i>,<i> and Escherichia coli</i>) activities were determined by disk diffusion and MIC assays. Molecular docking to DNA gyrase B (PDB: 6RK7) and ADMET predictions (SWISS ADME) were performed. Binuclear Fe complex <b>5</b> showed the highest catecholase efficiency (kcat/ K_m = 2.32 × 10⁷ M^<b>‒</b>¹ h⁻¹; V_max = 39.28 µmol L⁻¹ min⁻¹), and Fe complexes outperformed other metals. In situ mixtures were more active than isolated complexes. Ligand 3 exhibited the strongest antifungal effect (30.00% inhibition at 150 µg/disk); metalation reduced antifungal potency. Antibacterial effects were limited: Zn complex 6 (MIC = 50–100 mg/mL) and Co complex 7 (MIC = 50–100 mg/mL), Gram-negative preference) showed reproducible activity; Cu complex 8 was inactive. Docking scores did not correlate with biological activity. ADMET predicted bRo5 profiles, very low aqueous solubility (logS − 9.04 to − 15.18), poor GI absorption, lack of BBB penetration, and P-gp substrate status for dinuclear species. Binuclear Fe(II) centers in this tetradentate scaffold enable exceptional biomimetic catecholase catalysis, especially when formed in situ. Strong tetradentate chelation limits metal-release–mediated antimicrobial action, explaining reduced activity upon complexation and Cu inactivity. Moderate lipophilicity (Co 7) favored Gram-negative interaction. These results highlight the trade-off between chelation stability and biological availability and identify ligand 3 and selected metal complexes as leads for topical antifungal or Gram-negative antibacterial designs, contingent on addressing solubility and delivery limitations.</p></div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":"51 6","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149339113","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Baicalein- phenanthroline copper complex: synthesis, DNA/BSA binding, DFT studies, molecular dynamics simulations, cytotoxic, cell migration and invasive activity","authors":"Poonam Inamdar,&nbsp;Adityaraj Bhope,&nbsp;S. A. Arvindekar,&nbsp;Bhupesh S. Bhatt,&nbsp;Prashant Joshi,&nbsp;Gayatri Sasane,&nbsp;Aakanksha P. Patil,&nbsp;Neeta Rai,&nbsp;Avani Joshi","doi":"10.1007/s11243-026-00788-1","DOIUrl":"10.1007/s11243-026-00788-1","url":null,"abstract":"<div><p>A novel Copper(II) complex based on mixed ligands, the phytochemical compound baicalein and ancillary ligand 1,10-phenanthroline, [Cu(baic)(phen)NO₃], was synthesized and characterized by UV–visible, FTIR, EPR, and mass spectrometry. The analysis of the geometry was further analyzed using DFT, yielding a narrow HOMO–LUMO gap (2.63 eV), reflecting enhanced reactivity. The complex was found to have copper in the +2-oxidation state and to be penta-coordinated. Studies of DNA and BSA interaction were carried out using UV and FL spectroscopic assays revealed satisfactory binding affinity to DNA, with statistical values of <i>K</i>_b = 1.26 × 10⁴ M⁻¹ and <i>K</i>_sv = 2.71 × 10³ M ¹, and to BSA, with <i>K</i>_sv = 1.15×10⁵ M⁻¹, respectively. EtBr quenching studies gave us insight into the partial intercalative mode of complexation, and to correlate the same, we performed molecular docking studies. It revealed that the experimentally observed DNA-binding affinity, with a binding constant of (1.26 ± 0.10) × 10⁴ M⁻¹, was complemented by molecular docking against the 2D55 DNA duplex, which produced a binding score of −6.9 kcal/mol and a mixed, partially intercalative binding orientation; redocking of the native ligand yielded an RMSD of 0.376 Å, supporting the reliability of the docking protocol. This agreement was extended over 100 ns MD simulations, which confirmed stable, low-RMSD/RMSF binding of the complex to both DNA (2D55) and riboflavin kinase (1QS9), a metastasis-associated enzyme, thereby providing a plausible molecular rationale for the anti-metastatic phenotype observed in the cell-based assays. The complex exhibited moderate selective cytotoxicity against A549 cells (IC₅₀ = 115 µg/ml [201 µM]) relative to L929 cells (IC₅₀ = 458.21 µg/ml [800 µM]), with a ~4-fold increase in apoptosis and dose-dependent caspase−3 activation. To understand the [Cu(baic)(phen)NO₃]’s anti-metastasis activity, wound healing assays were performed, and they demonstrated 38% suppression of cell motility at 48 h, whereas Transwell invasion assays confirmed &gt;50% inhibition at the IC₅₀ concentration of the complex. The complex was found to be more effective as an anti-metastasis agent than as a cytotoxic agent.Taken together, the mutual reinforcement of spectroscopic, cellular, and computational evidence indicates that the complex behaves as a considerably more effective anti-metastatic than cytotoxic agent.</p></div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":"51 6","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149234778","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rosin-based gemini surfactant-controlled synthesis of NiO for dye adsorption","authors":"Xiaojun Tang,&nbsp;Yin Lou,&nbsp;Zhiguang Li,&nbsp;Change Zhou,&nbsp;Rong Li,&nbsp;Shaohai Fu","doi":"10.1007/s11243-026-00789-0","DOIUrl":"10.1007/s11243-026-00789-0","url":null,"abstract":"<div><p>To overcome the low dye adsorption efficiency of pristine nickel oxide (NiO) arising from its limited specific surface area and underdeveloped pore structure, a hierarchically porous nano-NiO adsorbent was constructed via a combined hydrothermal and low-temperature calcination process, using a rosin-based gemini surfactant (DA-n-CYS) as the structural modulator. The structure and morphology of the synthesized material were systematically characterized using Fourier transform infrared (FT-IR), X-ray diffraction(XRD), scanning electron microscopy(SEM), and Brunauer-Emmett-Teller(BET). The adsorption kinetics and thermodynamic mechanisms for methyl orange (MO) and methylene blue (MB) were comprehensively investigated. The directional growth of NiO crystals was demonstrated to be effectively induced by DA-n-CYS, which resulted in a meso-macroporous hierarchical structure with a specific surface area ranging from 90 to 110 m²/g. Superior dye adsorption performance was exhibited by the obtained material, and the adsorption process was well-described by the pseudo-second-order kinetic model and the Langmuir isotherm model, yielding remarkably high theoretical maximum adsorption capacities of 202.1 mg/g and 146.8 mg/g for MB and MO, respectively. Furthermore, a preferential adsorption selectivity towards the cationic dye (MB) was demonstrated by the nano-NiO, and a high removal efficiency of over 93% was maintained even after ten regeneration cycles. Consequently, a crucial theoretical basis is provided by this study for the structural design and industrial application of NiO-based adsorbents in dye wastewater treatment.</p></div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":"51 6","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149234779","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A multifunctional luminescent Zn(II)-MOF as recyclable sensor for detecting Fe3+ cation and 2,4,6-trinitrophenol (TNP) with high selectivity and sensitivity","authors":"Jie-Wei Rong,&nbsp;Yue Li,&nbsp;Guo-Quan Xie,&nbsp;Meng-Zu Ma,&nbsp;Mai Xu","doi":"10.1007/s11243-026-00785-4","DOIUrl":"10.1007/s11243-026-00785-4","url":null,"abstract":"<div><p>A new metal-organic framework [Zn(4-cptpy)(HCOO)(H₂O)]·DMF (<b>1</b>)(Hcptpy = 4-[4,2’:6’,4’’-terpyridine]-4’-yl-benzoic acid), has been solvothermally synthesized, and its structure has been characterized by single crystal X-ray diffraction, infrared spectroscopy, elemental analysis, X-ray powder diffraction and thermogravimetric analysis. <b>1</b> is composed of Zn(II) ions, 4-cptpy⁻ ligands, formate and coordination water molecules. Each Zn(II) ion is in a twisted <i>cis</i>-N₂O₄ octahedral environment and is connected with three ligands, and each ligand coordinates with three Zn(II) ions to form a hexagonal honeycomb with a 2D layered (6,3)-connected net. Two 2D porous nets are interlaced with each other to produce a 2-fold interpenetrated net. In addition, the fluorescent properties of <b>1</b> in various metal nitrate@DMF solutions and nitroaromatic compounds (NACs)@DMF solutions were studied. The results show that: <b>1</b> exhibits a highly sensitive and selective response to Fe³⁺ and 2,4,6-trinitrophenol (TNP) through fluorescence quenching effect, and it is expected to become a fluorescence sensor for Fe³⁺ and TNP. Finally, the possible fluorescence quenching mechanisms of Fe³⁺ and TNP detection are discussed: (a) photoinduced electron transfer (PET) and (b) fluorescence resonance energy transfer (FRET) through the HOMO-LUMO energy gap of density functional.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div><div><p>A new metal–organic framework based on 4-[4,2’:6’,4’’-terpyridine]-4’-yl-benzoic acid ligand was synthesized and structurally characterized in detail, and complex 1 is promising bifunctional fluorescent probe for highly sensitive and selective sensing Fe3+ ions and TNP through fluorescence quenching effect. The quenching mechanisms and recyclabilites of complex 1 were studied based on both experiments and calculation.</p></div></div></figure></div></div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":"51 6","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149234554","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Metal–hydrogen interactions in Li- and Sc-functionalized [3,3]paracyclophane: a density functional theory study of bonding and adsorption mechanisms","authors":"Ridha Ben Said,&nbsp;Youghourta Belhocine,&nbsp;Seyfeddine Rahali","doi":"10.1007/s11243-026-00786-3","DOIUrl":"10.1007/s11243-026-00786-3","url":null,"abstract":"<div><p>A density functional theory investigation was performed to elucidate the nature of metal–hydrogen interactions and hydrogen-storage behavior in Li- and Sc-functionalized [3]paracyclophane. Geometry optimizations show that Li and Sc preferentially bind above the benzene ring centers, with metal binding energies of − 0.683 and − 1.364 eV for the monometallic Li-PCP and Sc-PCP systems, respectively. For single H₂ adsorption, Li functionalization increases the adsorption energy to − 0.126 eV, with Li–H distances of 2.08–2.14 Å and only a slight H–H elongation from 0.74 to 0.75 Å, consistent with predominantly polarization-assisted electrostatic adsorption. Sc functionalization produces substantially stronger adsorption of − 0.344 eV, with Sc–H distances of 2.15–2.17 Å and an H–H bond length of 0.77 Å, indicating a stronger but still molecular interaction. Complementary EDA, PDOS, CDA/ECDA, and IGMH analyses show that Sc–H₂ binding involves significant electrostatic and polarization contributions together with donation-dominated orbital interaction and limited back-donation. Sequential adsorption calculations show that 2Li-PCP and 2Sc-PCP accommodate up to 8 and 10 H₂ molecules, respectively, within the loading range examined, corresponding to theoretical gravimetric capacities of 6.1 and 5.8 wt%. Thermodynamic analysis yields effective reversible capacities of 1.3 wt% for Li-PCP and 4.4 wt% for Sc-PCP, demonstrating the superior practical retention behavior of the Sc-functionalized system. Comparison with previously reported paracyclophane homologues confirms that the [3] framework provides an intermediate regime of metal stabilization and hydrogen binding. Overall, these results clarify how metal identity and bridge length govern molecular H₂ adsorption and reversible storage in functionalized paracyclophanes.</p></div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":"51 6","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149234552","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Strained Ruthenium(II) photosensitizers for light-induced apoptosis in non-small-cell lung cancer","authors":"Yi-Fang Zhong,&nbsp;Yuchen Li,&nbsp;Hong-Ze Zhang,&nbsp;Zitong Peng,&nbsp;Yujun He,&nbsp;Chaodong Zhang,&nbsp;Jincan Chen,&nbsp;Yongcun Wang,&nbsp;Lanmei Chen","doi":"10.1007/s11243-026-00787-2","DOIUrl":"10.1007/s11243-026-00787-2","url":null,"abstract":"<div><p>Two well-known strained ruthenium(II) complexes, [Ru(phen)(dmphen)₂](PF₆)₂ (<b>1</b>) and [Ru(phen)₂(dmphen)](PF₆)₂ (<b>2</b>), where phen = 1,10-phenanthroline, dmphen = 2,9-dimethyl-1,10-phenanthroline, were synthesized and their photo-induced anticancer activities were explored. Results showed that complex <b>1</b>, which possessed a bulkier configuration, exhibited potent phototherapeutic activity against the non-small-cell lung carcinoma cell line (A549), with an IC₅₀ of 1.1 µM and a phototoxicity index (PI) of 18.6 under white light irradiation. Mechanistic studies revealed that <b>1</b> underwent ligand dissociation, promoted reactive oxygen species (ROS) generation, and effectively triggered DNA damage response and cell cycle arrest, ultimately inducing apoptosis in A549 cells.</p></div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":"51 6","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149234553","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}