Inorganic Chemistry Frontiers最新文献_第8页

Design of bifunctional pyridinophane ligands as Mn MRI agents for diagnostic imaging of Alzheimer's disease 双功能吡啶配体用于阿尔茨海默病诊断成像的Mn MRI试剂设计

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2026-09-09 DOI: 10.1039/d6qi01745b

Tarek El Sayed,Akhil Patel,Jennifer A Salaiza,Husna Azhakath Valappil,Liviu M. Mirica,Kerui Xu,Shreyan Majumdar,Brad Sutton

{"title":"Design of bifunctional pyridinophane ligands as Mn MRI agents for diagnostic imaging of Alzheimer's disease","authors":"Tarek El Sayed,Akhil Patel,Jennifer A Salaiza,Husna Azhakath Valappil,Liviu M. Mirica,Kerui Xu,Shreyan Majumdar,Brad Sutton","doi":"10.1039/d6qi01745b","DOIUrl":"https://doi.org/10.1039/d6qi01745b","url":null,"abstract":"Alzheimer's disease (AD) is a progressive neurodegenerative disorder whose prevalence is rising with the aging of the global population. Among the proposed pathological hallmarks, the amyloid-beta (Aβ) peptide aggregates and soluble Aβ oligomers are established biomarkers and remain valuable diagnostic targets. While positron emission tomography (PET) imaging agents dominate AD diagnostic imaging, there are no FDA-approved MRI agents for AD. Herein, we report five bifunctional chelators built on the 2,11-diaza[3.3](2,6)pyridinophane framework, and which were evaluated as chelators for Mn 2+ -based MRI contrast agents. Based on in vitro studies, including thermodynamic stability and kinetic inertness measurements, T1 relaxivity and 17O transverse relaxivity measurements to extract hydration numbers and water-exchange parameters, we obtained a clear structure-activity correlation for the corresponding bifunctional chelators: anionic picolinate and acetate arms increase thermodynamic stability and kinetic inertness, while the benzothiazolyl-phenol arm accelerates water exchange. Importantly, a high hydration number alone is insufficient, as a rapid water exchange is also needed for an appreciable contrast. Moreover, we show both the bifunctional chelators and their Mn2+ complexes exhibit appreciable affinity for Aβ aggregates, both in vitro and in 5xFAD mouse brain sections. [Mn(TE-8)], the most kinetically inert complex with favorable relaxivity, log D, and Aβ affinity, was advanced to in vivo MRI studies. Unlike MnCl2, which accumulates non-specifically, [Mn(TE-8)] cleared through renal and hepatobiliary routes and produced measurable brain contrast enhancement. Together, these results establish the diazapyridinophane scaffold as a viable first generation platform for blood-brain-barrier-permeable Mn2+ MRI contrast agents.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"10 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148909065","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Ligand-Modulated CuI Cubane Clusters for Circularly Polarized Luminescence and Polarization-Dependent X-ray Scintillation 圆偏振发光的配体调制CuI立方体簇和偏振相关的x射线闪烁

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2026-09-08 DOI: 10.1039/d6qi01494a

Xueqian Wu,Xiaodong Gu,Jingwen Chen,Minghui Zhang,Kang Zhou,Feng Xu,Xiuze Hei

{"title":"Ligand-Modulated CuI Cubane Clusters for Circularly Polarized Luminescence and Polarization-Dependent X-ray Scintillation","authors":"Xueqian Wu,Xiaodong Gu,Jingwen Chen,Minghui Zhang,Kang Zhou,Feng Xu,Xiuze Hei","doi":"10.1039/d6qi01494a","DOIUrl":"https://doi.org/10.1039/d6qi01494a","url":null,"abstract":"Chiral copper(I) iodide hybrids are promising candidates for circularly polarized luminescence (CPL) and multifunctional radiation-responsive photonics, yet understanding how subtle ligand variations regulate the chiroptical response of Cu4I4 cluster emitters remains challenging. Herein, three pairs of zero-dimensional chiral Cu4I4L4 cubane-like clusters were constructed using structurally related enantiopure amine ligands. The structurally related series reveals that small changes in ligand structure modulate Cu···Cu distances, chiral core distortion, and excited-state structural relaxation without changing the cluster-centered emissive nature. Among them, S-1 combines pronounced ground-state chiral distortion with reduced excited-state structural reorganization, leading to efficient yellow-green emission, a PLQY of 96.9 ± 1.5%, and clear mirror-image CPL with |glum| up to 2.7 × 10−3. Benefiting from its high emission efficiency, S-1 also exhibits promising X-ray scintillation performance, with a light yield of 70.1 ± 1.8k photons MeV−1, a low detection limit of 127.3 nGy s−1, and a measurable polarization-dependent radioluminescence response. This work highlights the combined influence of ligand-controlled core distortion and excited-state rigidity on the development of multifunctional chiral Cu4I4 cluster materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"375 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148902521","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Strong Quadratic Optical Nonlinearity and Multi-Photon Absorption at Tricyanofuran-Functionalized Porphyrins 三氰呋喃功能化卟啉的强二次光学非线性和多光子吸收

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2026-09-08 DOI: 10.1039/d6qi00940a

Huan Wang,Pratima Sharma,Mahbod Morshedi,Eleni Notaras,Mahesh Kodikara,Yovan de Coene,Koen Clays,Chi Zhang,Mark G Humphrey

{"title":"Strong Quadratic Optical Nonlinearity and Multi-Photon Absorption at Tricyanofuran-Functionalized Porphyrins","authors":"Huan Wang,Pratima Sharma,Mahbod Morshedi,Eleni Notaras,Mahesh Kodikara,Yovan de Coene,Koen Clays,Chi Zhang,Mark G Humphrey","doi":"10.1039/d6qi00940a","DOIUrl":"https://doi.org/10.1039/d6qi00940a","url":null,"abstract":"The syntheses of (5-(4-N,N-diethylanilinoalkynyl donor)-15-(2-dicyanomethylene-3-cyano-4-methyl-2,5-dihydrofuran-containing acceptor)-10,20-diphenylporphyrinato)nickel(II) complexes, comprising metallated porphyrin cores unsymmetrically functionalized with strongly electron-donating dialkylanilino and strongly electron-withdrawing tricyanofuran (TCF) substituents, are reported. These dipolar complexes exhibit strong quadratic optical nonlinearity towards ns pulsed radiation, with hyper-Rayleigh scattering-derived first hyperpolarizabilities up to 3600 x 10^-30 esu (1064 nm) and 3800 x 10^-30 esu (1300 nm). They also demonstrate remarkable nonlinear absorption activity towards femtosecond pulsed radiation over the spectral range 800-2150 nm, with Z-scan-derived maximal values up to 11,000 GM (950 nm, two-photon absorption), 8400 x 10^-80 cm^6 s^2 photon^-2 (1250 nm, three-photon absorption), and 480 x 10^-110 cm^8 s^3 photon^-3 (1650 nm, four-photon absorption). The two-, three-, and four-photon absorption maxima are close to the corresponding multiples of intense linear absorption bands that time-dependent density functional theory assigns as admixtures of porphyrin-localized π* <- π and charge-transfer transitions.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"15 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148902429","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Reversible Supramolecular Dynamic Binder Enables Stress-Regulated SiO with Long-Term Stable Lithium Storage 可逆的超分子动态粘合剂使应力调节SiO具有长期稳定的锂存储

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2026-09-05 DOI: 10.1039/d6qi01338d

Wenyi Li,Yudai Huang,Wei Wang,Weihua Wang,Siyi Jing,Haozhe Liu,Yingde Huang,Zhouliang Tan

{"title":"Reversible Supramolecular Dynamic Binder Enables Stress-Regulated SiO with Long-Term Stable Lithium Storage","authors":"Wenyi Li,Yudai Huang,Wei Wang,Weihua Wang,Siyi Jing,Haozhe Liu,Yingde Huang,Zhouliang Tan","doi":"10.1039/d6qi01338d","DOIUrl":"https://doi.org/10.1039/d6qi01338d","url":null,"abstract":"Mechanical-chemical failure of SiO anodes, driven by severe volume expansion (≈200%) and the associated strain propagation during cycling, causes pronounced capacity decay and kinetic hysteresis, thereby limiting practical application.Herein, natural humic acid (HA), rich in polar functional groups such as hydroxymethyl (-CH 2 OH), carboxyl (-COOH) and phenolic hydroxyl (-C 6 H 5 -OH), is proposed as a supramolecular binder to enhance the mechano-chemical stability of micro-sized SiO anodes. Advanced structural characterization and theoretical calculation results show that HA, anchored onto the SiO surface, form an \"elastic buffer network\" through dense supramolecular interactions (multivalent hydrogen bonds) that can reversibly dissociate to dissipate stress, thereby preventing irreversible network fracture during SiO expansion. Moreover, the conjugated aromatic domains in HA promote interparticle electron transport via π-π stacking and their intrinsic carbon-like conductivity. As a result, the HA/SiO demonstrates remarkable cycling performance (The capacity decay rate is merely 0.05% per cycle over 1000 cycles at 1.9 A g -1 ) and excellent rate capability (907.9 mAh g -1 at 4 A g -1 ). Furthermore, the assembled PVDF/NCM811||HA/SiO full cell achieves a capacity retention of 76.6% after 350 cycles at 0.5 C, demonstrating its excellent practical viability. This work highlights supramolecular-chemistry-enabled binder design as an effective route toward highperformance and sustainable SiO anodes.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"40 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148893489","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Light-and Metal-Controlled Structural Reorganization in a Pd(II) Double-Walled Triangle Pd（II）双壁三角形中光与金属控制的结构重组

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2026-09-04 DOI: 10.1039/d6qi01683a

Sidharth Walia,Mangili Venkateswarulu,Grzegorz Markiewicz,Andrew Tarzia,Artur Ryszard Stefankiewicz

{"title":"Light-and Metal-Controlled Structural Reorganization in a Pd(II) Double-Walled Triangle","authors":"Sidharth Walia,Mangili Venkateswarulu,Grzegorz Markiewicz,Andrew Tarzia,Artur Ryszard Stefankiewicz","doi":"10.1039/d6qi01683a","DOIUrl":"https://doi.org/10.1039/d6qi01683a","url":null,"abstract":"Herein, we report an azobenzene-based pyridylimine ligand that self-assembles with Pd(II) ions into a well-defined double-walled triangular metallacycle, [Pd₃L₆]⁶⁺. The precise ligand design allows for selective Pd(II)-driven self-assembly via pyridyl coordination sites, leaving the flexible imine linkers non-coordinated under the conditions employed, thereby preserving the photoactivity of the azo unit within the assembly. Upon UV irradiation, the metallacycle undergoes trans→cis photoisomerization, leading to structural strain and partial disassembly into oligomeric species, while complete regeneration of the discrete [Pd₃L₆]⁶⁺ architecture occurs under ambient conditions. Notably, addition of Pd(II) to a photostationary mixture of cis/trans ligands results exclusively in the formation of the trans-based metallacycle, revealing an unexpected metal-ion-mediated cis→trans isomerization pathway. Kinetic analysis shows that Pd(II) significantly accelerates this isomerization compared to the free ligand, highlighting an active role of the metal center in isomer selection.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"32 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148893492","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Pnictogen Atom Transfer within a Transition Metal Coordination Sphere: Efficient Routes to -Phosphaazallene and -Arsaazallene Complexes 过渡金属配位球内的烟原原子转移：-磷氮杂烯和-砷氮杂烯配合物的有效途径

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2026-09-04 DOI: 10.1039/d6qi02076c

Ellis Joseph Mason,Tyler G. Saint-Denis,Matthew S. See,Qingchuan Chen,Gabor Balazs,Christophe Raynaud,Odile Eisenstein,Manfred Scheer,T. Don Tilley

{"title":"Pnictogen Atom Transfer within a Transition Metal Coordination Sphere: Efficient Routes to -Phosphaazallene and -Arsaazallene Complexes","authors":"Ellis Joseph Mason,Tyler G. Saint-Denis,Matthew S. See,Qingchuan Chen,Gabor Balazs,Christophe Raynaud,Odile Eisenstein,Manfred Scheer,T. Don Tilley","doi":"10.1039/d6qi02076c","DOIUrl":"https://doi.org/10.1039/d6qi02076c","url":null,"abstract":"A metal-mediated migration of pnictogen atoms Pn (Pn = P, As) to form phosphaazaallene and arsaazaallene complexes Cp*(CO)(IPr)Ru–Pn=C=N–Xyl results from clean reactions of the ruthenium carbene complex Cp*(XylNC)(IPr)RuCl (1, XylNC = 2,6-dimethylphenyl isocyanide; IPr = 1,3-bis(Dipp)-imidazol-2-ylidene; Dipp = 2,6-diisopropylphenyl) with sodium phosphaethynolate (NaOCP) or potassium arsaethynolate (KAsCO). First principles computations reveal that Pn (P and As)–atom migrations are associated with low free energy barriers (lower for As than P) and are exergonic. The low activation energy associated with migration is due to the ability of heavy Pn atoms to maintain an interaction with the metal and ligands during the migration pathway. These results contrast with alternative methods of phosphaazaallene syntheses reported previously, which involve migration of CO to an empty coordination site in 16-electron Cp*(IPr)Ru–PCO intermediates. Formation of phosphaazaallene complexes from this previous route required extensive heating and reaction times, and notably could not be extended to arsenic.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"9 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148893488","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Cation-Directed Spatial Engineering of Brønsted Acid Sites in Mordenite for Enhanced DME Carbonylation 丝光沸石中Brønsted酸位的阳离子定向空间工程增强二甲醚羰基化

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2026-09-03 DOI: 10.1039/d6qi01734g

Jiani Xu,Xinzhi Ding,Tongtong Meng,Svetlana Mintova,Shutao Xu,Zhengxing Qin

{"title":"Cation-Directed Spatial Engineering of Brønsted Acid Sites in Mordenite for Enhanced DME Carbonylation","authors":"Jiani Xu,Xinzhi Ding,Tongtong Meng,Svetlana Mintova,Shutao Xu,Zhengxing Qin","doi":"10.1039/d6qi01734g","DOIUrl":"https://doi.org/10.1039/d6qi01734g","url":null,"abstract":"Mordenite (MOR) is a promising catalyst for dimethyl ether (DME) carbonylation; however, its catalytic performance is constrained by the coexistence of beneficial 8-membered-ring (8-MR) and undesired 12-membered-ring (12-MR) Brønsted acid sites (BASs). Here, we develop a cation-directed selective dealumination strategy to spatially regulate the distribution of BASs in MOR. By introducing metal cations prior to mild oxalic acid treatment, framework Al species located in 8-MR channels are preferentially protected against extraction, whereas less protected 12-MR Al sites are selectively removed. Structural and spectroscopic analyses reveal that the effectiveness of cation protection is governed by the spatial compatibility between cations and local pore environments: monovalent cations (Na+, K+, and Cs+) effectively stabilize 8-MR framework Al species, whereas divalent cations (Zn2+ and Cu2+) exhibit limited protection due to their preferential accommodation in larger pore regions. As a result, K+-protected MOR achieves a twofold enhancement in DME conversion compared with untreated H-MOR, while sustaining a high methyl acetate (MA) selectivity of 98.4% during the stable catalytic period and exhibiting improved catalytic stability. These findings demonstrate that pore-environment-matched cation protection provides a versatile strategy for site-selective engineering of zeolite acidity, enabling the rational design of high-performance zeolite catalysts.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"17 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148877657","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A TREN-Based Tripodal Tris(germylene) as a Tridentate Ligand for Mononuclear Copper(I) Complexes 作为单核铜(I)配合物的三齿配体的trenn基三脚三（germylene）

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2026-09-03 DOI: 10.1039/d6qi01330a

Vishal Singh,Tanya Batra,Manjeet Kumar,Upendra Yadav,Vivek Kumar Singh,Hemant Kumar,Vinee Chandrakar,Senthilkumar Muthaiah,Gopalan Rajaraman,Nagendran Selvarajan

{"title":"A TREN-Based Tripodal Tris(germylene) as a Tridentate Ligand for Mononuclear Copper(I) Complexes","authors":"Vishal Singh,Tanya Batra,Manjeet Kumar,Upendra Yadav,Vivek Kumar Singh,Hemant Kumar,Vinee Chandrakar,Senthilkumar Muthaiah,Gopalan Rajaraman,Nagendran Selvarajan","doi":"10.1039/d6qi01330a","DOIUrl":"https://doi.org/10.1039/d6qi01330a","url":null,"abstract":"This study introduces a novel tripodal tris(germylene) 2, stabilized by TREN-tris(aminotroponimine) 1. Compound 2 was synthesized by treating the in situ-generated tri(lithium) salt of compound 1 with GeCl2·(1,4-dioxane). Interestingly, in its reactivity with various carboxylate salts, compound 2 exhibited divergent behavior. The reaction of 2 with sodium acetate and sodium pivalate yielded tris(germylene carboxylates), 3 and 4, respectively. However, 2’s reaction with sodium formate resulted in the unprecedented cationic µ3-oxo-bridged trigermanium derivative 5. It can be considered a hitherto unknown digermylene oxide-stabilized germylene cation, revealing that TREN-based tris(germylenes) can function as tripodal ligands. This aspect is realized in the mononuclear Cu(I) complexes 6 and 7 isolated in the reactions of tris(germylenes) 3 and 4 with CuI, where all three germylenes were coordinated simultaneously with one copper atom, confirming that TREN-based tris(germylene) can indeed function as tripodal ligands. Furthermore, the utility of these copper complexes, 6 and 7, as catalysts in the azide-alkyne cycloaddition (CuAAC) reactions is also demonstrated.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"19 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148877656","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2026-09-03 DOI: 10.1039/d6qi01591c

Vladimir Arion,Oleg Palamarciuc,Ciubotaru Bianca-Iulia,Alexandru-Constantin Stoica,Michaela Hejl,Marta Hammerstad,Mihaela Balan-Porcarasu,Sergiu Shova,Gerda T. Gátszegi,Ana Popovic Bijelic,Johannes Reynisson,Michael Jakupec,Michal Zalibera,P. Rapta,Eva A. Enyedy,Dragos Peptanariu,Mihaela Dascalu,Maria Cazacu,Ernest Hamel

{"title":"","authors":"Vladimir Arion,Oleg Palamarciuc,Ciubotaru Bianca-Iulia,Alexandru-Constantin Stoica,Michaela Hejl,Marta Hammerstad,Mihaela Balan-Porcarasu,Sergiu Shova,Gerda T. Gátszegi,Ana Popovic Bijelic,Johannes Reynisson,Michael Jakupec,Michal Zalibera,P. Rapta,Eva A. Enyedy,Dragos Peptanariu,Mihaela Dascalu,Maria Cazacu,Ernest Hamel","doi":"10.1039/d6qi01591c","DOIUrl":"https://doi.org/10.1039/d6qi01591c","url":null,"abstract":"Cancer cells exploit multiple proliferation pathways, making single-target therapies vulnerable to resistance. Here, a thiosemicarbazone-based strategy is introduced for striking two validated oncotargets, the R2 subunit of ribonucleotide reductase (RNR) and the colchicine site of tubulin, with one agent. Guided by molecular docking, quinoline-8-carboxaldehyde N4-(3,4,5-trimethoxyphenyl)thiosemicarbazone (HL) and its metal complexes [CuII(L)(Cl2CHCOO)](1), [CuII(L)Cl] (2), [PdII(L)Cl] (3), and [FeIII(L)2Cl] (4) were synthesized and characterized by spectroscopic, spectrometric, electrochemical, and crystallographic techniques. Complexes 1, 2, and 4 effectively quench the R2 tyrosyl radical and inhibit tubulin polymerization in cell-free assays, yet only coordination to Cu(II) translates this activity into sub- to low-micromolar cytotoxicity toward MCF-7 breast cancer cells, while the parent Schiff base and its Pd(II) and Fe(III) complexes remain largely inactive. Strikingly, cell cycle profiling shows that this activity manifests almost exclusively as mitotic arrest mirroring the microtubule poison nocodazole, with no detectable S-phase signature. This paradox is resolved by a kinetic model in which RNR inhibition acts as a transient brake on S-phase rather than a hard block, whereas tubulin inhibition creates an irreversible mitotic trap that captures every cell. These findings establish Cu(II) thiosemicarbazonates as dual-target chemotype and provide a conceptual framework for interpreting multi-target anticancer mechanisms in cells.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"13 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148877659","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Super-flexible coordination: the metal matters 超灵活的协调：金属很重要

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2026-09-03 DOI: 10.1039/d6qi01256f

Cedric Uhlmann,Steven Kebernik,Luca Münzfeld,Tim P. Seifert,Ralf Köppe,Peter W. Roesky

{"title":"Super-flexible coordination: the metal matters","authors":"Cedric Uhlmann,Steven Kebernik,Luca Münzfeld,Tim P. Seifert,Ralf Köppe,Peter W. Roesky","doi":"10.1039/d6qi01256f","DOIUrl":"https://doi.org/10.1039/d6qi01256f","url":null,"abstract":"Herein, we report a unique tripodal system, a tin-chelated trisphosphine oxide scorpionate ligand that coordinates to hard metal atoms through the oxygen atoms and, upon full skeletal rearrangement, to soft metals through the phosphorus atoms. The reactions of the previously reported potassium salt [κ3O-Sn(P(O)Ph2)3K] with rare-earth complexes based on the cyclooctatetraenediide ligand yielded the compounds [κ3O-Sn(P(O)Ph2)3LnIII(η8-Cot)] (Ln = Y, Ce, Tb, Er; Cot = C8H82−) and [κ3O-Sn(P(O)Ph2)3LnIII(η8-CotTIPS)] (Ln = Y, Dy, Er; CotTIPS = 1,4-(iPr3Si)2C8H62−), in which the trivalent lanthanide ions are coordinated by the oxygen atoms, analogous to the potassium ions in the starting material. The reactions of the potassium salt and transition metal chlorides led to the isolation of the compounds [κ3P-Sn(P(O)Ph2)3MCl] (M = Co, Fe). Interestingly, an in situ ligand rearrangement was observed for the transition metals, whereby the arrangement of the P(O)Ph2 groups inverted. This results in a coordination of the oxygen atoms to the tin atom, while the phosphorus atoms bind to the d-metal ions. Quantum chemical calculations were performed to rationalize this observation.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"9 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148877658","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0