Inorganic Chemistry最新文献_第10页

Earth-Abundant Manganese Catalysts for DehydrogenativeCoupling of Alcohols and Silanols with Hydrosilanes 氢硅烷与醇、硅醇脱氢偶联的富锰催化剂

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-15 DOI: 10.1021/acs.inorgchem.6c04822

Marcin Gruszczyński,Dariusz Lewandowski,Miłosz Makowski,Maciej Kubicki,Grzegorz Hreczycho

引用次数: 0

Structural Evolution in Paraelectric–AntiferroelectricPhase Transitions of Tungsten Bronze-Type K2NdNb5O15 钨青铜型K2NdNb5O15准电-反铁电相变的结构演变

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-15 DOI: 10.1021/acs.inorgchem.6c04469

Hodaka Abe,Sou Yasuhara,Takuya Hoshina

{"title":"Structural Evolution in Paraelectric–Antiferroelectric\u0000Phase Transitions of Tungsten Bronze-Type K2NdNb5O15","authors":"Hodaka Abe,Sou Yasuhara,Takuya Hoshina","doi":"10.1021/acs.inorgchem.6c04469","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c04469","url":null,"abstract":"Abstract Tungsten bronze (TB)-type K2RNb5O15 (R: rare-earth element) compounds exhibit antiferroelectric (AFE) properties and are promising for energy-storage and high-voltage applications. However, the structural origin of their antiferroelectricity remains unclear, hindering the establishment of rational design principles. Here, we investigated the structural evolution of K2NdNb5O15 from its aristotype P4/mbm phase to the AFE phase by combining high-resolution synchrotron X-ray and neutron powder diffraction experiments with machine-learning-assisted molecular dynamics (MD) simulations. The diffraction data revealed three successive phase transitions between 300 and 600 K, with a previously undetected intermediate phase lying between the aristotype P4/mbm and AFE phases. The MD simulations and Rietveld analysis consistently identified the soft modes that drive the structural phase transitions from the P4/mbm phase to the AFE phase. Condensation of a NbO6 octahedral tilting mode gives rise to the intermediate phase, whereas out-of-phase twisting of NbO6 octahedra and antipolar displacements of Nd and Nb cations emerge together at the transition to the AFE phase. These findings resolve the multiple structural distortions responsible for the antiferroelectricity in K2NdNb5O15 and provide microscopic insight into the design of TB-type AFEs.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"32 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210291","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}

引用次数: 0

Dual-FunctionalInterface Molecular Engineering ofConductive MOF Nanoarrays for Oxygen Evolution Reaction 用于析氧反应的导电MOF纳米阵列的双功能界面分子工程

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-15 DOI: 10.1021/acs.inorgchem.6c04573

Chong Lin,Xinyi Luo,Xuetong Zhang,Cuiping Zeng,Lin Liu,Mingyang Ma,Minghui Cao,Jingyang Tian,Yong Qian

{"title":"Dual-Functional\u0000Interface Molecular Engineering of\u0000Conductive MOF Nanoarrays for Oxygen Evolution Reaction","authors":"Chong Lin,Xinyi Luo,Xuetong Zhang,Cuiping Zeng,Lin Liu,Mingyang Ma,Minghui Cao,Jingyang Tian,Yong Qian","doi":"10.1021/acs.inorgchem.6c04573","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c04573","url":null,"abstract":"Abstract Drawing conceptual inspiration from the inorganic–organic hybrid architecture of natural Photosystem II, this work presents a dual-functional interface molecular engineering strategy. A Ni(TCNQ)2-FcDA nanoarrays (NAs) composite catalysts were constructed by anchoring ferrocene dicarboxylic acid (FcDA), featuring both proton-relay and redox activities, onto conductive Ni(TCNQ)2 nanoarrays (Ni(TCNQ)2 NAs). Structural characterizations indicate that carboxyl groups in FcDA participate in interfacial proton transport, while Ni–Fe coupling synergistically modulates the electronic structure of the active Ni centers. Theoretical calculations indicate that this interfacial engineering induces a significant downshift in the Ni 3d orbital d-band center, effectively lowering the energy barrier for the OH to O conversion step. Consequently, the catalyst achieves a current density of 10 mA cm–2 at an overpotential of only 226 mV in 1.0 mol L–1 KOH, with a low Tafel slope of 30.4 mV dec–1 and stability exceeding 24 h. Kinetic analysis further reveals a concerted proton-coupled electron transfer (PCET) mechanism. This work presents a strategy for synergistically addressing mass transport bottlenecks and electronic structure mismatches in conductive MOFs via dual-functional molecular interface engineering.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"32 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210290","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}

引用次数: 0

SpatiallySeparated Redox Sites in an RP/In2S3 Photocatalystfor Dual-Channel H2O2 Production in Pure Water RP/In2S3光催化剂在纯水中双通道生成H2O2的空间分离氧化还原位点

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-15 DOI: 10.1021/acs.inorgchem.6c03525

Lele Wang,Ruiyang Hu,Zhiqing Hua,Miao Zhang,Weiran Wu,Chao Meng,Yinlu Gao,Yingcong Wei

{"title":"Spatially\u0000Separated Redox Sites in an RP/In2S3 Photocatalyst\u0000for Dual-Channel H2O2 Production in Pure Water","authors":"Lele Wang,Ruiyang Hu,Zhiqing Hua,Miao Zhang,Weiran Wu,Chao Meng,Yinlu Gao,Yingcong Wei","doi":"10.1021/acs.inorgchem.6c03525","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c03525","url":null,"abstract":"Abstract Spatially separated redox site engineering for dual-channel hydrogen peroxide (H2O2) photosynthesis has emerged as a promising strategy for the sustainable production of liquid solar fuels through artificial photosynthesis. Herein, a core–shell heterojunction composed of resorcinol-p-phthalaldehyde (RP) resin and In2S3 nanosheets is constructed to enhance H2O2 formation. The introduction of oxidative and π-conjugated RP kinetically accelerates charge separation and increases the surface charge density of the In2S3 photocatalyst significantly. Thermodynamically, the high redox potential and spatially separated active sites of RP/IS expand the H2O2 generation pathway from a single ORR route to a dual-channel mechanism incorporating both the oxygen reduction reaction (ORR) and water oxidation reaction (WOR). DFT calculations reveal that the synergistic enhancement of O2 and H2O adsorption further facilitates efficient H2O2 production. Upon visible-light irradiation, the optimized RP/IS achieves an impressive H2O2 production rate of 4193 μmol·g–1·h–1 in pure water. This study presents an innovative approach for enhancing H2O2 generation through the modulation of reaction pathways.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"18 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210105","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}

引用次数: 0

Reaction ofCysteine and Selenocysteine with a ModelAu(I)-N-Heterocyclic Carbene Complex: A QM and QM/MM MD ComparativeStudy 半胱氨酸和硒代半胱氨酸与au (I)- n -杂环卡宾配合物的反应：QM和QM/ mmmd的比较研究

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-15 DOI: 10.1021/acs.inorgchem.6c04543

Milan Říha,Markéta Munzarová,Jaroslav V. Burda

{"title":"Reaction of\u0000Cysteine and Selenocysteine with a Model\u0000Au(I)-N-Heterocyclic Carbene Complex: A QM and QM/MM MD Comparative\u0000Study","authors":"Milan Říha,Markéta Munzarová,Jaroslav V. Burda","doi":"10.1021/acs.inorgchem.6c04543","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c04543","url":null,"abstract":"Abstract The substitution reaction of a model Au(I)-N-heterocyclic carbene (NHC) complex with cysteine and selenocysteine represents a key elementary step in the inhibition mechanism of thioredoxin reductase by gold-based metallodrugs. We present a systematic quantum-mechanical (QM) and combined QM/MM investigation of this reaction with the aim of assessing the consistency and reliability of activation and reaction free energies obtained at different theoretical levels. The reaction was first studied at the QM level using several density functional theory (DFT) functionals and basis sets and subsequently within a QM/MM framework, employing multiple QM descriptions of the reactive region and explicit molecular-mechanics (MM) treatment of the solvent (water). Comparison of QM and QM/MM results reveals how the inclusion of the surrounding environment affects both activation barriers and reaction energies. Several protonation states of cysteine and selenocysteine were considered, and a pH-dependent model was constructed using a grand-canonical transformation of the free energy. Combining QM/MM reaction energetics with pKa values yielded pH-dependent Gibbs–Alberty free energy profiles with a coordination-preference switch at pH ≈ 8. In acidic and neutral solutions the Au(I) complex coordinates with selenocysteine, while in a basic environment, coordination with cysteine is energetically more stable.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"168 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210112","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}

引用次数: 0

Jahn-TellerDistortion-Enabled Interfacial ChemicalRecognition for Chiral Hybrid Halides: ( R/S -3AP)BiCl5 手性杂化卤化物的jhn - teller -畸变激活界面化学识别[j]

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-15 DOI: 10.1021/acs.inorgchem.6c04759

Yuxuan Wu,Can Pei,Yujie Zhang,Haonan Liu,Hongping Wu,Zhanggui Hu,Hongwei Yu

{"title":"Jahn-Teller\u0000Distortion-Enabled Interfacial Chemical\u0000Recognition for Chiral Hybrid Halides: (\u0000 R/S\u0000 -3AP)BiCl5","authors":"Yuxuan Wu,Can Pei,Yujie Zhang,Haonan Liu,Hongping Wu,Zhanggui Hu,Hongwei Yu","doi":"10.1021/acs.inorgchem.6c04759","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c04759","url":null,"abstract":"Abstract Noncentrosymmetric (NCS) materials with intrinsic chirality are highly desirable for diverse symmetry-dependent functional applications, yet their rational construction remains challenging because asymmetric building units frequently undergo centrosymmetric packing during crystallization. Herein, we develop a Jahn–Teller distortion-enabled interfacial chemical recognition strategy to realize the chiral hybrid halides (R/S-3AP)BiCl5 crystallizing in the chiral NCS space group P212121. The stereochemically active 6s2 lone pair of Bi3+ induces anisotropic distortion of the [BiCl6] octahedra, creating chemically differentiated chloride acceptor sites. Meanwhile, the chiral 3-aminopyrrolidine cations (3AP2+) exhibit two chemically distinct nitrogen centers with differentiated protonation behaviors, producing pyrrolidinium and ammonium N–H donors with distinct hydrogen-bonding capabilities. The stronger donor ability of exocyclic ammonium (NH3+) sites enables preferential N–H···Cl interactions with chloride sites possessing enhanced acceptor characteristics, establishing a chemically complementary organic–inorganic interface. This directional donor–acceptor recognition regulates chiral cation orientations and promotes chirality transfer from molecular units to the extended crystalline framework. This work demonstrates that coupling Jahn–Teller distortion-mediated acceptor regulation with protonation-dependent donor differentiation provides an effective strategy for programming directional interfacial chemical recognition and translating local structural asymmetry into macroscopic chiral ordering in NCS crystals.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"22 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210059","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}

引用次数: 0

A Dichalcogenide-ProtectedPt@Au12@Ag8 Nanocluster Dichalcogenide-ProtectedPt@Au12@Ag8纳米簇

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-15 DOI: 10.1021/acs.inorgchem.6c04087

Tzu-Hao Chiu,Michael N. Pillay,Samia Kahlal,Jean-Yves Saillard,C. W. Liu

{"title":"A Dichalcogenide-Protected\u0000Pt@Au12@Ag8 Nanocluster","authors":"Tzu-Hao Chiu,Michael N. Pillay,Samia Kahlal,Jean-Yves Saillard,C. W. Liu","doi":"10.1021/acs.inorgchem.6c04087","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c04087","url":null,"abstract":"Abstract Precise control over the location of heterometal atoms in alloy nanoclusters is essential for understanding how metal distribution governs superatomic structure and properties. Herein we show that PtAg20[S2P(OPr)2]12 (PtAg20) can serve as a structurally defined precursor for constructing a PtAu12 superatom copassivated by ligands and Ag atoms through redox-mediated Au-for-Ag exchange. Treatment of PtAg20 with an excess of Au(I) affords PtAu12Ag8[S2P(OPr)2]12 (PtAu12Ag8), in which substitution of Ag by Au occurs exclusively on the PtAg20 icosahedral core. Single-crystal X-ray diffraction reveals a compact PtAu12 core encapsulated by two Ag4(dtp)6 (dtp = dithiophosphate) units. Unlike all the known silver-rich isoelectronic nanoclusters featuring a centered icosahedron protected by a Ag8(dtp)12 outer shell that adopt C3-type or C3-derived shell arrangements, PtAu12Ag8 displays a C2 geometry. Spectroscopic and mass-spectrometric measurements support the formation of the Au-rich cluster, while DFT calculations identify the [PtAu12]4+ core as an eight-electron superatom with a closed-shell 1S21P61D0 electronic configuration. This work demonstrates that selective replacement of the icosahedral cage can generate not only a new trimetallic superatomic core but also an unusual reconstruction of the surrounding Ag–ligand passivating layer.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"37 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210060","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}

引用次数: 0

Ligand Topologyand Secondary-Sphere InteractionsDirect the Mechanistic Pathways of Chemical and Electrochemical OxygenReduction Reactions Catalyzed by Copper(II) Complexes 配体拓扑结构和次级球相互作用指导铜（II）配合物催化化学和电化学氧化还原反应的机理途径

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-15 DOI: 10.1021/acs.inorgchem.6c03725

Rajib Samanta,Srijan Narayan Chowdhury,Arpan Mondal,Pradip Bhunia,Tapan Kanti Paine

{"title":"Ligand Topology\u0000and Secondary-Sphere Interactions\u0000Direct the Mechanistic Pathways of Chemical and Electrochemical Oxygen\u0000Reduction Reactions Catalyzed by Copper(II) Complexes","authors":"Rajib Samanta,Srijan Narayan Chowdhury,Arpan Mondal,Pradip Bhunia,Tapan Kanti Paine","doi":"10.1021/acs.inorgchem.6c03725","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c03725","url":null,"abstract":"Abstract The oxygen reduction reaction (ORR) is crucial for renewable energy and peroxide production, but understanding the factors influencing catalytic efficiency and selectivity remains an important topic. Although a number of copper-based ORR catalysts using polydentate ligands of varying denticity and flexibility have been developed, the roles of ligand topology and secondary coordination sphere (SCS) interactions have been largely unexplored. To address these issues, we have developed four mononuclear copper(II) complexes supported by isomeric ethylenediamine-derived ligands and their amide-functionalized analogues. Structural, spectroscopic, electrochemical, and kinetic studies reveal that subtle changes in ligand architecture profoundly alter the electronic structure, redox properties, and catalytic behavior of the copper(II) complexes. Under chemical ORR conditions, all complexes selectively mediate the direct 4e–/4H+ reduction of O2 through a rate-determining proton-coupled electron transfer (PCET) step. The tripodal ligand framework enhances catalytic activity through proton-responsive modulation of Cu-oxygen intermediates, whereas amide incorporation accelerates ORR via SCS interaction that facilitates PCET. In contrast, electrochemical studies uncover a distinct mechanism in which O2 binding to Cu(I) becomes rate-limiting and the overall 4e– reduction proceeds via a sequential [2 + 2]e– pathway. These findings offer insights into design principles for molecular oxygen reduction catalysts with tunable activity and selectivity.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"26 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210061","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}

引用次数: 0

Surface LigandComposition of Polyoxovanadate-AlkoxidesInfluences Hole Transfer from CdSe Quantum Dots 多钒氧烷酸盐表面配体组成对CdSe量子点空穴转移的影响

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-15 DOI: 10.1021/acs.inorgchem.6c01486

Chari Y. M Peter,Benjamin Hancock,John J. Caruso,Nicholas B. Flemings,Margaret C. Hintz,Todd D. Krauss,Ellen M. Matson

{"title":"Surface Ligand\u0000Composition of Polyoxovanadate-Alkoxides\u0000Influences Hole Transfer from CdSe Quantum Dots","authors":"Chari Y. M Peter,Benjamin Hancock,John J. Caruso,Nicholas B. Flemings,Margaret C. Hintz,Todd D. Krauss,Ellen M. Matson","doi":"10.1021/acs.inorgchem.6c01486","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c01486","url":null,"abstract":"Abstract In this study, we evaluate the impact of the modulation of the surface structure of polyoxovanadate-alkoxides (POV-alkoxides) on their hole transfer capabilities with cadmium selenide quantum dots (CdSe QDs). Initial studies probe the consequences of increasing the carbon chain length of bridging alkoxide ligands, through comparison of efficiencies of hole transfer to methoxide- and ethoxide-capped POV-alkoxides, [V6O7(OR)12]1– (R = CH3, CH2CH3). While [V6O7(OCH2CH3)12]1– is able to quench the photoluminescence of CdSe QDs, reduced efficiency is observed in comparison to its methoxide congener. This observation indicates that increasing steric bulk at the surface of the POV-alkoxide inhibits interactions of the hole acceptor with the surface of the nanocrystal. Subsequent studies investigate a POV-alkoxide capped with a tridentate ligand containing a pyridine substituent that we hypothesized would promote coordination of the cluster to the surface of the nanocrystal. Steady-state photoluminescence quenching experiments indicate improved hole transfer in comparison to structural controls, while time-correlated single-photon counting photoluminescence decay dynamics confirm an increase in the number of QD-cluster associations. However, slower hole transfer lifetimes per cluster are noted for the pyridine-substituted assembly. Collectively, our experiments provide insight into design criteria for molecular redox mediators that enhance the efficiency of hole transfer from CdSe QDs.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"47 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210108","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}

引用次数: 0

M(IV)- andM(V)-Substituted {MW5} Lindqvist-TypePolyoxometalates from Plenary [W6O19]2– or WO3·H2O: A Gateway to Wider SystematicReactivity Studies [W6O19]2 -或WO3·H2O中M(IV)-和M(V)-取代{MW5} lindqvist型多金属氧酸盐：更广泛的系统活性研究的门户

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-14 DOI: 10.1021/acs.inorgchem.6c03884

Dominic Shiels,Daniel Lebbie,Amar Mohammed,Magda Pascual-Borràs,Rosie Black,Corinne Wills,Paul G. Waddell,Benjamin R. Horrocks,R. John Errington

{"title":"M(IV)- and\u0000M(V)-Substituted {MW5} Lindqvist-Type\u0000Polyoxometalates from Plenary [W6O19]2– or WO3·H2O: A Gateway to Wider Systematic\u0000Reactivity Studies","authors":"Dominic Shiels,Daniel Lebbie,Amar Mohammed,Magda Pascual-Borràs,Rosie Black,Corinne Wills,Paul G. Waddell,Benjamin R. Horrocks,R. John Errington","doi":"10.1021/acs.inorgchem.6c03884","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c03884","url":null,"abstract":"Abstract The reactivity of polyoxometalates (POMs) may be tuned by heterometal substitution into the POM framework, and systematic reactivity studies of these nanoscale molecular metal oxide structures require reliable, efficient synthetic methods. We have now shown that nonaqueous base degradation of either WO3·H2O or plenary (TBA)2[W6O19] (TBA)21 followed by reaction with heterometal precursors provides convenient, high-yield access to MIV- and MV-substituted {MW5} Lindqvist-type hexametalates [(iPrO)TiW5O18]3–2, [(MeO)MW5O18]3– (M = Ti 3, Sn 4), [{(MeO)MW5O18}2]6– (M = Zr 5, Hf 6) and [MW5O19]3– (M = V 7, Nb 8, Ta 9). Crystal structures of (TBA)65 and (TBA)66 showed the anions to be isostructural, and kinetic studies of CD3OD exchange revealed slightly slower exchange at Hf than Zr. For 5, DFT analysis of MeOH exchange revealed a transition state involving a six-membered ring via insertion of MeOH into a Zr(μ-OMe)Zr bridge. Alkoxide protonolysis reactions provided monomeric {LMW5} derivatives with 7-coordinate Zr or Hf, and X-ray crystal structures of (TBA)3[(PhCO2)ZrW5O18] (TBA)312, (TBA)3[(PhCO2)HfW5O18] (TBA)313 and (TBA)3[(acac)HfW5O18] (TBA)314 were obtained. Cyclic voltammetry showed one-electron couples for 3, 4, 7, 8, and 9 but not for dimeric 5 and 6, consistent with calculated reduction potentials for these {MW5} anions.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"17 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210114","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}

引用次数: 0