Inorganic Chemistry最新文献_第2页

Beyond Structural Analogy: Electronic and Functional Divergence in Isostructural Zr, Hf, and Th Metal–Organic Frameworks 超越结构类比：等结构Zr、Hf和Th金属有机框架中的电子和功能发散

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-11-09 Epub Date: 2026-10-22 DOI: 10.1021/acs.inorgchem.6c05024

Xiangyu Zhang, Yaoyao Bai, Yunyi Cui, Guangtao Zhang, Junpu Yang, Jingqi Ma, Jian Lin

{"title":"Beyond Structural Analogy: Electronic and Functional Divergence in Isostructural Zr, Hf, and Th Metal–Organic Frameworks","authors":"Xiangyu Zhang, Yaoyao Bai, Yunyi Cui, Guangtao Zhang, Junpu Yang, Jingqi Ma, Jian Lin","doi":"10.1021/acs.inorgchem.6c05024","DOIUrl":"10.1021/acs.inorgchem.6c05024","url":null,"abstract":"Zr(IV), Hf(IV), and Th(IV) exhibit closely related coordinationchemistry and can form structurally analogous materials, underpinningthe widespread use of Zr as a nonradioactive surrogate for Th(IV).Here we demonstrate that such structural analogy does not necessarilyextend to electronic and functional properties through a comparativestudy of three isostructural M6-ADC (M = Zr, Hf, and Th;ADC= 9,10-anthracenedicarboxylate) metal–organic frameworks. Despitetheir nearly identical framework structures, Th6-ADC exhibitsoptical and electronic characteristics distinct from its Zr and Hfanalogues, including distinctive red coloration, extended visible-to-near-infraredabsorption, and a pronounced ligand-centered radical signature. Theseelectronic differences are further manifested in their functionalbehavior, with Th6-ADC displaying substantially enhancedphotothermal conversion under near-infrared irradiation. These resultsreveal a clear divergence between structural and electronic similarityamong Zr-, Hf-, and Th-based frameworks.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 44","pages":"25663–25667"},"PeriodicalIF":4.6,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149230063","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}

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Carbon Dot Composites Exhibiting Time-Dependent Phosphorescence Color and Circularly Polarized Room-Temperature Phosphorescence 具有时变磷光色和圆偏振室温磷光的碳点复合材料

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-11-09 Epub Date: 2026-10-23 DOI: 10.1021/acs.inorgchem.6c04231

Yushuang Wu, Yijie Wang, Linbo Yu, Shengju Zhou, Xiaofeng Sun

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Tuning the Photoinduced Magnetic Coupling in Terbium Porphyrazines: The Effect of Thiadiazole Electron-Withdrawing Groups and an Asymmetric Secondary Coordination Environment 调节卟啉铽的光致磁耦合：噻二唑吸电子基团和不对称二次配位环境的影响

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-11-09 Epub Date: 2026-10-26 DOI: 10.1021/acs.inorgchem.6c03212

Mohammad A. Ferryansyah, Hiroyuki Komatsu, Akira Fuyuhiro, Anas Santria, Naoto Ishikawa

{"title":"Tuning the Photoinduced Magnetic Coupling in Terbium Porphyrazines: The Effect of Thiadiazole Electron-Withdrawing Groups and an Asymmetric Secondary Coordination Environment","authors":"Mohammad A. Ferryansyah, Hiroyuki Komatsu, Akira Fuyuhiro, Anas Santria, Naoto Ishikawa","doi":"10.1021/acs.inorgchem.6c03212","DOIUrl":"10.1021/acs.inorgchem.6c03212","url":null,"abstract":"Modulatingintramolecular magnetic interactions between localized4f electrons and delocalized photoexcited macrocyclic π-systems(J–L interaction) provides a strategyfor designing magneto-optical materials. However, the effects of ligandelectronic structure and asymmetric coordination environments remainpoorly understood. Here, we report the synthesis and magneto-opticalproperties of an asymmetric terbium(III) complex featuring a thiadiazoleelectron-withdrawing group (EWG)-containing porphyrazine ligand andan acetylacetonate ligand, [TbTTDPz(acac)(DMF)(H2O)]. Variable-temperature,variable-field magnetic circular dichroism (VTVH-MCD) spectroscopyat the Q-band confirms parallel-type J–L coupling. A comparative analysis with the symmetric [TbPc(cyclen)]Clanalogue suggests that the asymmetric environment contributes to reducedligand-centered orbital angular momentum (Lz(π) = 1.5), while the thiadiazole substitutionenhances the J–L interaction (ΔJL = 1.5 cm–1). Multiconfigurationaland DFT calculations demonstrate that explicitly including acac πorbitals in the active space is essential for accurately evaluating Lz(π) and ΔJL, as its highest occupied orbital residesin close energetic proximity to the TTDPz HOMO, facilitating hybridization.Spatial distribution analyses reveal that the thiadiazole EWG createsan electropositive core, forcing the excited-state LUMOs to contractinward. This maximizes spatial overlap with the lanthanide centerto enhance the J–L interaction. Thus,modifying the primary π-framework and the asymmetric secondarycoordination environment enables systematic tuning of J–L interactions.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 44","pages":"25759–25770"},"PeriodicalIF":4.6,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149248677","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}

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Mechanistic Insights into Nicotinamidase by CoII EPR Spectroscopy 用CoII EPR光谱分析烟酰胺酶的机理

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-11-09 Epub Date: 2026-10-27 DOI: 10.1021/acs.inorgchem.6c04023

Isabella E. Acosta, Melissa M. Bollmeyer, R. David Britt

{"title":"Mechanistic Insights into Nicotinamidase by CoII EPR Spectroscopy","authors":"Isabella E. Acosta, Melissa M. Bollmeyer, R. David Britt","doi":"10.1021/acs.inorgchem.6c04023","DOIUrl":"10.1021/acs.inorgchem.6c04023","url":null,"abstract":"Nicotinamidases catalyze the metal-dependent hydrolysisof nicotinamidein the NAD+ salvage pathway in most nonmammalian organisms.Their essential role in pathogenic bacteria, but not mammals, hasmade them an attractive target for new antibiotic treatments. Mostof the characterized nicotinamidases rely on a ZnII activesite for catalysis, which has limited spectroscopic studies of theseenzymes. Herein, we employ CoII-substitution as a spectroscopicprobe to investigate the mechanism of nicotinamidase from the pathogen Streptococcus pneumoniae (SpPncA). The CoII-substituted enzyme features a spin S = 3/2 EPRsignal with resolved hyperfine splitting consistent with a five-coordinatemetal center. Analysis of a conserved second-sphere Asp9 residue viasite-directed mutagenesis reveals an unexpected role in maintainingthe geometry of the metal coordination site through an extended networkof electrostatic interactions. Characterization of substrate, intermediate,product, and inhibitor-bound complexes demonstrates that subtle changesin the ligand impact the rhombicity of the EPR spectrum. Leveragingthese spectroscopic features, we characterize a catalytically relevantthioester intermediate formed during turnover with nicotinamide forthe first time. Together, these results provide new mechanistic insightsinto nicotinamidase catalysis.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 44","pages":"25986–25994"},"PeriodicalIF":4.6,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149250956","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}

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Chemical Origins of Line Broadening in the f–f Transitions of a Molecular Yb(III) Complex 分子Yb（III）配合物f-f跃迁中谱线展宽的化学来源

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-11-09 Epub Date: 2026-10-27 DOI: 10.1021/acs.inorgchem.6c03913

Taras Khvorost, Pavel Rublev, Jaeeun Lee, Xinang Yang, Yongjia He, Justin R. Caram, Anastassia N. Alexandrova

{"title":"Chemical Origins of Line Broadening in the f–f Transitions of a Molecular Yb(III) Complex","authors":"Taras Khvorost, Pavel Rublev, Jaeeun Lee, Xinang Yang, Yongjia He, Justin R. Caram, Anastassia N. Alexandrova","doi":"10.1021/acs.inorgchem.6c03913","DOIUrl":"10.1021/acs.inorgchem.6c03913","url":null,"abstract":"Lanthanide molecular complexes are promising platformsfor quantuminformation science (QIS), where narrow optical line widths are essentialfor coherent light–matter interaction. Rational design of suchcolor centers requires understanding how the chemical environmentsets the line width, yet predictive modeling of lanthanide electronicstructure remains challenging. Here we compute the energy gaps andline widths of f–f optical transitions in a model Yb(III) solvate,Yb(2Me–THF)3Cl3, using CASSCF/NEVPT2and compare them with high-resolution absorption spectra. We simulatebroadening by scanning the PES along all 150 normal modes and by conformationalsampling of the ligand environment. The simulated envelopes reproducethe main features of the experimental spectrum and can be decomposedinto contributions from individual nuclear motions. Our analysis showsthat the broadening is set by fluctuations of the ligand field andis dominated by low-frequency collective motions of the first coordinationsphere. We further find that 4f energy gaps are highly sensitive tothe Yb-ligand bond distances, and that oscillator strength variesnonmonotonically with geometry, so that brighter transitions neednot be broader. These results suggest that spectral broadening inmolecular Yb(III) absorbers may be reduced by ligand designs thatfix the first coordination sphere and limit conformational freedom.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 44","pages":"25959–25969"},"PeriodicalIF":4.6,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149250959","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}

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Enhanced Antithermal Quenching of Hybrid Pb(II)- and Bi(III)-Based Metal Halides for Phosphor-Converted Light-Emitting Diodes 用于磷转换发光二极管的混合Pb（II）和Bi（III）基金属卤化物的增强抗热猝灭

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-11-09 Epub Date: 2026-10-27 DOI: 10.1021/acs.inorgchem.6c04788

Shuang Wang, Hui-Lin Wang, Min Li, Hua-Rui Wang, Yun-Long Wu, Xiao-Gang Yang

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Sb2TeO7: A Chiral Antimony Tellurite with Phase-Matchable Second-Harmonic Generation 具有相位匹配二次谐波产生的手性碲锑酸盐Sb2TeO7

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-11-09 Epub Date: 2026-10-27 DOI: 10.1021/acs.inorgchem.6c05188

Chunmei Huang, Huaiqiang Xun, Mengqiu Wei, Huan Yu, Xiaoshuang Li, Qingyue Cui, Yi Feng, Rui Wu, Zhaohui Chen

{"title":"Sb2TeO7: A Chiral Antimony Tellurite with Phase-Matchable Second-Harmonic Generation","authors":"Chunmei Huang, Huaiqiang Xun, Mengqiu Wei, Huan Yu, Xiaoshuang Li, Qingyue Cui, Yi Feng, Rui Wu, Zhaohui Chen","doi":"10.1021/acs.inorgchem.6c05188","DOIUrl":"10.1021/acs.inorgchem.6c05188","url":null,"abstract":"Noncentrosymmetric (NCS) structures are uncommon amongcompositionallysimple inorganic solids, even when their constituent polyhedra arelocally asymmetric. Here, we establish the binary tellurite Sb2TeO7 as a chiral NCS crystal that adopts the orthorhombicspace group P212121 (No. 19). Stereochemically active trigonal-pyramidal [TeO3] units bridge two types of distorted Sb–O zigzag chains intoa three-dimensional framework, preventing cancellation of the localasymmetric distortions. The structure was obtained through prolongedoxidative solid-state treatment and validated by single-crystal andpowder X-ray diffraction. Sb2TeO7 exhibits highthermal stability up to approximately 800 °C and well-balancednonlinear optical properties. It possesses a wide transparent windowfrom 299 nm to 5.75 μm, a suitable birefringence of 0.106 at546 nm, and a moderate phase-matchable second-harmonic generation(SHG) response (1.36 × KDP at 1064 nm). Although the SHG responseis moderate relative to optimized tellurites, these results demonstratethat an NCS framework and optical anisotropy can be realized in abinary antimony tellurite when the constituent polyhedra assemblecooperatively.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 44","pages":"25672–25677"},"PeriodicalIF":4.6,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149250966","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}

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ANb2(PS4)2(S2)2 (A = K, Rb) Synthesized by Metal Oxide–Boron–Chalcogen (MOBQ) Method: Featuring [Nb2S8(S2)2] Dimers and [PS4] Tetrahedra for Infrared Nonlinear Optical Properties 金属氧化物-硼-硫（MOBQ）法合成ANb2(PS4)2(S2)2 (A = K, Rb)：具有[Nb2S8(S2)2]二聚体和[PS4]四面体的红外非线性光学性质

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-11-09 Epub Date: 2026-10-28 DOI: 10.1021/acs.inorgchem.6c04097

Jia-Qi Ren, Zheng-Ren Chen, Xue-Zhu Shen, Mao-Yin Ran, Sheng-Ping Guo

{"title":"ANb2(PS4)2(S2)2 (A = K, Rb) Synthesized by Metal Oxide–Boron–Chalcogen (MOBQ) Method: Featuring [Nb2S8(S2)2] Dimers and [PS4] Tetrahedra for Infrared Nonlinear Optical Properties","authors":"Jia-Qi Ren, Zheng-Ren Chen, Xue-Zhu Shen, Mao-Yin Ran, Sheng-Ping Guo","doi":"10.1021/acs.inorgchem.6c04097","DOIUrl":"10.1021/acs.inorgchem.6c04097","url":null,"abstract":"NbnSm clusterscontaining S–S and Nb–Nb bonds are promising as infrarednonlinear optical (IR NLO) functional motifs, yet their study in thethiophosphate system remains scarce. Here, ANb2(PS4)2(S2)2 (A = K (1), Rb (2)) were synthesized by the metal oxide–boron–chalcogen(MOBQ) solid-state routine, and their structures feature a three-dimensionaldouble-helical tunnel framework costructed by alternately connected[Nb2S8(S2)2] dimers and[PS4] tetrahedra. Both compounds exhibit narrow band gaps(1.59 and 1.58 eV), large birefringences (0.20 and 0.21 @ 2.1 μm),second-harmonic generation (SHG) responses, and photocurrent responses.Theoretical calculations indicate that their weak SHG response originatesfrom the multidirectional cancellation of dipole moment vectors atthe microscopic scale. This work enriches the IR NLO research on Nb-basedthiophosphates and clarifies the application potential and structurallimitations of Nb-based sulfides in the NLO field.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 44","pages":"25640–25645"},"PeriodicalIF":4.6,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149274945","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}

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Fluoride-Enabled Assembly of Iron–Hydrogen-Bonded Frameworks as Bifunctional Lewis Acid–Base Catalysts for Knoevenagel Condensation 铁-氢键框架的氟化组装作为Knoevenagel缩合的双官能Lewis酸碱催化剂

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-11-09 Epub Date: 2026-10-29 DOI: 10.1021/acs.inorgchem.6c04482

Zi-Jian Xue, Lai-Min Wang, Yu-Han-Xu Zhou, Yu-Hui Luo, Dong-En Zhang

{"title":"Fluoride-Enabled Assembly of Iron–Hydrogen-Bonded Frameworks as Bifunctional Lewis Acid–Base Catalysts for Knoevenagel Condensation","authors":"Zi-Jian Xue, Lai-Min Wang, Yu-Han-Xu Zhou, Yu-Hui Luo, Dong-En Zhang","doi":"10.1021/acs.inorgchem.6c04482","DOIUrl":"10.1021/acs.inorgchem.6c04482","url":null,"abstract":"The development of recyclable heterogeneouscatalyststhat enableefficient organic transformations without solvents is important forsustainable chemical synthesis. In this work, two new fluoride-mediatedmetal–hydrogen-bonded organic frameworks (M-HOFs), labeledas JOU-40 and JOU-41, were successfully synthesized. Single-crystalX-ray diffraction reveals that both M-HOFs feature [Fe3F11]n chains that are extendedinto three-dimensional supramolecular networks through O–H···Fhydrogen bonds. The resulting frameworks integrate Lewis-acidic ironcenters and basic fluoride sites within a confined porous environment,enabling efficient Lewis acid–base catalysis. As heterogeneouscatalysts, JOU-40 and JOU-41 efficiently promote the solvent-freeKnoevenagel condensation of benzaldehyde with malononitrile, affording>99.00% conversion and selectivity. The catalyst also exhibitsgoodsubstrate compatibility across a range of substituted aldehydes. Morefascinatingly, kinetic analyses reveal that the reaction can be describedby the Avrami nucleation–growth model, highlighting the coupledcontributions of chemical conversion and product crystallization.Density functional theory (DFT) calculations demonstrate that theadjacent Fe3+ and F– sites activate thetwo reactants and facilitate C═C bond formation, providinga molecular-level basis for the observed catalytic activity. Thiswork offers new design insights for developing highly efficient, stable,and recyclable catalytic systems for solvent-free Knoevenagel condensation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 44","pages":"26141–26149"},"PeriodicalIF":4.6,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149281805","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}

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Dynamic Electronic Structure of the FeMoco Enables Mechanistic Coupling between N2 Binding and H2 Evolution in Nitrogenase FeMoco的动态电子结构实现了氮酶中N2结合和H2演化的机制耦合

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-11-09 Epub Date: 2026-10-29 DOI: 10.1021/acs.inorgchem.6c03876

Janavi Rajput, Bhaskar Mondal

{"title":"Dynamic Electronic Structure of the FeMoco Enables Mechanistic Coupling between N2 Binding and H2 Evolution in Nitrogenase","authors":"Janavi Rajput, Bhaskar Mondal","doi":"10.1021/acs.inorgchem.6c03876","DOIUrl":"10.1021/acs.inorgchem.6c03876","url":null,"abstract":"The mechanistic coupling of N2 binding andH2 evolution through reductive elimination from the E4 intermediateconstitutes a critical step in the nitrogenase catalytic cycle. Despiteextensive mechanistic investigations, how the Fe centers within theFeMoco cofactor dynamically reorganize their local electronic structuresto facilitate this coupled process remains unresolved. Here, usingdensity functional theory (DFT) combined with intrinsic atomic orbital/intrinsicbond orbital (IAO/IBO) and natural bond orbital (NBO) analyses, weuncover the electronic structure evolution of FeMoco along the coupledN2-binding/H2-evolution reaction coordinate.Comparative analyses of reaction energetics, with appropriate transitionstates, support an “intermediate” mechanism over purely“associative” or “dissociative” pathways,revealing a key intermediate E4(H2N2) in which N2 and H2 are simultaneously coordinated to the same Fe center. Detailed molecular-orbitalanalyses demonstrate that the coupled reaction is enabled by highlysynchronized electronic reorganization across neighboring Fe centers,which dynamically redistribute electron density to stabilize concurrentH2 release and N2 activation. In particular,cooperative Fe–Fe electronic coupling allows the reactive Fesite to adapt its local bonding interactions. These findings providean electronic-level rationale for the functional necessity of themultinuclear FeMoco architecture and reveal how orchestrated electronicflexibility within the cluster governs the critical mechanistic stepof nitrogenase catalysis.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 44","pages":"25929–25944"},"PeriodicalIF":4.6,"publicationDate":"2026-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149281883","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