Inorganic Chemistry最新文献

{"title":"Phase-Selective Synthesis of Copper Phosphosulfide Nanocrystals","authors":"Haley L. Young,&nbsp;Danushki N. Suriyawansa,&nbsp;Raymond E. Schaak","doi":"10.1021/acs.inorgchem.6c04130","DOIUrl":"10.1021/acs.inorgchem.6c04130","url":null,"abstract":"<p>Copper phosphosulfides,including Cu₇PS₆ andCu₃PS₄, are important materials for their ionic,electronic, and thermal conductivity properties. However, nanocrystalsof these copper phosphosulfides are surprisingly rare. Here, we showthat both Cu₇PS₆ and Cu₃PS₄ nanocrystals can be synthesized by reacting CuCl, P₂S₅, 1-dodecanethiol, and oleylamine at 250 °C for 1 h,with all reagents playing key roles in the synthesis. Phase selectivityis achieved by controlling reagent concentration, which is relatedto the reaction chemistry that is implicated in the formation of thenanocrystal products. Cu₇PS₆ forms tetrahedron-shapednanocrystals while Cu₃PS₄ forms tetrapods, whichcan be rationalized by crystal structure relationships. The successfulformation of Cu₇PS₆ and Cu₃PS₄ represents an important addition to the library of syntheticallyaccessible nanocrystals with well-defined morphologies.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24483–24491"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091906","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}

{"title":"Solution Spectroscopic Analysis of Ligand Exchange in Uranium Mono-Oxo Complexes","authors":"Florian Ressnik,&nbsp;Tyler-Rayne Nero,&nbsp;Maximilian G. Bernbeck,&nbsp;Johannes Leisen,&nbsp;Bess Vlaisavljevich,&nbsp;Julie E. Niklas,&nbsp;Henry S. La Pierre","doi":"10.1021/acs.inorgchem.6c03607","DOIUrl":"10.1021/acs.inorgchem.6c03607","url":null,"abstract":"<p>Four uranium mono-oxoimidophosphorane complexes witha closedset of systematically changed substituents (pyrrolidine vs piperidineand introduction of one <em>tert</em>-butyl group) are presented.All complexes exhibit an inverse <em>trans</em>-influence(ITI). The rapid exchange of axial and equatorial ligands at roomtemperature, the unique ³¹P nuclear magnetic resonance(NMR) handle of the ligands, and the complexes’ overall closed-shellsinglet ground state facilitate the determination of ligand-exchangebarriers via variable-temperature (VT) and exchange spectroscopy (EXSY)NMR. Computational analysis delineates electronic and steric contributionsto the experimentally determined exchange barriers.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24331–24342"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091941","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}

{"title":"Influence of the Cation Size on Symmetry Breaking and Optical Performances in Ae2Mg3(BO3)2F4 (Ae = Sr, Ba)","authors":"Yu Qiu,&nbsp;Haonan Liu,&nbsp;Yujie Zhang,&nbsp;Hongping Wu,&nbsp;Hongwei Yu","doi":"10.1021/acs.inorgchem.6c04224","DOIUrl":"10.1021/acs.inorgchem.6c04224","url":null,"abstract":"<p>The rational design of noncentrosymmetric (NCS) boratesremainschallenging because subtle variations in the arrangement of microscopicfunctional units can profoundly influence macroscopic symmetry andnonlinear optical (NLO) behavior. Herein, we report two new alkaline-earthborate fluorides, Sr₂Mg₃(BO₃)₂F₄ and Ba₂Mg₃(BO₃)₂F₄, featuring identical [BO₃]triangles and Mg–O/F polyhedra, but crystallizing in distinctspace groups, namely <em>P</em>1̅ for Sr₂Mg₃(BO₃)₂F₄ and <em>Fdd</em>2 for Ba₂Mg₃(BO₃)₂F₄. Structural analysis indicates that replacingSr²⁺ with the larger Ba²⁺ cation modifies thelocal coordination environment around the alkaline-earth cation andthe distortion of the Mg–O/F framework, which results in thereorganization of [BO₃] units from an antiparallel arrangementto a cooperative polar alignment. Property measurements indicate thatBa₂Mg₃(BO₃)₂F₄ exhibits a significant second-harmonic generation response, suitablebirefringence, and a short UV cutoff edge down to 190 nm. A structure–propertyrelationship study confirms that the [BO₃] units are theprimary source of the optical response. This work not only providesa promising deep-ultraviolet NLO crystal but also reveals a cation-mediatedsymmetry engineering strategy to design NCS borates.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24505–24512"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091951","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}

{"title":"Polyoxometalate-Incorporated Metal–Organic Frameworks for Electrochemical Sensing of Dihydroxybenzene Isomers","authors":"Shuang Liu,&nbsp;Li-Ping Wang,&nbsp;Jia-Jia Li,&nbsp;Xiang-Jie Bo,&nbsp;Dong-Ying Du,&nbsp;Zhong-Min Su","doi":"10.1021/acs.inorgchem.6c02898","DOIUrl":"10.1021/acs.inorgchem.6c02898","url":null,"abstract":"<p>Dihydroxybenzene isomers are highlytoxic and resistantto naturaldegradation and pose a serious threat to the ecological environment.Therefore, developing efficient and accurate detection methods iscrucial for preventing and controlling their environmental risks.A series of polyoxometalate-incorporated bimetallic metal–organicframeworks, MIL-101(Cr_<em>x</em>Al)-POM-T (<em>x</em> = 1.6 or 2, POM = SiW₁₂ or PW₁₂, <em>T</em> =180 or 220), were synthesized via a hydrothermal method.They were employed as electrochemical sensors determining dihydroxybenzeneisomers (including hydroquinone (HQ), catechol (CC), and resorcinol(RS)). By introducing different ratios of chromium(III) to aluminum(III)centers and POM types within MIL-101(Cr_<em>x</em>Al)-POM-T, the current responses and selectivity toward differentdihydroxybenzene isomers were judiciously optimized. Among them, MIL-101(Cr_1.6Al)-PW₁₂-220 exhibited the optimal electrochemicalbehavior with wide linear response ranges (2–120, 2–100,and 20–260 μM) and low limits of detection (0.102, 0.225,and 4.615 μM, S/N = 3) for the individual detection of HQ, CC,and RS. In addition, the excellent selectivity, reproducibility, andstability endow MIL-101(Cr_1.6Al)-PW₁₂-220 withgreat potential to detect dihydroxybenzene isomers in real water samples.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24165–24174"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091952","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}

{"title":"Bimetallic Aluminum Hydride s-Block (Li, Na, K) Compounds in Catalytic Hydroboration","authors":"Enric Sabater,&nbsp;Benedikt Meiser,&nbsp;Daniel Schroeder,&nbsp;Bernd Morgenstern,&nbsp;Eva Hevia,&nbsp;Diego M. Andrada","doi":"10.1021/acs.inorgchem.6c02398","DOIUrl":"10.1021/acs.inorgchem.6c02398","url":null,"abstract":"<p>Hydroboration is an important transformation for preparingsyntheticintermediates that participate in numerous reactions. While traditionallycatalyzed by transition metals, the pursuit of more sustainable methodologieshas prompted the development of catalysts based on earth-abundantelements. Aluminum hydrides have been employed as (pre)catalysts forthe hydroboration of unsaturated functional groups, exhibiting enhancedactivity in their ate complexes through alkali-metal cooperativity,yet the identity of the active species, particularly in carbonyl hydroboration,remains under debate. Herein, we report the isolation and full characterizationof a series of alkali metal (Li, Na, and K) aluminate hydride complexeswith bis(aminophosphino-borane)naphthalene as a supporting ligand.We explore and benchmark their catalytic activity in the hydroborationof benzophenone and phenylacetylene using pinacolborane (HBpin). Therole of the aluminates, the origin of synergistic effects, and theproposed reaction mechanisms are examined through stoichiometric studies,the isolation of intermediates, and DFT calculations.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24129–24144"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151421","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}

{"title":"Dipyridylamine-Functionalized N-Heterocyclic Carbene Ligands for Structurally Diverse Silver(I) and Gold(I) Complexes: Topology, Metallophilic Interactions, and Structure–Property Relationships","authors":"Xun-Rong Wang,&nbsp;Zhi-Lin Wang,&nbsp;Su-Ying Chien,&nbsp;Shao-An Hua","doi":"10.1021/acs.inorgchem.6c03372","DOIUrl":"10.1021/acs.inorgchem.6c03372","url":null,"abstract":"<p>Macrocyclic N-heterocyclic carbene (NHC) ligands incorporatingmultidentate donor motifs offer opportunities for constructing structurallydiverse coordination complexes. Herein we report a family of dipyridylamine(DPA)-functionalized NHC ligands comprising acyclic ([<strong>H</strong>_{<strong>2</strong>}<strong>L</strong>^{<strong>1</strong>}](PF₆)₂) and macrocyclic architectures ([<strong>H</strong>_{<strong>4</strong>}<strong>L</strong>^{<strong>2</strong>}](OTf)₄ and [<strong>H</strong>_{<strong>4</strong>}<strong>L</strong>^{<strong>3</strong>}](OTf)₄) with distinct coordinationtopologies. Structural studies reveal linker-dependent ligand conformationsranging from Z-shaped and double-V structures to folded and extendedmacrocycles, enabling tunable cavity sizes and coordination environments.Metalation with Ag(I) and Au(I) affords mono-, di-, and trinuclearcomplexes. The trinuclear silver complex [(<strong>AgL</strong>^{<strong>1</strong>})_{<strong>2</strong>}<strong>Ag</strong>](PF₆)₃ and heterometallic complex [(<strong>AuL</strong>^{<strong>1</strong>})_{<strong>2</strong>}<strong>Ag</strong>](PF₆) feature short metal–metal separations consistent with metallophilicinteractions. In solution, DOSY NMR and mass spectrometry identify[<strong>AgL</strong>^{<strong>1</strong>}]⁺ and [<strong>AuL</strong>^{<strong>1</strong>}]⁺ as the predominantspecies, suggesting dissociation of the trinuclear assemblies. Variable-temperatureNMR and thermodynamic analyses reveal comparable exchange dynamicsfor the ethylene-linked [<strong>Ag</strong>_{<strong>2</strong>}<strong>L</strong>^{<strong>2</strong>}](OTf)₂ and [<strong>Au</strong>_{<strong>2</strong>}<strong>L</strong>^{<strong>2</strong>}](OTf)₂. Selected complexes exhibit enhanced solid-state luminescencearising from cooperative π–π stacking and metallophilicinteractions, whereas antibacterial studies reveal enhanced activityupon metal coordination, with the Ag(I) complexes showing pronouncedactivity toward <em>Escherichia coli</em> (<em>E. coli</em>) and the Au(I) complexes exhibiting greatersolution stability and broader antibacterial activity. These resultsestablish DPA-functionalized NHC ligands as versatile platforms forcoinage-metal assemblies with tunable topology, metal–metalinteractions, photophysical properties, and biological activity.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24259–24272"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091903","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}

{"title":"Halogen-Regulated Noncovalent Interactions in Coordination Polymers Enable Photothermal Conversion","authors":"Rui Wang,&nbsp;Mingru Yin,&nbsp;Jun Pan,&nbsp;Jiaoyang Chen,&nbsp;Zhiqiang Fang,&nbsp;Zhao-Peng Qi","doi":"10.1021/acs.inorgchem.6c02919","DOIUrl":"10.1021/acs.inorgchem.6c02919","url":null,"abstract":"<p>Regulatingintermolecular noncovalent interactions at the atomiclevel poses a significant challenge for the design and optimizationof photothermal conversion materials in coordination polymers. Herein,we develop a series of one-dimensional zinc-based coordination polymers,[ZnX₂(μ-dptz)]_<em>n</em> (X =Cl, Br, I; 4,4′-dptz = 3,6-di(pyridin-4-yl)-1,2,4,5-tetrazine),where systematic variation of the terminal halogen modulates interchainC–H···X hydrogen bonds and anion···πinteractions, whose strengths decrease in the order <strong>ZnCl</strong>_{<strong>2</strong>}<strong>-dptz</strong> &gt; <strong>ZnBr</strong>_{<strong>2</strong>}<strong>-dptz</strong> &gt; <strong>ZnI</strong>_{<strong>2</strong>}<strong>-dptz</strong>. Halogen substitutioneffectivelymodulates the crystal packing and electronic distribution, endowingall CPs with broad visible-light absorption and excellent thermalstability. Under 525 nm laser irradiation, the CPs exhibit stableand reversible photothermal performance, and the photothermal conversionefficiency (η) follows <strong>ZnCl</strong>_{<strong>2</strong>}<strong>-dptz</strong> (52.3%) &gt; <strong>ZnBr</strong>_{<strong>2</strong>}<strong>-dptz</strong> (44.0%) &gt; <strong>ZnI</strong>_{<strong>2</strong>}<strong>-dptz</strong> (41.9%). Photoluminescence resultsconfirmthat the strengthened noncovalent networks in <strong>ZnCl</strong>_{<strong>2</strong>}<strong>-dptz</strong> significantly restrain radiativedecay and maximize thermal energy dissipation. This work elucidatesthe halogen-modulated supramolecular interaction–photothermalperformance relationship, offering a rational strategy for designinghigh-efficiency photothermal CPs.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24155–24164"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091944","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}

{"title":"Bi12Rh3Ag6I9: Mobile Silver Ions and Surface-Dominated Transport in a Layered Weak Topological Insulator","authors":"Eduardo Carrillo-Aravena,&nbsp;Johannes Heßdörfer,&nbsp;Christian N. Saggau,&nbsp;Armando Consiglio,&nbsp;Shailja Sharma,&nbsp;Friedrich Reinert,&nbsp;Giorgio Sangiovanni,&nbsp;Domenico Di Sante,&nbsp;Oleg Janson,&nbsp;Kornelius Nielsch,&nbsp;Nicolás Pérez,&nbsp;Michael Ruck","doi":"10.1021/acs.inorgchem.6c02517","DOIUrl":"10.1021/acs.inorgchem.6c02517","url":null,"abstract":"<p>Bi₁₂Rh₃Ag₆I₉ extendsthe Bi₁₄Rh₃I₉ family of layered bismuth-richiodides in which intermetallic topological-insulator sheets alternatewith salt-like spacer layers. High-temperature synthesis yields phase-purepowders and millimeter-sized platelets. Single-crystal X-ray diffractionreveals a rhombohedral structure composed of [Bi₁₂Rh₃I]²⁺ layers and [Ag₆I₈]^2– spacers. In this spacer, Ag⁺ cations occupy75% of the tetrahedral voids of a double iodide layer, giving riseto intrinsic two-dimensional cation disorder and mobility. Electrochemicalimpedance spectroscopy reveals a room-temperature ionic conductivityof about 10^–6 S cm^–1. Density-functionaltheory including spin–orbit coupling predicts band inversionand weak-topological-insulator invariants, while angle-resolved photoemissionspectroscopy corroborates the calculated bulk electronic structure,yielding an experimental bulk band gap of 286 meV. Transport measurementsshow strongly anisotropic, initially <em>n</em>-type conduction.During the initial measurement cycle, applied bias reduces the electrondoping through slow electrochemical deintercalation of silver. Afterconditioning, bulk conduction is strongly reduced; transport belowabout 130 K becomes nonactivated, the bias-induced drift ceases belowabout 50 K as Ag⁺ motion freezes, and a pronounced resistivitydrop perpendicular to the layers below 3.2 K is suggestive of a boundary-sensitivelow-dimensional transport regime. Bi₁₂Rh₃Ag₆I₉ demonstrates that spacer chemistry providesa chemical lever for carrier-density control in layered topologicalinsulators.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24145–24154"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091947","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}

{"title":"Where Are Eu? Structural Diversity from Coloring Variants in Tellurides Eu(Al1–xGax)2Te4","authors":"Pritam Das,&nbsp;Trinanjan Dey,&nbsp;Vidyanshu Mishra,&nbsp;Chloe F. McLeod,&nbsp;Dmitry Vrublevskiy,&nbsp;Zhongqi Lin,&nbsp;Arthur Mar","doi":"10.1021/acs.inorgchem.6c04306","DOIUrl":"10.1021/acs.inorgchem.6c04306","url":null,"abstract":"<p>The mixed-cation tellurides Eu(Al_{1–<em>x</em>}Ga_<em>x</em>)₂Te₄ (<em>x</em> = 0–1) were synthesizedusing two thermal profiles,resulting in subtly different structural features. Samples preparedby one-step annealing at 700 °C exhibit a composition-dependenttransformation from a body-centered orthorhombic structure with alarger cell (space group <em>Ibam</em>, <em>x</em> = 0–0.50) to a side-centered orthorhombic structure witha smaller cell (space group <em>Cccm</em>, <em>x</em> = 0.75–1.0) as the Ga content increases. Samples preparedby two-step annealing at 700 and 400 °C retain the <em>Ibam</em> structure throughout the entire composition range, implying thatthe Ga-richest samples such as EuGa₂Te₄ undergoa temperature-dependent structural transition, as confirmed from variable-temperaturepowder X-ray diffraction experiments. The structures consist of acommon framework of infinite linear chains of edge-sharing <em>M</em>Te₄ (<em>M</em> = Al, Ga) tetrahedrabut differ in terms of the site distribution of intervening Eu atoms.These compounds are semiconductors with narrow optical band gaps of0.6–0.9 eV. Based on calculated transport properties, theymay be suitable candidates for thermoelectric applications at hightemperatures. They undergo electrocatalysis for water splitting, butwith room for improvement in their performance.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24535–24547"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091948","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}

{"title":"Hypercoordinated Dicarbanion-Bonded Ag19 Cluster: Synergistic Substrate Activation and Dynamic Surface Reorganization in Catalysis","authors":"Cong Jin,&nbsp;Keting Zhou,&nbsp;Yu Xia,&nbsp;Jinbing Li,&nbsp;Cui-Cui Li,&nbsp;Wei Li,&nbsp;Liang Zhao","doi":"10.1021/acs.inorgchem.6c04565","DOIUrl":"10.1021/acs.inorgchem.6c04565","url":null,"abstract":"<p>Surfaceligands are crucial for maintaining the structural stabilityand integrity of metal nanoclusters, yet high ligand coverage oftenhinders substrate access to active metal sites. In this work, we demonstratethat an in situ generated aryl dianion ligand <strong>Py-Indole</strong> with a high coordination mode of μ₅-C,C,N-η³,η²,η¹ can significantlyreduce surface coverage and expose accessible metal sites. As a result,only six <strong>Py-Indole</strong> ligands are enough to stabilize anellipsoidal Ag₁₉ nanocluster core. The low ligand coverageon the Ag₁₉ cluster surface exposes two Ag₃ caps,which enable the binding and activation of terminal alkynes and leadto the isolation of several acetylide-bonded Ag₁₉ intermediates.Meanwhile, the basic dicarbanion sites of <strong>Py-Indole</strong> readilydeprotonate the hydroxyl group in substrates, which together withthe alkyne activation by silver atoms synergistically promote an intramolecularcyclization reaction at room temperature. The newly formed aryl dicarbanionsundergo a recurring double proton exchange process with incoming substratemolecules to sustain the catalytically active state and drive thecyclization reaction forward with aturnover number up to 320. Thesynergistic integration of low-coverage ligand architecture, polymetallicactivation, and substrate–ligand-product role-switching mechanismprovides a transformative strategy for developing highly active andstructurally resilient cluster catalysts in the future.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24603–24611"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151418","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}