Inorganic Chemistry最新文献

{"title":"Exploring Charge Redistribution at the Cu/Co6Se8 Interface","authors":"Sebastian M. Krajewski, Robert J. Love, Jr., Jonathan A. Kephart, Andrew C. Boggiano, Henry S. La Pierre, Werner Kaminsky, Alexandra Velian","doi":"10.1021/acs.inorgchem.4c02639","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c02639","url":null,"abstract":"This study investigates the electronic interactions and charge redistribution at the dopant–support interface using a Cu/Co₆Se₈ cluster construct. Specifically, the redox cluster series [Cu₃Co₆Se₈L₆]^<i>n</i> ([<b>1</b>-Cu₃]^<i>n</i>; <i>n</i> = 0, −1, −2, −3; L = Ph₂PNTol^–, Ph = phenyl, Tol = <i>p</i>-tolyl) spanning four distinct oxidation states is synthesized and characterized using a multitude of techniques, including multinuclear NMR, UV–vis, XANES, and X-ray crystallography. Structural investigations indicate that the clusters are isostructural and chiral, adopting a pseudo-<i>D</i>₃ symmetry. Paramagnetic ³¹P NMR spectroscopy and solution-phase magnetic measurements together with DFT calculations are employed to interrogate the electronic structure and spin-state changes across the [<b>1</b>-Cu₃]^3– to <b>1</b>-Cu₃ redox series, revealing that the copper edge sites retain a +1 oxidation state while the Co/Se core becomes increasingly oxidized, yielding a highly zwitterionic cluster.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142451951","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":"Stereoelectronic Tuning of Bioinspired Nonheme Iron(IV)-Oxo Species by Amide Groups in Primary and Secondary Coordination Spheres for Selective Oxygenation Reactions","authors":"Rahul Dev Jana, Abhishek Das, Rajib Samanta, Sridhar Banerjee, Satadal Paul, Tapan Kanti Paine","doi":"10.1021/acs.inorgchem.4c03155","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03155","url":null,"abstract":"Two mononuclear iron(II) complexes, [(6-amide₂-BPMEN)Fe^II](OTf)₂ (<b>1</b>) and [(6-amide-Me-BPMEN)Fe^II(OTf)](OTf) (<b>2</b>), supported by two BPMEN-derived (BPMEN = <i>N</i>¹,<i>N</i>²-dimethyl-<i>N</i>¹,<i>N</i>²-bis(pyridine-2-yl-methyl)ethane-1,2-diamine) ligands bearing one or two amide functionalities have been isolated to study their reactivity in the oxygenation of C–H and C═C bonds using isopropyl 2-iodoxybenzoate (<i>i</i>Pr-IBX ester) as the oxidant. Both <b>1</b> and <b>2</b> contain six-coordinate high-spin iron(II) centers in the solid state and in solution. The 6-amide₂-BPMEN ligand stabilizes an <i>S</i> = 1 iron(IV)-oxo intermediate, [(6-amide₂-BPMEN)Fe^IV(O)]²⁺ (<b>1A</b>). The oxidant (<b>1A</b>) oxygenates the C–H and C═C bonds with a high selectivity. Oxidant <b>1A</b>, upon treatment with 2,6-lutidine, is transformed into another oxidant [{(6-amide₂-BPMEN)-(H)}Fe^IV(O)]⁺ (<b>1B</b>) through deprotonation of an amide group, resulting in a stronger equatorial ligand field and subsequent stabilization of the triplet ground state. In contrast, no iron-oxo species could be observed from complex <b>2</b> and [(6-Me₂-BPMEN)Fe^II(OTf)₂] (<b>3</b>) under similar experimental conditions. The iron(IV)-oxo oxidant <b>1A</b> shows the highest A/K selectivity in cyclohexane oxidation and 3°/2° selectivity in adamantane oxidation reported for any synthetic nonheme iron(IV)-oxo complexes. Theoretical investigation reveals that the hydrogen bonding interaction between the −NH group of the noncoordinating amide group and Fe═O core smears out the equatorial charge density, reducing the triplet–quintet splitting, and thus helping complex <b>1A</b> to achieve better reactivity.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452305","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":"Silyl- and Germyl-Substituted Boranes: Synthesis and Investigation as Potential Atomic Layer Deposition Precursors","authors":"Majeda Al Hareri, Patricio Romero, James F. Britten, David J. H. Emslie","doi":"10.1021/acs.inorgchem.4c03416","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03416","url":null,"abstract":"Boranes featuring bulky hypersilyl or supersilyl groups and/or sterically unencumbered trimethylgermyl substituents were synthesized for investigation as potential precursors for atomic layer deposition (ALD) of elemental boron. The envisaged ALD process would employ a boron trihalide coreactant, exploiting the formation of strong silicon-halogen and germanium-halogen bonds as a driving force. The alkali metal silyl and germyl compounds hypersilyl lithium, {(Me₃Si)₃Si}Li(THF)₃ (<b>1</b>), supersilyl sodium, (^<i>t</i>Bu₃Si)Na(THF)_<i>n</i> (<b>2</b>, <i>n</i> = 2–3), and trimethylgermyl lithium, {Me₃GeLi(THF)₂}₂ (<b>3</b>), were used for the synthesis of the silyl- and germyl-substituted boranes in this work. Compounds <b>1</b> and <b>2</b> were synthesized as previously reported, and compound <b>3</b> was isolated from the reaction of trimethylgermane with <i>tert</i>-butyl lithium. Compounds <b>2</b> and <b>3</b> were crystallographically characterized. Reaction of B(NMe₂)Cl₂ with 2 equiv of <b>1</b> afforded previously reported {(Me₃Si)₃Si}₂B(NMe₂) (<b>4</b>), whereas reactions of B(NMe₂)Cl₂ or {B(NMe₂)F₂}₂ with excess <b>2</b> only afforded the monosilyl boranes (^<i>t</i>Bu₃Si)B(NMe₂)X {X = Cl (<b>5</b>) and F (<b>6</b>)}. Reaction of <b>5</b> with 0.5 equiv of {Me₃GeLi(THF)₂}₂ (<b>3</b>) provided the first example of a mixed silyl/germyl-substituted borane, (^<i>t</i>Bu₃Si)(Me₃Ge)B(NMe₂) (<b>7</b>). Attempts to synthesize (Me₃Ge)₂B(NMe₂) from the 1:1 reaction of B(NMe₂)Cl₂ with {Me₃GeLi(THF)₂}₂ afforded a mixture of two major products, one of which was identified as the tri(germyl)(amido)borate {(Me₃Ge)₃B(NMe₂)}Li(THF)₂ (<b>8</b>); compound <b>8</b> was isolated from the 1:1.5 reaction. Reaction of more sterically encumbered B(TMP)Cl₂ with 1 equiv of {Me₃GeLi(THF)₂}₂ afforded the di(germyl)(amido)borane (Me₃Ge)₂B(TMP) (<b>9</b>). Boranes <b>4</b>, <b>7</b>, and <b>9</b> and borate <b>8</b> were crystallographically characterized. The thermal stability and volatility of boranes <b>4</b>, <b>7</b>, and <b>9</b> was evaluated, the solution reactivity of <b>4</b> and <b>7</b> with boron trihalides was assessed, and ALD was attempted using <b>4</b> in combination with BCl₃ and BBr₃ at 150 and 300 °C.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142451953","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":"Crystal and Local Structures of Pr2Co7Dx during Its Deuterium Absorption Process Determined by Neutron Diffraction","authors":"Kenji Iwase, Yuhei Shitoh, Kazuhiro Mori","doi":"10.1021/acs.inorgchem.4c03680","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03680","url":null,"abstract":"We investigated crystal and local structures of Pr₂Co₇, Pr₂Co₇D_2.7 and Pr₂Co₇D_7.2 by neutron diffraction. The determined structural model of Pr₂Co₇D_2.7 was the Ce₂Ni₇-type structure by Rietveld refinement, where the deuterium atoms occupied both the CaCu₅-type (I) and the MgZn₂-type cells. The deuterium contents in these cells were 0.10 and 0.80 D/M, respectively. The expansions of the lattice parameters of Pr₂Co₇D_2.7 from the original intermetallics were Δ<i>a</i> = 0.3% and Δ<i>c</i> = 7.3%. The crystal structure transformed in the order Ce₂Ni₇-type Pr₂Co₇ → Ce₂Ni₇-type Pr₂Co₇D_2.7 → orthorhombic Pr₂Co₇D_7.2. The expansions of the lattice parameters of Pr₂Co₇D_7.2 from the original intermetallics were Δ<i>a</i> = 5.9%, Δ<i>b</i> = 6.2%, and Δ<i>c</i> = 6.4%; nearly isotropic expansion was observed. The deuterium contents in the MgZn₂-type, CaCu₅-type (I), and CaCu₅-type (II) cells were 1.11, 0.44, and 0.83 D/M, respectively. The refined structural parameters by a pair distribution function (PDF) analysis on Pr₂Co₇ (0.18 &lt; <i>r</i> &lt; 5.0 nm) and Pr₂Co₇D_2.7 (0.13 &lt; <i>r</i> &lt; 5.0 nm) obtained were consistent with those obtained by Rietveld refinement. The Rietveld refinement results of the refined lattice parameters of Pr₂Co₇D_7.2 corresponded with the PDF analysis results in the region of 0.13 &lt; <i>r</i> &lt; 5.0 nm, whereas the refined atomic coordinates of the atoms D1, D2, D4, D6, and D9 obtained by the two methods differed. The refined structural parameters of the short-range structure (0.13 &lt; <i>r</i> &lt; 1.0 nm) in Pr₂Co₇D_7.2 did not correspond to those of the long-range structure (0.13 &lt; <i>r</i> &lt; 5.0 nm). The local distortion within the domain of approximately 1.0 nm in size exists in Pr₂Co₇D_7.2.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452308","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":"Reactivity of Diruthenium Bisborylene Complexes: Formation of B–C and B–H Bonds via Borylene Ligand Coupling","authors":"Yongliang Wei, Xiaowen Yang, Min Liu, Xue Wang, Yang Li, Tongdao Wang","doi":"10.1021/acs.inorgchem.4c04093","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04093","url":null,"abstract":"Thermal or photoinduced isomerization of diruthenium bridging bisborylene complexes [{Cp*(H)₂Ru}₂(μ-BAr)₂] (<b>1a</b>, Ar = Ph; <b>1b</b>, Ar = 3,4,5-F₃C₆H₂) led to <i>nido</i>-ruthenacarboranes <b>2a</b> and <b>2b</b> with newly formed B–C and B–H bonds. The reaction mechanism was analyzed by deuterium-labeling experiments and density functional theory calculations. Additionally, 2-fold B–H coupling between borylene and two hydrido ligands of <b>1a</b> can be achieved, assisted by Lewis base IPr₂Me₂ to generate a dinuclear bridging borylene complex [(Cp*Ru)₂(μ-H)₂(μ-BPh)] (<b>3</b>). Our results provide new reactivity patterns for borylene-based functionalizations.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142451952","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":"Structural Phase Transitions of Mg2NiH4 Induced by NiH4 Molecular Ion Distortion and Metal Lattice Deformation under High Pressures","authors":"Takuma Shiga, Takashi Yagi, Hiroshi Fujihisa","doi":"10.1021/acs.inorgchem.4c03336","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03336","url":null,"abstract":"Experimental observations indicate that pressure treatments transform the monoclinic and orthorhombic low-temperature phases of Mg₂NiH₄ into an unresolved pseudocubic phase even at room temperatures, resembling the temperature-induced phase transformation of the material. This pressure-induced phase transformation is anticipated to involve deformations of the tetrahedrally bonded NiH₄ molecular ion and the metal lattice. However, the precise mechanism underlying this transformation remains unclear. To elucidate this behavior, this study adopted first-principles density functional theory calculations to investigate the effect of applied pressure on the observed phase transition. The results revealed that the phase transition from the low-temperature phases to the pseudocubic phase occurs at approximately 8–9 GPa. Furthermore, at this pressure, the metal lattice deforms into an antifluorite-like structure, and the NiH₄ molecular ion undergoes substantial distortion, resulting in the alignment of hydrogen atoms along the crystal axes of the metal lattice. Furthermore, through a comprehensive structural exploration, we successfully identified several tetragonal and orthorhombic models that are energetically more stable than the low-temperature phases at low pressures. These models are potential candidates for elucidating the pseudocubic phase observed in experiments. Overall, our findings are anticipated to enhance the current understanding of the structural changes occurring during pressure and temperature-induced phase transitions.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452307","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":"Thermal Quenching Mechanism of Mn4+ in Na2SiF6, NaKSiF6, and K2SiF6 Phosphors: Insights from the First-Principles Analysis","authors":"Mekhrdod S. Kurboniyon, Alok M. Srivastava, Bibo Lou, Dilshod D. Nematov, Amondulloi Burhonzoda, Tomoyuki Yamamoto, Chong-Geng Ma, Mikhail G. Brik","doi":"10.1021/acs.inorgchem.4c03589","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03589","url":null,"abstract":"This study aims to identify the key factors governing the thermal quenching of Mn⁴⁺ ion luminescence in fluoride-based phosphor materials used as red emitters in modern-day phosphor-converted LED devices. Here, we employ first-principles calculations for Mn⁴⁺-doped Na₂SiF₆, NaKSiF₆, and K₂SiF₆ hosts to explore how host properties and local coordination environments influence thermal quenching behavior. The ΔSCF method was used to model the geometric structures of the Mn⁴⁺⁴A₂ (ground) and ²E, ⁴T₂ (excited) states and the energies of the optical transitions between these states. Our results reveal that thermal quenching in Na₂SiF₆ and K₂SiF₆ phosphors occurs through thermally activated ²E → ⁴T₂ → ⁴A₂ crossover. In contrast, thermal quenching in NaKSiF₆ is due to other nonradiative decay pathways. Investigations of the mechanical stability of these fluorides show that NaKSiF₆ is mechanically unstable. We suggest that this property of the host limits the luminescence efficiency of the embedded Mn⁴⁺ ions. We also determined the reason for the difference in the intensity of the ²E → ⁴A₂ emission transition (ZPL) in the systems. These findings advance our fundamental understanding of the thermal quenching mechanism of Mn⁴⁺ ion luminescence in fluorides, and the results can aid future discoveries of technologically useful phosphors through high-throughput design methodologies.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452344","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":"Proton-Coupled Electron Transfer between a Pendant Thiol and a Ferrous Dioxygen Adduct","authors":"Souvik Dinda, Triparna Roy, Soumya Samanta, Kumarjit Banerjee, Nicholas Cox, Abhishek Dey","doi":"10.1021/acs.inorgchem.4c03802","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03802","url":null,"abstract":"The mechanism of thiol oxidation by O₂, as catalyzed by ferrous porphyrins, is investigated by trapping intermediates of the transformation at low temperatures and subsequently characterizing them using continuous wave and pulsed electron paramagnetic resonance and resonance Raman spectroscopy. A Fe(III)-O₂^•– species is initially formed in an iron porphyrin with a pendant thiol functional group, which undergoes proton-coupled electron transfer (PCET) (not HAT) to form an Fe(III)-OOH species. Following O–O bond homolysis, this forms a Fe(IV)═O species with concomitant oxidation of the thiol to an RSO₃H group.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142451954","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":"Improving the Electrocatalytic Activity of a Core/Shell NiCo–ZIF@PBA Catalyst by Co–O–Fe Bridge Bonds for Water Oxidation","authors":"Tianhao Yu, Peng Gao, Yu Wang, Maidina Muhetaer, Hong Du","doi":"10.1021/acs.inorgchem.4c02204","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c02204","url":null,"abstract":"In response to the limitations of slow reaction kinetics and elevated overpotentials in the OER, a novel core–shell structured electrocatalyst, termed NiCo–ZIF-67@Fe–Co–Ni-PBA or NiCo–ZIF@PBA, has been developed. This material demonstrates exceptional catalytic performance, exhibiting a minimal overpotential of approximately 188 mV at 10 mA cm^–2, alongside a Tafel slope of 109 mV dec^–1. Its robust stability in a 1 M KOH solution during the OER operations is noteworthy. Theoretical insights from DFT calculations reveal that a Co–O–Fe bridging configuration within NiCo–ZIF@PBA lowers the energy barrier for the reaction to 1.79 eV, a significant reduction from 2.67 eV observed with NiCo–ZIF-67. The improvement in electrochemical performance is primarily due to the emergence of Co³⁺ ions, which results from the efficient charge transfer occurring at the interface of the PBA and NiCo–ZIF core–shell structure. These findings suggest a promising strategy for designing advanced core–shell materials for electrocatalytic applications.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452303","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":"Mixed-Linker Zr-Metal–Organic Framework with Improved Lewis Acidic Sites for CO2 Fixation Reaction Catalysis","authors":"Behnam Habibi, Paria Soleimani Abhari, Mohsen Eisari, Ali Morsali, Xiao-Wei Yan","doi":"10.1021/acs.inorgchem.4c03887","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03887","url":null,"abstract":"Applying the mixed-linker strategy in synthesizing metal–organic frameworks (MOFs) has drawn considerable attention as a heterogeneous catalyst owing to their easy synthesis and different functional ligands in their frameworks. Following this strategy, we have developed a mixed linker Zr(IV)-based MOF, [Zr₆O₄(OH)₄(FUM)_<i>n</i>(PZDC-NO₂)_6-<i>n</i>] (PZDC-NO₂ = 4-nitro-3,5-pyrazoledicarboxylic acid, FUM = fumaric acid) denoted as MOF-801(PZDC-NO₂) synthesized via this strategy which possess an electron-withdrawing group (–NO₂) on secondary linkers. The MOF-801(PZDC-NO₂) has been fully characterized via various analyses, such as Fourier transform infrared, powder X-ray diffraction, ¹³C/¹H nuclear magnetic resonance, XPS, TGA, and N₂ adsorption/desorption, SEM, EDX, etc. By considering the concurrent existence of acid–base active sites and the synergistic role of these sites, this mixed-linker MOF was used as a catalyst for the cycloaddition reaction of CO₂ and epoxides under mild without-solvent conditions. MOF-801(PZDC-NO₂) displays significant catalytic performance by producing the highest catalytic conversion of epoxide to cyclic carbonate (93%) with a turnover number of 130.7 in 8 h reaction time and 100 °C temperature under low-pressure CO₂ pressure. The mixed-linker Zr-MOF exhibits exceptional stability and reusability, maintaining its structure and functionality after consecutive cycles of utilization. Finally, the reaction mechanism was further investigated by density functional theory calculations. The total energy of the reactants, intermediates, and products involved in the process.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452345","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}