Inorganic Chemistry最新文献_第8页

Auto-Tandem Catalyst: From Allylic Alcohols to Secondary Alcohols via Redox Isomerization/Atmospheric Hydrogenation in Water Catalyzed by a Water-Soluble Iridium Complex Bearing a Functional Ligand

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-13 DOI: 10.1021/acs.inorgchem.4c04283

Xiaozhong Chen, Beixuan Dong, Guoqiang Zhao, Jing Xu, Feng Li

引用次数: 0

From (C₆H₅N₂)₂CdCl₄ to (C₆H₅N₂)₂ZnCl₄, Chirality Transformation to Realize a Nonlinear Optical Organic-Inorganic Hybrid Halide with Balanced Comprehensive Performance.

IF 4.3 2区化学

Inorganic Chemistry Pub Date : 2025-02-13 DOI: 10.1021/acs.inorgchem.5c00076

Die-Xue Yang, Yi-Lei Lv, Jian-Dong Guo, Wen-Ye Gao, Wenlong Liu, Ru-Ling Tang

{"title":"From (C6H5N2)2CdCl4 to (C6H5N2)2ZnCl4, Chirality Transformation to Realize a Nonlinear Optical Organic-Inorganic Hybrid Halide with Balanced Comprehensive Performance.","authors":"Die-Xue Yang, Yi-Lei Lv, Jian-Dong Guo, Wen-Ye Gao, Wenlong Liu, Ru-Ling Tang","doi":"10.1021/acs.inorgchem.5c00076","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00076","url":null,"abstract":"Nonlinear optical (NLO) crystals are critical for modern optical devices. In this study, two new hybrid metal halides, (C6H5N2)2CdCl4 (1) and (C6H5N2)2ZnCl4 (2), were synthesized by a mild solution method. 1 and 2 crystallize in different chiral space groups of P43212 and P212121, respectively. Their crystal structures are composed of [MX4]2- (M = Cd, Zn) tetrahedrons and (C6H5N2)+ cations with different arrangements. They both have wide band gaps (3.98 and 3.83 eV). Attractively, 2 exhibits a SHG (second-harmonic generation) effect of 1.2 × KDP, large birefringence (0.22@546 nm), and a high laser damage threshold (35 × AgGaS2), and can be grown up to centimeter level. Theoretical calculations show that these properties result from the ordered arrangement of organic cations and the synergistic effect of [MX4] tetrahedra, providing a new example to develop high-performance NLO materials by cation regulation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":""},"PeriodicalIF":4.3,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143412300","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

Mechanistic Insights into Solvent-Mediated Halide-Specific Irreversible Transformation of Cu-MOF with Iodide Detection Capability

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-13 DOI: 10.1021/acs.inorgchem.4c04816

Ahamad Irfan, Naga Venkateswara Rao Nulakani, Upendar Reddy Gandra, Robert Gyepes, Petr Henke, Martin Kubu, Jiří Mosinger, Youssef Belmabkhout, Ahsanulhaq Qurashi, Jiri Čejka, Russell Morris, Zhehao Huang, Mohamad Akbar Ali, M. Infas H. Mohideen

{"title":"Mechanistic Insights into Solvent-Mediated Halide-Specific Irreversible Transformation of Cu-MOF with Iodide Detection Capability","authors":"Ahamad Irfan, Naga Venkateswara Rao Nulakani, Upendar Reddy Gandra, Robert Gyepes, Petr Henke, Martin Kubu, Jiří Mosinger, Youssef Belmabkhout, Ahsanulhaq Qurashi, Jiri Čejka, Russell Morris, Zhehao Huang, Mohamad Akbar Ali, M. Infas H. Mohideen","doi":"10.1021/acs.inorgchem.4c04816","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04816","url":null,"abstract":"The fascinating feature of metal–organic frameworks is that they can respond to external stimuli, unlike other inorganic materials. This feature corresponds to the framework’s flexibility, which originates with the long-range crystalline order of the framework accompanied by cooperative structural transformability. We have synthesized a novel metal–organic framework comprised of Cu(I) nodes with pyrazine linkers and benzene-1,3,5-tricarboxylate acting as template anions, named CUCAM-1 [Cu(Py)2(BTC)]n. In the presence of polar solvent systems, CUCAM-1 undergoes an irreversible structural transformation to yield a mixed phase that consists of HKUST-1 [Cu3(BTC)2(H2O)3]n and another CUCAM-2 [Cu(Py)(BTC)]n MOFs, whose novel structure is successfully revealed by continuous rotation electron diffraction from the mixture. In this structural transformation, a new ligand exchange occurs where template anions become ligands, confirmed by single crystal X-ray analysis. Further, structural transformation and the mechanism are explained by ab initio molecular dynamics (AIMD) simulations. Interestingly, different halides (F–, Cl–, and Br–) can be accompanied to affect/control the composition of the second phase by favoring the formation of the HKUST-1 phase over CUCAM-2, which was evident by the powder X-ray diffraction studies. Furthermore, the structural transformation induced by I– resulted in a colorimetric response due to the formation of a new MOF CUCAM-3, paving the way for use as an iodide detector.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"16 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143401915","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

Isolation and Reactivity of Carbene-Stabilized Carbon Disulfide Radical Anions.

IF 4.3 2区化学

Inorganic Chemistry Pub Date : 2025-02-13 DOI: 10.1021/acs.inorgchem.4c05030

Michael J Stopper, Akachukwu D Obi, Haleigh R Machost, Noah D McMillion, Andrew Molino, Emma N Cook, Asa W Nichols, Lucas A Freeman, Sarah G Stegner, Diane A Dickie, David J D Wilson, Charles W Machan, Robert J Gilliard

{"title":"Isolation and Reactivity of Carbene-Stabilized Carbon Disulfide Radical Anions.","authors":"Michael J Stopper, Akachukwu D Obi, Haleigh R Machost, Noah D McMillion, Andrew Molino, Emma N Cook, Asa W Nichols, Lucas A Freeman, Sarah G Stegner, Diane A Dickie, David J D Wilson, Charles W Machan, Robert J Gilliard","doi":"10.1021/acs.inorgchem.4c05030","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05030","url":null,"abstract":"The reaction of CAAC-CS2 betaine (1; CAAC = cyclic(alkyl)(amino)carbene) and alkali metal reductants under ambient conditions yields carbene-stabilized carbon disulfide radical anions as crystalline alkali metal salts. The radicals 3-5 form multinuclear clusters featuring diverse metal sulfide and disulfide interactions, which promote unusual reductive coupling and cyclization of adjacent CS2 units to C2S3 heterocycles (6). The addition of crown ethers to 3-5 sequesters the alkali cations and facilitates disulfide cleavage to yield stable [CAAC-CS2]·- monomers (7 and 8). Calculated natural atomic spin populations suggest that the spin densities in the clustered and monomeric species are comparable and evenly distributed between the CAAC and CS2 subunits. Subsequent reductions afford [CAAC-CS2]2- dianions (9-12), which can be reoxidized to radicals by comproportionation reactions with 1. The radicals are, in turn, oxidized to betaine 1 through salt elimination reactions with transition metals. Cyclic voltammograms of 1 feature reversible 1/1·-/12- couples with a small separation between the events (ΔΔG = 11.1 kcal mol-1). All isolated compounds were characterized by a combination of electron paramagnetic resonance spectroscopy, heteronuclear NMR spectroscopy, infrared spectroscopy, and single-crystal X-ray diffraction. Insights into their electronic structure are supported by density functional theory calculations.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":""},"PeriodicalIF":4.3,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143412301","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

Impact of Metal Species on Chain Transfer Mode in Bis(imino)pyridyl Complexes Catalyzed Ethylene Polymerization

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-12 DOI: 10.1021/acs.inorgchem.4c04941

Yuan Yuan, Zhengpeng Yan, Shengyu Dai

{"title":"Impact of Metal Species on Chain Transfer Mode in Bis(imino)pyridyl Complexes Catalyzed Ethylene Polymerization","authors":"Yuan Yuan, Zhengpeng Yan, Shengyu Dai","doi":"10.1021/acs.inorgchem.4c04941","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04941","url":null,"abstract":"Chain transfer reactions are pivotal in coordination polymerization, influencing catalytic efficiency, molecular weight adjustment, and control over the chain-end structure. In this study, we present the synthesis and characterization of two bis(imino)pyridyl ligands featuring flexible o-aryl cycloalkyl substituents, along with their corresponding iron(II) and cobalt(II) complexes. These complexes exhibited very high polymerization activities, reaching up to 1.8 × 107 g mol–1 h–1, and produced highly linear polyethylene with a wide range of molecular weights (MW = 2.1–232.8 kg/mol) during ethylene polymerization. The sizes of the cycloalkyl ring and the metal species were found to have a substantial impact on the polymerization process. Specifically, smaller cyclopentyl substituents enhanced polymerization activity and increased the molecular weight of the resulting polyethylene for both iron(II) and cobalt(II) complexes compared to their cyclohexyl counterparts. When complexes with the same ligand were compared, iron(II) species generated polyethylene with higher molecular weights and broader molecular weight distributions in comparison to the corresponding cobalt(II) species under identical conditions. The most striking finding is the significant selectivity of the metal species in our system for different chain transfer modes. Analysis of the molecular weight distributions and chain-end structures of the resulting polyethylene revealed that chain transfer to the cocatalyst MAO predominates in iron(II)-catalyzed ethylene polymerization, whereas in cobalt(II)-catalyzed ethylene polymerization, chain transfer to the monomer ethylene is the primary mode.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"22 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393673","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

Experimental and Computational Study on U(VI) Sorption Mechanisms of Single-Layered Ti3C2TX Nanosheets

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-12 DOI: 10.1021/acs.inorgchem.4c04835

Jianqiao Zhang, Zhongjie Zhu, Jiaxiang Liu, Panqi Song, Yiwen Li, Guangfeng Liu, Na Li, Jixiang Li, Qiang Tian

{"title":"Experimental and Computational Study on U(VI) Sorption Mechanisms of Single-Layered Ti3C2TX Nanosheets","authors":"Jianqiao Zhang, Zhongjie Zhu, Jiaxiang Liu, Panqi Song, Yiwen Li, Guangfeng Liu, Na Li, Jixiang Li, Qiang Tian","doi":"10.1021/acs.inorgchem.4c04835","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04835","url":null,"abstract":"Environmental contamination by U(VI) from radioactive wastewater has become a challenging concern in the development of nuclear energy. A highly efficient recovery of U(VI) from wastewater is essential for environmental remediation and can mitigate the depletion of conventional uranium resources. This study describes the synthesis of single-layered Ti3C2TX nanosheets by chemical exfoliation using ultrasonography. The single-layered structure promoted a high sorption capacity of 3.20 mmol/g for U(VI) (distribution constant Kd > 104 mL/g) and excellent selectivity in mine wastewater that contained numerous coexisting ions. Fragmentation of the Ti3C2TX nanosheets from micron-scale to nanoscale upon uranyl sorption was detected by small-angle X-ray scattering and transmission electron microscopy. Extended X-ray absorption fine structure spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations demonstrated that uranyl groups coordinated with the terminal −OH and −F on the surface of the Ti3C2TX nanosheets. These findings provide imperative insights into the design and application of nanomaterials to effectively treat uranium-contaminated wastewater.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"63 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143401918","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

Sustainable Synthesis of MCM-22 Zeolite as a Catalytic Platform for Propane Dehydrogenation 可持续合成 MCM-22 沸石作为丙烷脱氢的催化平台

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-12 DOI: 10.1021/acs.inorgchem.4c04630

Xiaotao Yu, Yuxuan Chen, Min Guo, Song Lu, Jiadi Ying, Tiancun Liu, Qi Shen, Yeqing Wang, Zhixin Yu

{"title":"Sustainable Synthesis of MCM-22 Zeolite as a Catalytic Platform for Propane Dehydrogenation","authors":"Xiaotao Yu, Yuxuan Chen, Min Guo, Song Lu, Jiadi Ying, Tiancun Liu, Qi Shen, Yeqing Wang, Zhixin Yu","doi":"10.1021/acs.inorgchem.4c04630","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04630","url":null,"abstract":"The significant volume of solvent required for the hydrothermal synthesis of zeolites remains the primary hurdle impeding industrial applications. With the benefits of reduced manufacturing costs, safety, and energy savings, reducing the use of solvents is one of the significant sought-after objectives. In this study, borosilicate zeolite B-MCM-22 is successfully obtained using a solvent-free synthesis method. The as-synthesized sample exhibits good long-range order, high crystallinity, and high silica utilization (ca. 95%). Furthermore, the B-MCM-22 precursor serves as a platform for introducing Co active sites via deboronization and impregnation processes. The resulting Co-MCM-22-DB catalyst provides a propylene selectivity of >90% with an initial propane conversion of 38% in the propane dehydrogenation reaction and shows a higher initial catalytic performance than the Co/ITQ-1 catalyst. The essential interplay between the metal–support interaction and catalytic performance is demonstrated by ultraviolet–visible (UV–vis), H2-TPR, and catalytic assessments, further elucidating that Co2+ species are the active sites for propane to propylene conversion. We anticipate that B-MCM-22 will be a versatile and ideal platform for catalyst design through structural manipulation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"78 5 Pt 1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393612","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

Synthesis of YFeO3–Y3Fe5O12 Heterogeneous Structure Magnetic Nanomaterials and Preparation of Nanofibers by Coprecipitation Method

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-12 DOI: 10.1021/acs.inorgchem.4c05020

Jia-Li Wang, Xue Xi, Ke-Di Cai, Zhi-Han Chang, Jian-Fang Chi, Xiao-Shi Lang

{"title":"Synthesis of YFeO3–Y3Fe5O12 Heterogeneous Structure Magnetic Nanomaterials and Preparation of Nanofibers by Coprecipitation Method","authors":"Jia-Li Wang, Xue Xi, Ke-Di Cai, Zhi-Han Chang, Jian-Fang Chi, Xiao-Shi Lang","doi":"10.1021/acs.inorgchem.4c05020","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05020","url":null,"abstract":"The design and fabrication of yttrium iron oxide-based magnetic nanomaterials play an indispensable role in microelectronic-related fields. The bottleneck still remains, including limited reproducibility and the inability to control the size of the resulting material. In this study, a straightforward coprecipitation method was firstly used for the production of heterogeneous YFeO3–Y3Fe5O12 composite with (NH4)2CO3 as the precipitant. Under optimized conditions, the obtained YFeO3–Y3Fe5O12 nanoparticles exhibit high crystallinity and ferromagnetic properties at room temperature, and its saturation magnetization strength (Ms) reached 11.927 emu·g–1. Meanwhile, the particle size can be achieved at approximately 14.7 nm. The compact heterojunction between the yttrium iron oxide components gives rise to the obvious ferromagnetic property. Subsequently, YFeO3–Y3Fe5O12 nanoparticles were taken as the raw material for preparing flexible [(YFeO3–Y3Fe5O12)/PVP] nanofibers by electrospinning technology. By changing the proportion of magnetic particles in the nanofibers, the magnetic strength can be regulated. The integration between magnetism and the preparation of nanofiber membranes is realized. The encapsulation of magnetic particles in the nanofibers avoids not only aggregation but also the direct contact with the impurity, which promotes practicability and recycle life.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"208 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393667","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

Development of Ferrocenyl and Ruthenocenyl Zileuton Analogs with Enhanced Bioactivity toward Human 5-Lipoxygenase: Innovation in Drugs for Inflammatory Diseases

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-12 DOI: 10.1021/acs.inorgchem.4c05103

Elizabeth Navarrete, Pilar Morales, Tomas Caceres, Andrés Vega, Pierre Mesdom, Kevin Cariou, Fernando Godoy, Gilles Gasser, Erick Flores, Carolina Mascayano

{"title":"Development of Ferrocenyl and Ruthenocenyl Zileuton Analogs with Enhanced Bioactivity toward Human 5-Lipoxygenase: Innovation in Drugs for Inflammatory Diseases","authors":"Elizabeth Navarrete, Pilar Morales, Tomas Caceres, Andrés Vega, Pierre Mesdom, Kevin Cariou, Fernando Godoy, Gilles Gasser, Erick Flores, Carolina Mascayano","doi":"10.1021/acs.inorgchem.4c05103","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05103","url":null,"abstract":"Zileuton is the only FDA-approved 5-lipoxygenase (5-LOX) inhibitor for asthma treatment, but it produces hepatotoxicity associated with the benzothiophene fragment. Using the concept of organometallic derivatization pioneered by Jaouen and Brocard, we synthesized five new organometallic Zileuton derivatives, maintaining the urea fragment and incorporating ferrocenyl and ruthenocenyl moiety (3a–e). Their biological activity was evaluated against 5-LOX, 15-LOX, COX-1, and COX-2 enzymes. The ferrocenyl and ruthenocenyl N-hydroxyurea complexes coined Ferroleuton (3a) and Ruthenoleuton (3e) showed the highest selective inhibitory activity against 5-LOX, with IC50 values of 0.21 ± 0.12 and 3.49 ± 1.11 μM, respectively. Notably, 3a exhibited superior activity compared to Zileuton (IC50 0.67 ± 0.09 μM), demonstrating the key role of N-hydroxyurea and ferrocenyl fragments in the inhibitory process. Worthy of note, both compounds displayed low cytotoxicity in lung fibroblast healthy cells line (MRC-5) (CC50 of 116.40 and >200 μM, respectively). Enzyme kinetic studies indicated competitive and mixed types of inhibition for 3a and 3e, respectively. Additionally, they demonstrated superior antioxidant capacity compared to Zileuton (DPPH, ABTS, and FRAP assays). Electrochemical and molecular dynamics (MD) studies suggest a chelating-redox deactivation mechanism for 5-LOX. These findings position Ferroleuton (3a) and Ruthenoleuton (3e) as promising candidates for inflammatory disease treatment.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"87 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143401922","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

Synthesis and Characterization of Solvated and Base-Free Cerium(III) Mixed-Sandwich Complexes

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-12 DOI: 10.1021/acs.inorgchem.4c04840

Pragati Pandey, Aleksandr Zaichenko, Patrick W. Smith, Dominic R. Russo, Michael R. Gau, Patrick J. Carroll, Taylor M. Keller, Alexandra M. Bacon, Stefan G. Minasian, Jochen Autschbach, Eric J. Schelter

{"title":"Synthesis and Characterization of Solvated and Base-Free Cerium(III) Mixed-Sandwich Complexes","authors":"Pragati Pandey, Aleksandr Zaichenko, Patrick W. Smith, Dominic R. Russo, Michael R. Gau, Patrick J. Carroll, Taylor M. Keller, Alexandra M. Bacon, Stefan G. Minasian, Jochen Autschbach, Eric J. Schelter","doi":"10.1021/acs.inorgchem.4c04840","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04840","url":null,"abstract":"A series of solvated complexes: [(C8H8)Ln(C5Me4R)(DME)] Ln = La, R = −Me; (La-2) Ln = Ce, R = −Me, −SiMe3, −H; (Ce-2, Ce-3, Ce-4), [(dbCOT)Ln(C5Me5)(DME)] (Ln-6), (dbCOT2– = dibenzocyclooctadienide; Ln = Ce, La), [(dbCOT)Ce(C5Me4H)(DME)] (Ce-7) and [(hdcCOT)Ce(C5Me5)(DME)] (Ce-8) (hdcCOT2– = hexahydrodicyclopentacyclooctatetraenide) and base-free mixed-sandwich complexes [(C8H8)Ce(C5Me5)] (Ce-9), [(C8H8)Ce(C5Me4H) (Ce-10) and [(hdcCOT)Ce(C5Me5)] (Ce-11) of the early lanthanide metals cerium and lanthanum comprising variable cyclopentadienide (Cp–) and cyclooctatetraenide (COT2–) ligands is described. To evaluate the effect of cyclopentadienide and cyclooctatetraenide ligands on the characteristics of these complexes, their solid-state structural, electrochemical, and photophysical properties were studied and accompanied by theoretical calculations. To further evaluate the effect of ligands on the topology of the complexes and the reducing properties of the complexes, syntheses of several base-free congeners were pursued, which led to isolation of the first base-free monomeric and polymeric Ce(III) mixed-sandwich compounds.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"40 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393613","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