Pub Date : 2025-04-16DOI: 10.1021/acs.inorgchem.5c00216
Pablo Molinillo, Ana Gálvez Del Postigo, Maxime Puyo, Florencia Vattier, Ana M. Beltrán, Nuria Rendón, Patricia Lara, Andrés Suárez
Nickel nanoparticles (Ni·MIC) stabilized with mesoionic 1,2,3-triazolylidene (MIC) ligands were prepared via decomposition of the [Ni(COD)2] (COD = 1,5-cyclooctadiene) complex with H2 (3 bar) in the presence of 0.2 or 0.5 equiv of ligand. The obtained monodisperse and small-sized (3.2–3.8 nm) nanoparticles were characterized by high-resolution transmission electron microscopy (TEM, HRTEM) and inductively coupled plasma (ICP) analysis. Further analysis of the nickel nanoparticles by X-ray photoelectron spectroscopy (XPS) demonstrated the coordination of the MIC ligands to the metal surface. Finally, the Ni·MIC nanoparticles were applied in the isotopic H/D exchange in hydrides of group 14 elements (Si, Ge, Sn) using D2 gas under relatively mild conditions (1.0–1.8 mol % Ni, 1 bar D2, 55 °C). High and chemoselective deuterium incorporation at the E–H (E = Si, Ge, Sn) bond in these derivatives was observed.
{"title":"Selective H/D Exchange in E–H (E = Si, Ge, Sn) Bonds Catalyzed by 1,2,3-Triazolylidene-Stabilized Nickel Nanoparticles","authors":"Pablo Molinillo, Ana Gálvez Del Postigo, Maxime Puyo, Florencia Vattier, Ana M. Beltrán, Nuria Rendón, Patricia Lara, Andrés Suárez","doi":"10.1021/acs.inorgchem.5c00216","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00216","url":null,"abstract":"Nickel nanoparticles (Ni·MIC) stabilized with mesoionic 1,2,3-triazolylidene (MIC) ligands were prepared via decomposition of the [Ni(COD)<sub>2</sub>] (COD = 1,5-cyclooctadiene) complex with H<sub>2</sub> (3 bar) in the presence of 0.2 or 0.5 equiv of ligand. The obtained monodisperse and small-sized (3.2–3.8 nm) nanoparticles were characterized by high-resolution transmission electron microscopy (TEM, HRTEM) and inductively coupled plasma (ICP) analysis. Further analysis of the nickel nanoparticles by X-ray photoelectron spectroscopy (XPS) demonstrated the coordination of the MIC ligands to the metal surface. Finally, the Ni·MIC nanoparticles were applied in the isotopic H/D exchange in hydrides of group 14 elements (Si, Ge, Sn) using D<sub>2</sub> gas under relatively mild conditions (1.0–1.8 mol % Ni, 1 bar D<sub>2</sub>, 55 °C). High and chemoselective deuterium incorporation at the E–H (E = Si, Ge, Sn) bond in these derivatives was observed.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"8 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841206","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}
Redox-active quinoline-containing [NiII(2PyN2Q) (H2O)]2+ complex (1) has been developed for the electrocatalytic (e) hydrogen evolution reaction (HER) in the presence of organic acids and water and for the hydrogen-atom-transfer (HAT) reaction with styrene in the presence of acids. Complex 1 shows promising e-HER performance in water up to pH 9. It exhibits a stepwise (E)ECEC mechanism with AcOH, while a potential-dependent bimolecular homolytic pathway and CEEC mechanism is operative with p-toluene sulfonic acid during the e-HER. The one- and two-electron-reduced species of 1 are characterized by spectro-electrochemistry, optical, and EPR studies. Moreover, the inverse kinetic isotope effect (KIE = 0.83) between AcOH and d4-AcOH during the e-HER and e-HAT with styrene for the hydro-functionalization reaction using catalyst 1 possibly suggests the involvement of nickel hydride species. The e-HER and e-HAT reactivity of 1 have been compared with redox-inactive redox-inactive [NiII(N4Py)(H2O)]2+ (2), demonstrating the prominent effect of quinoline in the e-HER and pyridine in the e-HAT. The proposed mechanism of the e-HER with AcOH is well supported by DFT studies.
{"title":"Effect of Ligand Backbone on the Electrochemical Hydrogen Evolution Reaction and Hydrogen-Atom-Transfer Reactivity Using a Nickel Polypyridine Quinoline Complex","authors":"Sabarni Paul, Subhankar Sutradhar, Aniruddha Paik, Amit Biswas, Soumadip Das, Chandan Das, Rajib Maity, Alok Mahata, Siba P. Midya, Bholanath Maity, Sujoy Rana","doi":"10.1021/acs.inorgchem.4c05512","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05512","url":null,"abstract":"Redox-active quinoline-containing [Ni<sup>II</sup>(2PyN2Q) (H<sub>2</sub>O)]<sup>2+</sup> complex (<b>1</b>) has been developed for the electrocatalytic (<b>e</b>) hydrogen evolution reaction (HER) in the presence of organic acids and water and for the hydrogen-atom-transfer (HAT) reaction with styrene in the presence of acids. Complex <b>1</b> shows promising e-HER performance in water up to pH 9. It exhibits a stepwise (E)ECEC mechanism with AcOH, while a potential-dependent bimolecular homolytic pathway and CEEC mechanism is operative with <i>p</i>-toluene sulfonic acid during the e-HER. The one- and two-electron-reduced species of <b>1</b> are characterized by spectro-electrochemistry, optical, and EPR studies. Moreover, the inverse kinetic isotope effect (KIE = 0.83) between AcOH and <i>d</i><sub>4</sub>-AcOH during the e-HER and e-HAT with styrene for the hydro-functionalization reaction using catalyst <b>1</b> possibly suggests the involvement of nickel hydride species. The e-HER and e-HAT reactivity of <b>1</b> have been compared with redox-inactive redox-inactive [Ni<sup>II</sup>(N4Py)(H<sub>2</sub>O)]<sup>2+</sup> (<b>2</b>), demonstrating the prominent effect of quinoline in the e-HER and pyridine in the e-HAT. The proposed mechanism of the e-HER with AcOH is well supported by DFT studies.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"40 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841210","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}
Pub Date : 2025-04-16DOI: 10.1021/acs.inorgchem.5c00374
Kaitlyn M. Birkhoff, Ian Lin, Sam Yruegas
Synthetic access toward well-defined, monomeric s-block metal complexes is mired with chemical challenges, primarily attributed to the formation of homoleptic complexes promoted by the Schlenk equilibrium. Ligand redistribution is significantly pronounced for the heavier s-block metals, such as calcium, which form bischelate complexes readily through traditional synthetic routes such as transmetalation, amination, and ligand exchange. Mechanistic investigation of each of these routes with phenoxyimine (ONN) ligands was explored to ascertain the fundamental parameters promote bischelate formation. Donor effects from coordinated solvent proved to be deleterious, and in an effort to circumvent bischelation, a new calcium bisamide, {Ca[N(SiMe3)2]2(diox)2}∞, was synthesized and characterized as a coordination polymer with a unique square planar geometry, rarely seen for group 2 complexes. Amination with {Ca[N(SiMe3)2]2(diox)2}∞ was found to significantly shift the Schlenk equilibrium to favor heteroleptic species, allowing for the characterization of new phenoxyimine calcium-amido complexes: [ONN1Ca–N(SiMe3)2]2(diox) and [ONN3Ca–N(SiMe3)2(diox)]∞. Subsequent studies showed that solvent exchange from the isolated dioxane complexes with THF notably shortened the stability of the complex in solution. Although steric parameters have previously been regarded as the key to the stabilization of heteroleptic calcium complexes, it is equally important to consider the donor ability of coordinated solvent ligands to achieve longer-lived heavy s-block complexes.
{"title":"Manipulation of Solvent Donor Effects to Overcome the Calcium Schlenk Equilibrium","authors":"Kaitlyn M. Birkhoff, Ian Lin, Sam Yruegas","doi":"10.1021/acs.inorgchem.5c00374","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00374","url":null,"abstract":"Synthetic access toward well-defined, monomeric <i>s</i>-block metal complexes is mired with chemical challenges, primarily attributed to the formation of homoleptic complexes promoted by the Schlenk equilibrium. Ligand redistribution is significantly pronounced for the heavier <i>s</i>-block metals, such as calcium, which form bischelate complexes readily through traditional synthetic routes such as transmetalation, amination, and ligand exchange. Mechanistic investigation of each of these routes with phenoxyimine (<b>ONN</b>) ligands was explored to ascertain the fundamental parameters promote bischelate formation. Donor effects from coordinated solvent proved to be deleterious, and in an effort to circumvent bischelation, a new calcium bisamide, <b>{Ca[N(SiMe</b><sub><b>3</b></sub><b>)</b><sub><b>2</b></sub><b>]</b><sub><b>2</b></sub><b>(diox)</b><sub><b>2</b></sub><b>}</b><sub><b>∞</b></sub>, was synthesized and characterized as a coordination polymer with a unique square planar geometry, rarely seen for group 2 complexes. Amination with <b>{Ca[N(SiMe</b><sub><b>3</b></sub><b>)</b><sub><b>2</b></sub><b>]</b><sub><b>2</b></sub><b>(diox)</b><sub><b>2</b></sub><b>}</b><sub><b>∞</b></sub> was found to significantly shift the Schlenk equilibrium to favor heteroleptic species, allowing for the characterization of new phenoxyimine calcium-amido complexes: <b>[ONN1Ca–N(SiMe</b><sub><b>3</b></sub><b>)</b><sub><b>2</b></sub><b>]</b><sub><b>2</b></sub><b>(diox)</b> and <b>[ONN3Ca–N(SiMe</b><sub><b>3</b></sub><b>)</b><sub><b>2</b></sub><b>(diox)]</b><sub><b>∞</b></sub>. Subsequent studies showed that solvent exchange from the isolated dioxane complexes with THF notably shortened the stability of the complex in solution. Although steric parameters have previously been regarded as the key to the stabilization of heteroleptic calcium complexes, it is equally important to consider the donor ability of coordinated solvent ligands to achieve longer-lived heavy <i>s</i>-block complexes.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"31 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841211","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}
Pub Date : 2025-04-16DOI: 10.1021/acs.inorgchem.5c00587
Tao Zhang, Huiqing Wu, Naihan Li, Chen Li, Zhiqiang Wang, Guanghui Liu, Song Xu, Meng Wei, Jinzhan Su, Jiehu Cui
Bismuth vanadate (BiVO4) is a potential photoelectrode for photoelectrochemical (PEC) applications. Nevertheless, the rapid charge recombination and sluggish water oxidation kinetics greatly limit the PEC activity. To address these drawbacks, this study developed a cooperative modification strategy with simultaneous La doping and amorphous cobalt-phytate compound (Co-phy) as a cocatalyst on BiVO4 to raise the PEC performance. La doping increased the donor density, and the decoration of the Co-phy cocatalyst expedited water oxidation kinetics and further improved the utilization efficiency of charge carriers. As a result, the constructed hybrid photoelectrode (La-BVO/Co-phy) generated a photocurrent of 2.12 mA·cm–2 at 1.23 V vs RHE, about 4.8 times that of the pristine BiVO4 photoelectrode (0.44 mA·cm–2). Moreover, a significant reduction in onset potential and prominent improvement in conversion efficiency, stability, and charge separation efficiency were achieved for the synergistically modified photoanode. Furthermore, a profound exploration on the charge dynamics disclosed increased carrier density, decreased charge recombination, and enhanced charge transfer kinetics as a consequence of the synchronized effect of La doping and Co-phy cocatalyst, which greatly contributed to the elevated PEC activity. This work introduces a practical route to fabricating BiVO4-based photoelectrodes for solar water splitting applications.
{"title":"Exploring the Charge Dynamics in a Synergistically Modified BiVO4 Photoanode with La Doping and Cobalt-Based Phytate Compound Cocatalyst for Photoelectrochemical Water Oxidation","authors":"Tao Zhang, Huiqing Wu, Naihan Li, Chen Li, Zhiqiang Wang, Guanghui Liu, Song Xu, Meng Wei, Jinzhan Su, Jiehu Cui","doi":"10.1021/acs.inorgchem.5c00587","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00587","url":null,"abstract":"Bismuth vanadate (BiVO<sub>4</sub>) is a potential photoelectrode for photoelectrochemical (PEC) applications. Nevertheless, the rapid charge recombination and sluggish water oxidation kinetics greatly limit the PEC activity. To address these drawbacks, this study developed a cooperative modification strategy with simultaneous La doping and amorphous cobalt-phytate compound (Co-phy) as a cocatalyst on BiVO<sub>4</sub> to raise the PEC performance. La doping increased the donor density, and the decoration of the Co-phy cocatalyst expedited water oxidation kinetics and further improved the utilization efficiency of charge carriers. As a result, the constructed hybrid photoelectrode (La-BVO/Co-phy) generated a photocurrent of 2.12 mA·cm<sup>–2</sup> at 1.23 V vs RHE, about 4.8 times that of the pristine BiVO<sub>4</sub> photoelectrode (0.44 mA·cm<sup>–2</sup>). Moreover, a significant reduction in onset potential and prominent improvement in conversion efficiency, stability, and charge separation efficiency were achieved for the synergistically modified photoanode. Furthermore, a profound exploration on the charge dynamics disclosed increased carrier density, decreased charge recombination, and enhanced charge transfer kinetics as a consequence of the synchronized effect of La doping and Co-phy cocatalyst, which greatly contributed to the elevated PEC activity. This work introduces a practical route to fabricating BiVO<sub>4</sub>-based photoelectrodes for solar water splitting applications.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"121 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837398","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}
This study reports the synthesis of ten coordination compounds (1–10) derived from the ligand bis((3-aminopyridin-2-yl)selanyl)methane (L) and different metal centers (CoII, CuI, CuII, ZnII, and AgI). Single crystals of the complexes were obtained via slow diffusion from overlaid solutions of ligand L and the corresponding metal. Their crystalline structures were determined by single-crystal X-ray diffraction (SCXRD) and further characterized using spectroscopic, spectrometric, and voltammetric techniques. Complexes 1–5, 7, and 10 were evaluated as cocatalysts of mesoporous titanium dioxide (m-TiO2) for photocatalytic hydrogen production via water photolysis under solar light simulation, using triethanolamine (TEOA) as the sacrificial agent. The results showed that complexes 4, 5, 7, and 10 enhanced m-TiO2 photocatalytic activity, achieving hydrogen evolution rates at least four times higher than standard m-TiO2 and P25. Among these, the photocatalyst m-TiO2-7 (7 = [Cu2(μ-SO4)2L2]) exhibited the highest hydrogen production, reaching approximately 7800 μmol/g over a 6-h experiment–nearly 26 times greater than pure m-TiO2 (300 μmol/g). These findings highlight the potential of organoselenium metal complexes for the development of novel photocatalytic materials based on nonprecious metals.
{"title":"Structural Analysis of Selenium Coordination Compounds and Mesoporous TiO2-Based Photocatalysts for Hydrogen Generation","authors":"Rodrigo Cervo, Cândida Alíssia Brandl, Tanize Bortolotto, Camila Nunes Cechin, Natália de Freitas Daudt, Bernardo Almeida Iglesias, Ernesto Schulz Lang, Bárbara Tirloni, Roberta Cargnelutti","doi":"10.1021/acs.inorgchem.4c05325","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05325","url":null,"abstract":"This study reports the synthesis of ten coordination compounds (<b>1</b>–<b>10</b>) derived from the ligand bis((3-aminopyridin-2-yl)selanyl)methane (<b>L</b>) and different metal centers (Co<sup>II</sup>, Cu<sup>I</sup>, Cu<sup>II</sup>, Zn<sup>II</sup>, and Ag<sup>I</sup>). Single crystals of the complexes were obtained via slow diffusion from overlaid solutions of ligand <b>L</b> and the corresponding metal. Their crystalline structures were determined by single-crystal X-ray diffraction (SCXRD) and further characterized using spectroscopic, spectrometric, and voltammetric techniques. Complexes <b>1</b>–<b>5</b>, <b>7</b>, and <b>10</b> were evaluated as cocatalysts of mesoporous titanium dioxide (m-TiO<sub>2</sub>) for photocatalytic hydrogen production via water photolysis under solar light simulation, using triethanolamine (TEOA) as the sacrificial agent. The results showed that complexes <b>4</b>, <b>5</b>, <b>7</b>, and <b>10</b> enhanced m-TiO<sub>2</sub> photocatalytic activity, achieving hydrogen evolution rates at least four times higher than standard m-TiO<sub>2</sub> and P25. Among these, the photocatalyst m-TiO<sub>2</sub>-<b>7</b> (<b>7</b> = [Cu<sub>2</sub>(μ-SO<sub>4</sub>)<sub>2</sub><b>L</b><sub><b>2</b></sub>]) exhibited the highest hydrogen production, reaching approximately 7800 μmol/g over a 6-h experiment–nearly 26 times greater than pure m-TiO<sub>2</sub> (300 μmol/g). These findings highlight the potential of organoselenium metal complexes for the development of novel photocatalytic materials based on nonprecious metals.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"35 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837375","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}
Pub Date : 2025-04-16DOI: 10.1021/acs.inorgchem.4c05564
Jun-Bao Zhou, Zhuo-Hang Zhu, Min Chen, Nian Zhao, Hui Min
Mechanochromic luminescence molecules show great appeal in the realm of intelligent luminescent materials but face great challenges from aggregation-caused quenching and/or amorphization during mechanical processing. Integrating aggregation-induced emission (AIE) luminogens into the architecture of highly crystalline metal–organic frameworks (MOFs) could potentially address these issues. In this work, two isomorphic Zn-MOFs ({[Zn(TCPE)0.5(Lx)0.5]·guests}n, where H4TCPE = 1,1,2,2-tetra(4-carboxylphenyl)ethylene, L1 = triethylenediamine, and L2 = piperazine) are synthesized via a multiligand assembly approach. The mechanochromic luminescence behaviors observed in these Zn-MOFs have been thoroughly analyzed, with a focus on the influence of linker effects. Under mechanical grinding, the lattice contraction of Zn-MOFs is accompanied by the distortion of the benzene rings within TCPE4–, leading to altered intramolecular twisted charge transfer within the Zn-MOFs, which subsequently changes their luminescence properties. The potential application of this luminescence behavior in light-emitting diodes was preliminarily explored.
{"title":"Mechanochromic Luminescence Behavior in Multivariate Metal–Organic Frameworks Based on Linker Effects","authors":"Jun-Bao Zhou, Zhuo-Hang Zhu, Min Chen, Nian Zhao, Hui Min","doi":"10.1021/acs.inorgchem.4c05564","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05564","url":null,"abstract":"Mechanochromic luminescence molecules show great appeal in the realm of intelligent luminescent materials but face great challenges from aggregation-caused quenching and/or amorphization during mechanical processing. Integrating aggregation-induced emission (AIE) luminogens into the architecture of highly crystalline metal–organic frameworks (MOFs) could potentially address these issues. In this work, two isomorphic Zn-MOFs ({[Zn(TCPE)<sub>0.5</sub>(L<sub><i>x</i></sub>)<sub>0.5</sub>]·guests}<sub><i>n</i></sub>, where H<sub>4</sub>TCPE = 1,1,2,2-tetra(4-carboxylphenyl)ethylene, L<sub>1</sub> = triethylenediamine, and L<sub>2</sub> = piperazine) are synthesized via a multiligand assembly approach. The mechanochromic luminescence behaviors observed in these Zn-MOFs have been thoroughly analyzed, with a focus on the influence of linker effects. Under mechanical grinding, the lattice contraction of Zn-MOFs is accompanied by the distortion of the benzene rings within TCPE<sup>4–</sup>, leading to altered intramolecular twisted charge transfer within the Zn-MOFs, which subsequently changes their luminescence properties. The potential application of this luminescence behavior in light-emitting diodes was preliminarily explored.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"8 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841036","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}
Pub Date : 2025-04-16DOI: 10.1021/acs.inorgchem.5c00278
Zhuanling Bai, Joseph M. Sperling, Thomas E. Albrecht
Four trivalent, f-element tetrazolate hydrate complexes [M(H2O)9](Hdtb)3·nH2O (Nd1, n = 7 and Pu1, n = 9; dtb2– = 1,3-di(tetrazolate-5-yl)benzene) and [M(Hdtb)(H2O)8](dtb)·11H2O (Nd2 and Pu2) were prepared using metathesis reactions. These complexes contain hydrated M(III) cations, but in the latter complexes, Nd2 and Pu2, one of the water molecules has been displaced by a long interaction between the M(III) cation and a Hdtb– anion. Notably, the Pu(III)–N bond in Pu2, representing the longest IXPu(III)–N (IX = nine coordinate) bond reported has a length of 2.8338(15) Å and is slightly shorter than the Nd(III)–N bond length of 2.8425(13) Å in Nd2. Analysis of bond lengths, Wiberg bond indices (WBI), natural localized molecular orbitals (NLMOs), and quantum theory of atoms in molecules (QTAIM) reveals that the metal contribution to the Pu(III)–N bond is marginally greater than that of the Pu(III)–OH2 bonds in Pu2 and the Nd(III)–N bond in Nd2. Thus, this rather long M–N interaction provides an example where the expectation that An(III) compounds exhibit greater covalency with soft donor ligands compared to harder ligands fails. The absorption spectra of Pu1 and Pu2 further support this observation, highlighting a surprising degree of similarity in their electronic structures.
{"title":"Elucidation of an Unusually Long Pu–N Bond in a Plutonium(III)-Tetrazolate Complex","authors":"Zhuanling Bai, Joseph M. Sperling, Thomas E. Albrecht","doi":"10.1021/acs.inorgchem.5c00278","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00278","url":null,"abstract":"Four trivalent, <i>f</i>-element tetrazolate hydrate complexes [M(H<sub>2</sub>O)<sub>9</sub>](Hdtb)<sub>3</sub>·<i>n</i>H<sub>2</sub>O (<b>Nd1</b>, <i>n</i> = 7 and <b>Pu1</b>, <i>n</i> = 9; dtb<sup>2–</sup> = 1,3-di(tetrazolate-5-yl)benzene) and [M(Hdtb)(H<sub>2</sub>O)<sub>8</sub>](dtb)·11H<sub>2</sub>O (<b>Nd2</b> and <b>Pu2</b>) were prepared using metathesis reactions. These complexes contain hydrated M(III) cations, but in the latter complexes, <b>Nd2</b> and <b>Pu2</b>, one of the water molecules has been displaced by a long interaction between the M(III) cation and a Hdtb<sup>–</sup> anion. Notably, the Pu(III)–N bond in <b>Pu2</b>, representing the longest <sup>IX</sup>Pu(III)–N (<sup>IX</sup> = nine coordinate) bond reported has a length of 2.8338(15) Å and is slightly shorter than the Nd(III)–N bond length of 2.8425(13) Å in <b>Nd2</b>. Analysis of bond lengths, Wiberg bond indices (WBI), natural localized molecular orbitals (NLMOs), and quantum theory of atoms in molecules (QTAIM) reveals that the metal contribution to the Pu(III)–N bond is marginally greater than that of the Pu(III)–OH<sub>2</sub> bonds in <b>Pu2</b> and the Nd(III)–N bond in <b>Nd2</b>. Thus, this rather long M–N interaction provides an example where the expectation that An(III) compounds exhibit greater covalency with soft donor ligands compared to harder ligands fails. The absorption spectra of <b>Pu1</b> and <b>Pu2</b> further support this observation, highlighting a surprising degree of similarity in their electronic structures.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"4 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841209","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}
Transition metal-based electrocatalysts are active materials for the oxygen evolution reaction (OER). However, their activities depend heavily on the in situ reconstructed new catalytic layer, which severely curtails the rational design and screening of well-defined electrocatalysts during the synthesis stage. Here, we present a method to deliberately design the in situ reconstructed catalyst reaction layer by adding a small amount of Fe3+ ions to the electrolyte. We investigated the effect of Fe3+ ions on the reconstruction process of the NiCuOxHy catalyst and their subsequent contribution to the catalytic activity. The presence of Fe3+ ions promotes the formation of a well-defined catalytic layer with fewer oxygen vacancies. This structural feature allows for fast charge and active-species transfer near the reaction layer. Moreover, the Fe3+-ion-regulated reconstruction layer has a suitable electronic configuration for intermediate adsorption, thus reducing the reaction kinetics. With the assistance of the trace Fe3+ ions, an increase in the current density of up to 54.2% can be achieved. Moreover, the electrolyte concentration can be saved 50% (0.5 M) while maintaining a current density of 150 mA cm–2. This work provides insights into the ion-catalyst correlation in surface reconstruction and offers guidance for the design of efficient OER electrocatalysts.
{"title":"Dynamic Ion-Regulated Oxygen Evolution Catalyst Surface Reconstruction","authors":"Jinhui Hao, Zhilin Zhang, Zhenghao Zhang, Yitian Wu, Xiao Yang, Qianwen Qiu, Chenyang Cai, Yutao Hua, Wenshu Yang, Longhua Li, Weidong Shi","doi":"10.1021/acs.inorgchem.5c00938","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00938","url":null,"abstract":"Transition metal-based electrocatalysts are active materials for the oxygen evolution reaction (OER). However, their activities depend heavily on the <i>in situ</i> reconstructed new catalytic layer, which severely curtails the rational design and screening of well-defined electrocatalysts during the synthesis stage. Here, we present a method to deliberately design the <i>in situ</i> reconstructed catalyst reaction layer by adding a small amount of Fe<sup>3+</sup> ions to the electrolyte. We investigated the effect of Fe<sup>3+</sup> ions on the reconstruction process of the NiCuO<sub><i>x</i></sub>H<sub><i>y</i></sub> catalyst and their subsequent contribution to the catalytic activity. The presence of Fe<sup>3+</sup> ions promotes the formation of a well-defined catalytic layer with fewer oxygen vacancies. This structural feature allows for fast charge and active-species transfer near the reaction layer. Moreover, the Fe<sup>3+</sup>-ion-regulated reconstruction layer has a suitable electronic configuration for intermediate adsorption, thus reducing the reaction kinetics. With the assistance of the trace Fe<sup>3+</sup> ions, an increase in the current density of up to 54.2% can be achieved. Moreover, the electrolyte concentration can be saved 50% (0.5 M) while maintaining a current density of 150 mA cm<sup>–2</sup>. This work provides insights into the ion-catalyst correlation in surface reconstruction and offers guidance for the design of efficient OER electrocatalysts.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"67 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841213","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}
Pub Date : 2025-04-16DOI: 10.1021/acs.inorgchem.4c05574
Maryam Manafi Moghadam, Ali Ramazani, Ali Morsali, Sobhan Rezayati
This study explores the design and synthesis of the magnetic UiO-66-NH2(Zr) functionalized with a Schiff base copper(II) complex via the postsynthesis method, forming a core–shell structure that acts as a magnetically recyclable nanocatalyst. The nanocatalyst was synthesized using an affordable and straightforward method and abbreviated as magnetic@UiO-66-NH-SB-Cu(II). For this purpose, magnetic@UiO-66-NH2 was synthesized by modifying Fe3O4 with tetraethyl orthosilicate, ZrCl4, and 2-aminoterephthalic acid, stabilizing the core, and promoting Zr-MOF growth. The surface was functionalized with pyrrole-2-carboxaldehyde and CuCl2, followed by characterization through various techniques. Using particle size distributions from transmission electron microscopy images, the average size was determined to be roughly 10–22 nm. The presence of cupric ions (Cu2+) within the catalyst was confirmed through X-ray photoelectron spectroscopy analysis, which distinctly revealed two peaks at 940.2 and 960.1 eV corresponding to Cu 2p3/2 and Cu 2p1/2, respectively. The synthesized nanocatalyst exhibits improved performance in the formation of chromene-annulated heterocycles from various aromatic aldehydes and various phenols with malononitrile in ethanol under reflux conditions. The catalyst can be reused by a magnet field up to seven times with only a minimal drop in the yield of the product. Cu leaching is confirmed by inductively coupled plasma analysis to occur at a rate of 0.7 wt %.
{"title":"Functionalization of Magnetic UiO-66-NH2 with Schiff Base Copper(II) Complex for the One-Pot Synthesis of Pyran-Annulated Heterocyclic Scaffolds","authors":"Maryam Manafi Moghadam, Ali Ramazani, Ali Morsali, Sobhan Rezayati","doi":"10.1021/acs.inorgchem.4c05574","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05574","url":null,"abstract":"This study explores the design and synthesis of the magnetic UiO-66-NH<sub>2</sub>(Zr) functionalized with a Schiff base copper(II) complex via the postsynthesis method, forming a core–shell structure that acts as a magnetically recyclable nanocatalyst. The nanocatalyst was synthesized using an affordable and straightforward method and abbreviated as magnetic@UiO-66-NH-SB-Cu(II). For this purpose, magnetic@UiO-66-NH<sub>2</sub> was synthesized by modifying Fe<sub>3</sub>O<sub>4</sub> with tetraethyl orthosilicate, ZrCl<sub>4</sub>, and 2-aminoterephthalic acid, stabilizing the core, and promoting Zr-MOF growth. The surface was functionalized with pyrrole-2-carboxaldehyde and CuCl<sub>2</sub>, followed by characterization through various techniques. Using particle size distributions from transmission electron microscopy images, the average size was determined to be roughly 10–22 nm. The presence of cupric ions (Cu<sup>2+</sup>) within the catalyst was confirmed through X-ray photoelectron spectroscopy analysis, which distinctly revealed two peaks at 940.2 and 960.1 eV corresponding to Cu 2p<sub>3/2</sub> and Cu 2p<sub>1/2</sub>, respectively. The synthesized nanocatalyst exhibits improved performance in the formation of chromene-annulated heterocycles from various aromatic aldehydes and various phenols with malononitrile in ethanol under reflux conditions. The catalyst can be reused by a magnet field up to seven times with only a minimal drop in the yield of the product. Cu leaching is confirmed by inductively coupled plasma analysis to occur at a rate of 0.7 wt %.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"270 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837374","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}
Pub Date : 2025-04-16DOI: 10.1021/acs.inorgchem.5c00070
Siyu Ren, Linfeng Zhang, Yue Zhang, Ce Wang, Xiaofeng Lu
Tubular nanoreactors, which exhibit a distinctive void-confinement effect, have become intriguing for their prospective applications in catalysis. However, rationally constructing these structures remains a formidable challenge, particularly in realizing a significantly synergistic catalytic enhancement. In this study, we present a reliable template polymerization-guided synthetic strategy, creating hollow CoSn(OH)6 cubes inside polydopamine (PDA) nanotubes (CoSn(OH)6@PDA NTs). This sample functions as a potent peroxymonosulfate (PMS) activator for toxic contaminant oxidation. Diverse reactive oxygen species produced within the nanotubes significantly enhance this efficiency. The exceptional catalytic property results from the rich active sites of CoSn(OH)6 and the distinct nanotubular structure, which concentrates reactants and benefits the mass transfer process. This research opens possibilities for developing high-performance and robust catalysts with spatial confinement effects, advancing water treatment technology.
{"title":"Confining Hollow CoSn(OH)6 Cubes Inside Polydopamine Nanotubes To Significantly Promote Fenton-like Catalysis for Water Treatment","authors":"Siyu Ren, Linfeng Zhang, Yue Zhang, Ce Wang, Xiaofeng Lu","doi":"10.1021/acs.inorgchem.5c00070","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00070","url":null,"abstract":"Tubular nanoreactors, which exhibit a distinctive void-confinement effect, have become intriguing for their prospective applications in catalysis. However, rationally constructing these structures remains a formidable challenge, particularly in realizing a significantly synergistic catalytic enhancement. In this study, we present a reliable template polymerization-guided synthetic strategy, creating hollow CoSn(OH)<sub>6</sub> cubes inside polydopamine (PDA) nanotubes (CoSn(OH)<sub>6</sub>@PDA NTs). This sample functions as a potent peroxymonosulfate (PMS) activator for toxic contaminant oxidation. Diverse reactive oxygen species produced within the nanotubes significantly enhance this efficiency. The exceptional catalytic property results from the rich active sites of CoSn(OH)<sub>6</sub> and the distinct nanotubular structure, which concentrates reactants and benefits the mass transfer process. This research opens possibilities for developing high-performance and robust catalysts with spatial confinement effects, advancing water treatment technology.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"50 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837377","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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