Inorganic Chemistry最新文献

{"title":"Dinuclear Heteroleptic Erbium Complexes for Improving Molecular-Based Light Upconversion in Solution?","authors":"Inès Taarit, Quentin Sommer, Laure Guénée, Claude Piguet","doi":"10.1021/acs.inorgchem.4c05481","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05481","url":null,"abstract":"In an attempt to boost molecular-based excited-state absorption (ESA) via cross-relaxation (CR), the back-to-back ditridentate polyaromatic 2,2′,6,6′-tetrakis(1-methyl-1<i>H</i>-benzo[<i>d</i>]imidazole-2-yl)-4,4′-bipyridine ligand (<b>L4</b>) was reacted with neutral [Ln(hfac)₃] lanthanide cargoes (Ln = Y, Eu, and Er and H-hfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione) to give dinuclear erbium [(hfac)₃Ln<b>L4</b>Ln(hfac)₃] ≡ [<b>L4</b>Ln₂(hfac)₆] adducts. Their crystal structures confirm the formation of dimeric molecular scaffolds made of two nine-coordinated trivalent [LnN₃O₆] chromophores separated by a 4,4′-bipyridine bridge with Ln···Ln distances within the nanometric range (Eu···Eu = 11.69 Å, Y···Y = 11.65 Å, and Er···Er = 12.12 Å). Thermodynamic studies in dichloromethane provide critical insights into the formation and stability of these adducts. Under near-infrared (NIR) excitation at 801 nm in solution, [<b>L4</b>Er₂(hfac)₆] exhibits ESA light upconversion with blueish-green emissions at 525 and 542 nm corresponding to Er(²H_11/2,⁴S_3/2 → ⁴I_15/2) transitions. Thanks to the pertinent speciation in dichloromethane, we could extract a reliable upconversion quantum yield and brightness for the targeted dinuclear [<b>L4</b>Er₂(hfac)₆] adduct in solution. They largely overpass by 2 orders of magnitude those of the unsaturated mononuclear [<b>L4</b>Er(hfac)₃] intermediate but remain comparable to data reported for related saturated monomeric adducts in the same conditions. No global beneficial cross-relaxation effect could thus be unambiguously identified.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"18 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462453","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":"Sulfur Defect Tuning of CuS/BiVO4 and Understanding the Function of Hydrogen Radicals for Photoelectrochemical Ammonia Production","authors":"Kangkang Jia, Yajie Bai, Xiaohong Wang, Lili Yang, Pengpeng Yang, Hongye Bai, Guohai Xu, Weiqiang Fan","doi":"10.1021/acs.inorgchem.4c05229","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05229","url":null,"abstract":"Photoelectrochemical nitrate reduction has been a promising method for ammonia (NH₃) production under normal temperatures and neutral conditions. However, hydrogenation is a key process in the selective production of NH₃ during nitrate reduction; therefore, inducing the active hydrogen for nitrate hydrogenation and inhibiting hydrogen production are a noteworthy problem. In this study, BiVO₄/CuS (BVO/CS) heterostructure has been constructed for a photoelectrochemical nitrate reduction reaction (PEC NIRR). The introduction of CuS optimizes the electron-transfer ability and enhances the surface catalytic kinetics of BVO/CS. At the same time, the presence of sulfur vacancies on the surface promotes the adsorption and activation of nitrate, realizes the splitting of H₂O, and successfully generates abundant hydrogen radicals (H*). The generated H* is effectively utilized in the hydrogenation of NIRR. The NH₃ yield and selectivity of optimal BVO/CS reach 30.55 μg h^–1 cm^–2 and 43.8%, respectively, which are 2.65 and 2.39 times that of bare BVO. Therefore, this work determines the key role of H* for nitrate hydrogenation, providing a novel strategy for boosting PEC NIRR. CuS/BiVO₄ was successfully fabricated for photoelectrochemical nitrate reduction. Sulfur defects enabled the generation of hydrogen radicals, which effectively promoted nitrate hydrogenation and NH₃ production.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"41 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462452","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":"Insight into Luminescence Properties of Robust BaSi3Al3O4N5:Ce3+ Blue Persistent Phosphors for Optical Information Storage","authors":"Ying Lv, Wuqiang Li, Chaofeng Li, Yu Liu, Cunjian Lin, Zhongyuan Li, Shihai You","doi":"10.1021/acs.inorgchem.4c05470","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05470","url":null,"abstract":"The commercial blue persistent luminescent (PersL) phosphor (CaAl₂O₄:Eu²⁺,Nd³⁺) is renowned for its exceptional PersL duration, but it is hampered by its poor chemical stability. There is an urgent need to develop blue PersL phosphors that can combine the excellent PersL property with robust stability. In this work, we report on a series of highly stable Ce³⁺-doped oxynitride PersL phosphors. Notably, BaSi₃Al₃O₄N₅:Ce³⁺ has been identified to contain two distinct types of defects in the host: one associated with photoluminescence (PL) and the other with electron trapping and detrapping dynamics. These intrinsic defects have been systematically investigated and confirmed by analyzing both PL and PersL spectra, which could be generated by nitrogen deficiency and the existing oxygen vacancy in BaSi₃Al₃O₄N₅. BaSi₃Al₃O₄N₅:Ce³⁺ has a widely distributed trap from 0.21 to 1.02 eV, with a peak at 0.63 eV, as determined by the initial rise method. BaSi₃Al₃O₄N₅:Ce³⁺ exhibits not only excellent water-resistance stability but also superior heat-resistant stability. Leveraging its widely distributed traps and great chemical stability, we have successfully demonstrated the optical information storage ability of BaSi₃Al₃O₄N₅:Ce³⁺ by using a gradual optical writing method. This comprehensive study provides valuable insights into the development of stable oxynitride PersL phosphors for potential applications in optoelectronic devices.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"21 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462507","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":"Coordination Competition Strategy for Constructing High-Energy Photosensitive Complexes","authors":"Jinsong Li, Wenjia Hao, Ting Zhang, Dan Xu, Quancheng Liu, Hu Deng, Juan Shen, Rufang Peng, Changgen Feng, Bo Jin","doi":"10.1021/acs.inorgchem.4c04650","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04650","url":null,"abstract":"High-dimensional energetic coordination compounds (ECCs) exhibit high stability and low sensitivity owing to their complex network structure, making them valuable in functional energetic materials such as combustion catalysis and insensitive detonating explosives. Four ECCs, [Co(DNBT)(H₂O)₄]<i>_n</i> (ECC-1), [Ni(DNBT)(H₂O)₄] (ECC-2), [Cu₂(DNBT)₂(H₂O)₃MeOH] (ECC-3), and [Zn(DNBT)(H₂O)₄] (ECC-4), were synthesized by modifying the metal centers and using 5,5′-dinitro-4<i>H</i>,4’<i>H</i>-3,3′-bi(1,2,4-triazole) (DNBT) as ligands. After changing the solution environment and adding the auxiliary ligand 4<i>H</i>-1,2,4-triazol-4-amine (4-ATr), we obtained three ECCs with similar coordination structures once again: [Co₂(DNBT)₂(4-ATr)₃(H₂O)₂] (ECC-5), [Ni₂(DNBT)₂(4-ATr)₃(H₂O)₂] (ECC-6), and [Cu₂(DNBT)₂(4-ATr)₃] (ECC-7). ECCs with fewer water molecules were chosen for laser ignition and detonation tests to evaluate their laser-induced ignition and detonation capabilities, indicating potential applications as laser initiators. The laser response behavior differs between [Co₂(DNBT)₂(4-ATr)₃(H₂O)₂] and [Cu₂(DNBT)₂(4-ATr)₃]. [Cu₂(DNBT)₂(4-ATr)₃] exhibits excellent laser response, with a low minimum laser initiation energy of 11 mJ and a short lengthy ignition delay of 2.31 ms, whereas [Co₂(DNBT)₂(4-ATr)₃(H₂O)₂] is less sensitive under the same conditions. Theoretical calculations and tests at different laser power densities indicate that [Co₂(DNBT)₂(4-ATr)₃(H₂O)₂] possesses more efficient photothermal conversion. This reduced sensitivity to laser response may stem from the presence of water. The charge transfer behavior between these compounds is thoroughly analyzed through theoretical and structural studies.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"15 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451914","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":"New Fluorescent Chemodosimetric Mechanism for Selective Recognition of Selenocysteine by Dansyl-Appended Ruthenium Nitrosyl Complexes","authors":"Iván J. Bazany-Rodríguez, Pandiyan Thangarasu, M. Leticia Almada-Leyva, José Guadalupe Hernández, Diego Martínez-Otero, María K. Salomón-Flores, Alejandro Dorazco-González","doi":"10.1021/acs.inorgchem.4c05277","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05277","url":null,"abstract":"Selenocysteine (Sec) is a biologically essential amino acid that serves as a crucial component in selenoproteins that play a key role in various cellular functions. Thus, developing a reliable and rapid method for detecting Sec in physiological media is of paramount importance. This report introduces for the first time a novel fluorescent chemodosimetric mechanism for the selective recognition of Sec using dansyl-appended ruthenium nitrosyl complexes. These complexes consist of a tetradentate ligand featuring a π-extended system (<b>L</b> = <i>N</i>,<i>N</i>′-bis(2-hydroxy-1-naphthylidene)-1,2-phenylenediamine) and a monodentate ligand derived from the conjugated dansyl group, which acts as a strong fluorescent signaling unit (<b>ID</b> = dansyl-imidazole, <b>BD</b> = dansyl-benzimidazole). The reaction between Sec and the complexes {RuNO}⁶ = <b>[RuL(NO)(ID)]Cl</b> or <b>[RuL(NO)(BD)]Cl</b> in an aqueous phase enhances fluorescence; as a result, it releases NO^• that has been demonstrated through fluorimetric titrations, UV–vis titrations, ⁷⁷Se NMR, EPR, IR, MS, and electronic density calculations. <b>[RuL(NO)(ID)]Cl</b> and <b>[RuL(NO)(BD)]Cl</b> quantitatively detect Sec within a micromolar concentration range, achieving the limit of detection as low as 0.31 and 0.12 μM, respectively, within just 5 min. Remarkably, these chemodosimeters can also be conveniently employed to detect Sec in living <i>Saccharomyces cerevisiae</i> cells.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451917","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":"Flexible Intervention of Polyoxometalate Support on the Electronegativity of Single Atoms to Enhance Catalytic Activity","authors":"Yalei Zhang, Xiaofang Su, Tao Zheng, Waqas Ali Shah, Likai Yan, Shujun Li","doi":"10.1021/acs.inorgchem.4c04978","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04978","url":null,"abstract":"The construction of single-atom catalysts (SACs) using polyoxometalates (POMs) as supports has attracted significant attention. Specifically, POMs possess the unique ability to reversibly accept and donate electrons; yet, the potential benefits of this distinctive characteristic on the activity of single atoms have remained unexplored. In this study, we employ density functional theory (DFT) calculations to investigate the synthesis of CH₃COOH from CO, CH₄, and H₂O catalyzed by POM-supported SAC M1/POM (M = Pt, Rh, Ru, Pd, Co), aiming to gain a more comprehensive understanding of the role of POM support in SACs. Our proposed mechanism first involves CH₄ activation for producing •CH₃ and, at the same time, the catalytic intermediate [M1/POM]⁻. Then, CO and •CH₃ are sequentially adsorbed on the single-atom site of [M1/POM]⁻ and coupled to form COCH₃. Finally, as H₂O attacks CH₃CO, CH₃COOH is formed and released. The poorer activity of M1/POM (M = Rh, Ru, Pd, Co) compared with that of Pt1/POM is attributed to the low matching degree in the frontier molecular orbital energy between [M1/POM]⁻ and CO/•CH₃, which results in the inaccessibility of CO and •CH₃ adsorptions, thus hindering the subsequent CH₃COOH formation. Throughout the reaction process, the POM support promotes dynamic switching of single atoms between electron-rich and electron-poor states, leveraging its reversible electron transfer capability. The electron-deficient species •CH₃ adsorption and H₂O attack are enabled by the regular access of single atoms to electron-saturated state, while timely switching of single atoms to electron-deficient states facilitates CO adsorption and CH₃ attack.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"81 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462509","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":"Predicting Reduction Potentials of Blue Copper Proteins Using Quantum Mechanical Calculations","authors":"Maryam Haji Dehabadi, Mehdi Irani, Ulf Ryde","doi":"10.1021/acs.inorgchem.4c05183","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05183","url":null,"abstract":"We have calculated redox potentials of 12 blue copper protein sites comparing 64 computational methods, systematically varying the quantum mechanics (QM) system size, dielectric constants, density functional, and basis sets. All methods were based on structures optimized with combined QM and molecular mechanics (QM/MM) approaches. The redox potentials were evaluated using 10 quality metrics. The best results for relative potentials were achieved using a QM system of intermediate size (∼70 atoms), the TPSS density functional, and a SV(P) basis set, using QM-cluster calculations in a continuum solvent with a dielectric constant of 20, yielding a mean absolute deviation of 0.09 V and a maximum deviation of 0.26 V. For absolute redox potentials, methods using larger QM systems (∼340 atoms), the B3LYP density functional, and larger basis sets perform better, achieving mean signed errors down to −0.27 V. Compared to previous studies on iron–sulfur clusters, redox potentials for blue copper proteins show improved accuracy due to their narrower potential range and simpler coordination environments, but systematic errors are system-dependent. This study underscores the challenges of modeling redox-active sites in proteins and highlights the effectiveness of QM-cluster calculations in a continuum solvent in balancing computational cost with predictive power.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"25 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462518","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":"Synthesis, Crystal Structure, and Elementary Electrical Characterization of Quasi-One-Dimensional TiSe3","authors":"Danrui Ni, Teresa Lee, Stephen Zhang, Xianghan Xu, R. J. Cava","doi":"10.1021/acs.inorgchem.4c05396","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05396","url":null,"abstract":"The solid-state synthesis at an applied pressure of 6 GPa, crystal structure, and elementary electronic properties of the previously unreported compound TiSe₃ are described. The crystal structure, which is based on 1D chains of Ti–Se triangular prisms that are coupled to each other, with two-thirds of the Se involved in a Se–Se pair, is similar to that of TiS₃. Unlike the trisulfide, the triselenide is only made under pressure at temperatures between 800 and 900 °C. The material is semiconducting and weakly diamagnetic.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"50 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451920","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":"An Ambiphilic Phosphide with Three Different Coordination Modes to Group 7–10 Metals","authors":"Adrien T. Normand, Hélène Cattey, Marie-José Penouilh, Quentin Bonnin, Paul Fleurat-Lessard, Céline Pichon, Jean-Pascal Sutter","doi":"10.1021/acs.inorgchem.5c00201","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00201","url":null,"abstract":"Phosphide anions PX₂^– with electron-withdrawing substituents display ambiphilic properties. The use of P(V) thiophosphorane substituents enables the coordination of the resulting bis(thiophosphoranyl)phosphide anion (<b>BTPP</b> = <b>L</b>) to a variety of transition metals from groups 7 to 10. A series of homoleptic and heteroleptic complexes was synthesized and X-ray diffraction analysis revealed that, depending on the metal, <b>L</b> may adopt three coordination modes (κ³-(S, P, S); κ²-(S, S); κ²-(S, P)) supporting three distinct geometries (octahedral; tetrahedral; square planar). Complex <b>L</b>_<b>2</b><b>Co</b> displays Single Molecule Magnet (SMM) properties, and complex <b>LRh(COD)</b> (COD = 1,5-cyclooctadiene) catalyzes the hydrosilylation of terminal alkynes.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"23 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451924","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":"pts-Type Aluminoborate with Nonlinear Optical Properties","authors":"Lan Wang, Juan Chen, Guo-Yu Yang","doi":"10.1021/acs.inorgchem.4c05459","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05459","url":null,"abstract":"A noncentric 3D aluminoborate (ABO), NaCs₂[AlB₅O₁₀]·HCOO·H₂O (<b>1</b>), has been constructed through the solvothermal technique. The framework of <b>1</b> is formed by the alternation of AlO₄ tetrahedra and B₅O₁₀ clusters, featuring 7 types of channels. <b>1</b> belongs to the “10,10-linkage”, which features an unprecedented <i>pts</i> topology in the ABO field. The measurement of second-harmonic generation (SHG) shows that <b>1</b> displays an SHG value roughly 1.1 times that of KH₂PO₄ (KDP). The UV–vis diffuse reflectance spectrum suggests potential applications for <b>1</b> in the deep ultraviolet (DUV) field.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"29 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451921","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}