Inorganic Chemistry最新文献

{"title":"Visible Light-Activatable Organoboron Complexes Featuring Salicylaldehyde Azine Ligands for Rapid Cationic Polymerization and Mechanism Studies.","authors":"Yingzhu Sun, Lei Wang, Changjiang Yu, Zihao Wang, Jinsong Shao, Xinsheng Xu, Yaxiong Wei, Yangyang Xu, Lijuan Jiao, Erhong Hao","doi":"10.1021/acs.inorgchem.5c00783","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00783","url":null,"abstract":"<p><p>Rapid polymerization controlled by visible light holds great potential for advancing 3D printing technologies. However, a significant challenge limiting the implementation of visible-light-activated polymerizations is its low efficiency compared to UV light driven processes. To address this, we developed a series of visible-light-activatable organoboron (BOSHY) complexes featuring salicylaldehyde azine ligands for rapid cationic polymerization. These BOSHYs featuring different brominated BOSHY catalyze the polymerization of epoxides under 405 nm LED light in three-component systems with iodonium salt and amine, achieving a 78% epoxy conversion in just 52 s at low intensity irradiation of 50 mW cm^-2. Additionally, the mechanism of photopolymerization involves the formation of cations by EDB, which initiates the polymerization process. The triplet state lifetime (15.4-23.5 μs) indicates effective intersystem crossing, enabling efficient energy and electron transfer reactions. Experiments confirm nearly 100% electron transfer due to the extended triplet state lifetime. This study not only introduces novel BOSHY derivatives for cationic polymerization but also elucidates the reaction kinetics analysis of the photopolymerization, significantly expanding the use of visible light LEDs as an alternative to UV light in photopolymerization.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":""},"PeriodicalIF":4.3,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144558433","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":"Reactions of 2-Diphenylphosphino-benzaldehyde with Group 13 Lewis Acids.","authors":"Hui Li, Shaoying Ju, Ting Chen, Kun Ding, Weili Yan, Douglas W Stephan, Yile Wu","doi":"10.1021/acs.inorgchem.5c01899","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01899","url":null,"abstract":"<p><p>2-Diphenylphosphinobenzaldehyde <b>1</b> reacts with the group 13 Lewis acids to give simple phosphine adducts C₆H₄P(C(O)H)(Ph)₂InX₃; X = Br <b>2</b> and I <b>3</b>. In contrast, the Lewis acids GaCl₃, AlCl₃, E(C₆F₅)₃ (E = B or Al), and ClAl(C₆F₅)₂ affect Lewis acid/phosphine addition to a carbonyl group, affording zwitterions with either the eight-membered ring products [(C₆H₄C(H)(OER₃)P(Ph)₂)]₂ ER₃ = Al(C₆F₅)_<b>3</b> <b>4</b>, Al(C₆F₅)₂Cl <b>5</b>, AlCl₃ <b>6</b>, or GaCl₃ <b>7</b> or the six-membered ring species (C₆H₄C(H)(OB(C₆F₅)₃)P(Ph)₂(C₆H₄C(H)(O) P(Ph)₂)) <b>8</b>. These products derived from the frustrated Lewis pair additions to aldehyde fragments are fully characterized and described, and the differing reactivity is considered.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":""},"PeriodicalIF":4.3,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144558430","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":"Efficacy of Methylammonium Iodobismuthate: A Green Catalyst for Reduction of Nitrate to Ammonia.","authors":"Vivek Kumar Agrahari, Abhik Bhuin, Ankur Yadav, Sujoy Sarkar, Subha Sadhu, Daya Shankar Pandey","doi":"10.1021/acs.inorgchem.5c02618","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c02618","url":null,"abstract":"<p><p>Ammonia (NH₃) is vital in agriculture and industry, yet its large-scale production remains energy-intensive and environmentally hostile. Herein, for the first time we report the development of lead-free nontoxic hexagonal methylammonium iodobismuthate metal halide perovskite (MABI) as a highly efficient and sustainable electrocatalyst for green ammonia production from nitrate reduction. The unique structure of MABI, featuring an isolated BiI₆ octahedron stabilized by a methylammonium cation, offers a highly tunable electronic environment required for nitrogen activation and hydrogenation. The experimental and computational studies categorically established the formation of an interconnected pure hexagonal structure with a band gap of ∼2.1 eV. Electrocatalytic nitrate reduction revealed that MABI displays a remarkable ammonia yield (27.53 μg mg^-1 h^-1) with excellent stability and a quite impressive Faradaic efficiency (40%). This work highlights the potential of halide bismuthate perovskites as an alternative to traditional catalysts to produce ammonia in ambient conditions that address the dual challenges of energy efficiency and environmental sustainability.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":""},"PeriodicalIF":4.3,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144558412","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":"Nitrogen Oxyanion Reductive Borylation at Low-Coordinate Iron: A Struggle between Two Oxophiles.","authors":"Bao G Tran, Nobuyuki Yamamoto, Maren Pink, Yaroslav Losovyj, Kenneth G Caulton, Jeremy M Smith","doi":"10.1021/acs.inorgchem.5c01619","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01619","url":null,"abstract":"<p><p>With the advent of the Haber-Bosch process over a century ago, the world's population experienced tremendous growth due to the million tons of fixed nitrogen used in fertilizer each year. However, the majority of the fixed nitrogen is metabolized to various nitrogen oxyanions by soil organisms that are lost to waterways, leading to eutrophication and hypoxia. Therefore, there is a need to convert the anthropogenic nitrogen content to more useful forms. In this work, the synthesis and characterization of iron nitrate (PhB(ⁱPr₂Im)₃FeNO₃) complex (<b>2</b>) is reported. Subsequent stepwise deoxygenation via a bis(boryl) reduced N-heterocycle (BPin₂pz) to its downstream counterparts is thermodynamically favorable by DFT. Reaction of iron nitrate with (BPin₂)pz led to the formation of iron (pinacolato)boralanolate complex (<b>3</b>) and a proposed diiron dinitrosyl complex having bridged hydroxide ligands ([PhB(ⁱPr₂Im)₃Fe(NO)(OH)]₂) (<b>4</b>). The formation of these complexes demonstrates the oxophilicity of both iron and boron.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":""},"PeriodicalIF":4.3,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144558415","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":"Bader Charge Balance Mechanism Realizes Industrial-Grade Current Hydrogen Production.","authors":"Xi Zhou,Yu Cheng,Xinnan Xu,Lifang Zhang,Shu Tian,Xiaohui Xu,Baocong Guo,Weidong Tang,Chenglin Yan,Tao Qian","doi":"10.1021/acs.inorgchem.5c00590","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00590","url":null,"abstract":"The hydrogen production technology of water splitting under a high current density is the key to solve the efficient utilization of hydrogen energy. However, it is difficult for existing catalysts to exhibit bifunctional high-current activity in the same electrolyzer, considering that the bimetallic site can endow the catalytic material asymmetry and heterogeneity and then change the intrinsic electronic structure. Herein, we constructed a La-Fe dual-site coupled self-assembled membrane electrode (D-LaFe-SAME), and the introduction of the dual site reduced the Bader charge value of the La site from 0.87 to 0.83|e|, while the Bader charge of the Fe site increased from 0.69 to 0.70|e|, thus optimizing the Bader charge value of La-Fe active sites to a close equilibrium. Consequently, the free energy barrier of the rate-determining step is optimized, and the catalytic activity is greatly improved. Prominently, the optimal D-LaFe-SAME can achieve current densities of up to 2000 mA cm-2 at very low overpotentials (-640 mV for HER and 626 mV for OER), which is even better than the commercial precious metals Pt/C and IrO2. Surprisingly, when we use a large area of D-LaFe-SAME for overall water splitting, it can operate stably at currents up to 4 A. The dual-site coupled strategy based on the Bader charge balance mechanism proposed in this work is crucial for the construction of an efficient and high-current electrocatalytic system for hydrogen production in the same electrolyzer and plays a key role in achieving the goals of carbon neutrality.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"28 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144547751","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 Reactivity of the Benzene Tetraanion in a Neutral Inverse-Sandwich Lanthanum Complex.","authors":"Peng Deng, Yifan Gao, Xiaohui Kang, Jianhua Cheng","doi":"10.1021/acs.inorgchem.5c01490","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01490","url":null,"abstract":"<p><p>Neutral inverse-sandwich lanthanum arene complexes with the parent benzene tetraanion are still limited. Here, we report the neutral inverse-sandwich lanthanum benzene complexes [(Cp^Ar5)La(THF)_<i>n</i>]₂(μ-η⁶:η⁶-C₆H₆) (Cp^Ar5 = η⁵-C₅Ar₅, Ar = ^<i>i</i>Pr₂-C₆H₃-3,5; <i>n</i> = 0, <b>2</b>; <i>n</i> = 1, <b>2-THF</b>) supported by a superbulky penta-arylcyclopentadienyl ligand. Complex <b>2</b> was isolated from the reduction of the half-sandwich lanthanum diiodide precursor [(Cp^Ar5)LaI₂(THF)₂] (<b>1</b>) in benzene by the K/KI reductant, yielding 69%. The reaction of complex <b>2</b> with 0.5 equiv of (HBBN)₂ enabled C-H bond functionalization of the benzene tetraanion, generating a novel borylated product [(Cp^Ar5)La]₂(μ-η⁶:η⁶-C₆H₅BBN) (<b>3</b>). NMR analyses, single-crystal X-ray diffraction, and UV-vis spectroscopic studies demonstrated that complexes <b>2</b>, <b>2-THF,</b> and <b>3</b> share a [La³⁺-(arene)^4--La³⁺] electronic structure, which was further confirmed by density functional theory (DFT) calculations. Moreover, treatment of complex <b>2</b> with Me₃SiN₃ afforded a product [(Cp^Ar5)La{N(SiMe₃)₂}]₂(μ-N₃)₂ (<b>4</b>) via four-electron reduction and subsequent Si-N bond activation. Additionally, the dimeric peroxo complex [(Cp^Ar5)La(THF)]₂(μ-η²:η²-O₂)₂ (<b>5</b>) was detected in the reaction of <b>2</b> with O₂. The redox reactivity of <b>2</b> shows its great potential in the multielectron reduction of unsaturated substrates, functioning as a La(I) synthon.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":""},"PeriodicalIF":4.3,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144558413","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":"Ultra-Confined Environments May Restrict the Possible Configurations of Supported Metal Complexes.","authors":"Frédéric A Perras, Rashmi Jena, Sazia Sultana, M Matiar Rahman, Simin Sun, Sayak Banerjee, Scott A Southern, Aaron D Sadow, Wenyu Huang, Aaron L Odom","doi":"10.1021/acs.inorgchem.5c02067","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c02067","url":null,"abstract":"<p><p>The rotation frequencies of amido ligands are highly sensitive to the electronic structure of <i>d</i>⁰ transition metal complexes and have been used to study ligand donor properties. While attempting to study the donor properties of silanolate ligands in a silica-supported Cr complex, we observed highly restricted motions due to the added steric hindrance from the support, with only approximately half of the amides rotating on a 50 ms time scale. Surprisingly, when the same species is grafted into narrow 2.2 nm pores, all amido ligands are able to rotate. Density functional theory calculations suggest that confinement may limit the possible coordination sites and the configuration of the formed surface species, potentially enabling the formation of conformationally homogeneous surface site populations.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":""},"PeriodicalIF":4.3,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144558432","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":"Investigation of the Defect Cu²⁺ Centers in the Paddle Wheel MOF: Defective Structures, EPR Spectra, and H₂O Adsorption.","authors":"Chang-Chun Ding, Yong-Qiang Li, Yu-Jie Sun, Wei Jin, Tong Liu, Jun-Shan Hu","doi":"10.1021/acs.inorgchem.4c04694","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04694","url":null,"abstract":"<p><p>Due to the different Cu²⁺ centers, the _∞³[Cu₂^ICu₂^II(H₂O)₂L₂Cl₂] MOF has been widely studied using electron paramagnetic resonance (EPR) spectra, particularly regarding its capacity for gas molecule adsorption. In the present work, based on the occupation sites of Cu²⁺ in _∞³[Cu₂^ICu₂^II(H₂O)₂L₂Cl₂], three corresponding fragments, dimer [CuO₅]-[CuO₅] (C₀), defective [CuO₅] (C₁), and [CuN₄] (C₂), are established to investigate the two different EPR signals (S_a and S_b) and the local environment of Cu²⁺. By applying the order perturbation formulas of the spin-Hamiltonian parameters, C₀ and C₂ can be excluded because of the EPR silence of the antiferromagnetically coupled Cu²⁺ pair at low (7 K) temperatures and the silent signal of Cu¹⁺. Thus, two mononuclear Cu²⁺ ion defect species (C₁^a and C₁^b) in _∞³[Cu₂^ICu₂^II(H₂O)₂L₂Cl₂] can account for signals S_a and S_b, indicating two distinct surrounding environments of Cu²⁺. When the results from the density functional theory calculations are combined, the defective copper paddle wheel units are superior to the pristine ones in the adsorption of H₂O, which is beneficial to the electrochemical hydrogen evolution reaction (HER) and oxygen evolution reactions (OER). Therefore, the reliability of the perturbation method to investigate the EPR spectra and the adsorption behavior of MOFs is powerfully demonstrated, which can reduce the time consumed by current first-principles calculations.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":""},"PeriodicalIF":4.3,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144558414","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":"Triarylboron-Doped Polymer Matrix Ultralong Room-Temperature Phosphorescent Materials for Advanced Multidimensional Information Encryption.","authors":"Jin-Fa Chen, Xu-Xu Jia, Yu-Xi Yuan, Qi Lin, Bingbing Shi, Hong Yao, Wen-Juan Qu, Tai-Bao Wei","doi":"10.1021/acs.inorgchem.5c01025","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01025","url":null,"abstract":"<p><p>Constructing polymer-based ultralong organic room-temperature phosphorescence (UORTP) materials that exhibit time-dependent phosphorescent color variation holds profound significance. Triarylboranes, as a typical class of fluorophores, are widely used in the fabrication of various functional organic luminescent materials, and achieving UORTP materials from triarylboranes has become an important studied topic. In this study, a polymer-based UORTP material is fabricated by means of doping organic phosphor (<b>NBC</b>) composed of boronic acid-modified triarylborane unit into a poly(vinyl alcohol) (PVA) matrix, which is attributed to the hydrogen bonding between <b>NBC</b> and PVA, effectively suppressing the nonradiative decay. The experimental results show that the afterglow color of <b>NBC@PVA</b> film gradually changed from orange to green after irradiation with 365 nm UV light, thereby successfully realizing a polymer-doped phosphorescent material characterized by an ultralong lifetime and color variability. By employing two fluorescent dyes, namely, Rhodamine B and Fluorescein, as energy acceptors, we successfully engineered color-tunable UORTP emission. Furthermore, the excellent applicability of these materials in information encryption and anticounterfeiting has also been demonstrated.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":""},"PeriodicalIF":4.3,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144558431","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":"Correction to \"Interplay of Crystal Structure and Magnetic Properties of the Eu_{5.08-<i>x</i>}Sr_<i>x</i>Al₃Sb₆ Solid Solution\".","authors":"Luis Garay, Jose L Gonzalez Jimenez, James C Fettinger, S Olivia Gunther, Jacob A Branson, Stefan G Minasian, Weiwei Xie, Susan M Kauzlarich","doi":"10.1021/acs.inorgchem.5c02948","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c02948","url":null,"abstract":"","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":""},"PeriodicalIF":4.3,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144558411","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}