Inorganic Chemistry最新文献_第3页

Hydrolytic Cleavage and Deborylation of Boron(III) Subphthalocyanines─A Synthetic Approach to Fused Diazatripyrrins. 亚酞菁硼（III）的水解裂解和波酰化─熔融重氮吡啶的合成方法。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-23 DOI: 10.1021/acs.inorgchem.5c02123

Alina M Fazlyeva,Ivan A Skvortsov,Nikolay V Somov,Pavel A Stuzhin

{"title":"Hydrolytic Cleavage and Deborylation of Boron(III) Subphthalocyanines─A Synthetic Approach to Fused Diazatripyrrins.","authors":"Alina M Fazlyeva,Ivan A Skvortsov,Nikolay V Somov,Pavel A Stuzhin","doi":"10.1021/acs.inorgchem.5c02123","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c02123","url":null,"abstract":"Boron(III) subphthalocyanine analogues with enhanced electron affinity in the presence of water undergo hydrolytic cleavage of the macrocycle and deborylation, resulting in formation of noncyclic aza-bridged tris-isoindoles, which are fused derivatives of 5,10-diazatripyrrines (DATRIPY). Spectral data, kinetic studies, and DFT results allow us to suggest a plausible mechanism of DATRIPY formation, which includes nucleophilic addition of water to one of the CαNmeso bonds and its rupture as a key stage. This reaction is possible for perhalogenated or/and azasubstituted boron(III) subphthalocyanine analogues and occurs especially easily for hexachlorinated tripyrazinosubporphyrazinatoboron(III) chloride, affording the corresponding 14-amino-5,10-diazatripyrrin-1-one [DATRIPY1a] bearing fused dichloropyrazine fragments in each pyrrole unit. An X-ray diffraction study revealed that DATRIPY1a has an S-like conformation, which is stabilized by two intramolecular hydrogen bonds between pyrrolic NH groups and pyrrolenine and pyrazine nitrogens. DATRIPY1a reacts with BF3, forming a noncyclic tripyrrolic bis-boron(III) complex [BODATRIPY] in which two BF2 fragments are bonded by pyrrole-pyrrolenine and pyrrole-pyrazine coordination sites. Due to rearrangement of intramolecular H-bonds occurring in aprotic and proton donor solvents, DATRIPY1a exhibits strong solvatochromism and can also be used as a colorimetric sensor for the presence of hard anions (fluoride, hydroxide, cyanide, and cyanate).","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"18 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144693201","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

Green Synthesis of Dual-Emission Tin-Doped Cesium Manganese Halide Nanocrystals with High Performance. 绿色合成双发射高性能掺锡卤化铯锰纳米晶体。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-23 DOI: 10.1021/acs.inorgchem.5c02240

Zhipeng Xiong,Zhenyu Gao,Changhui Miao,Yanhua Fu,Xiaoling Zeng,Dandan Sun,Xingtao Chen,Lixin Yu

{"title":"Green Synthesis of Dual-Emission Tin-Doped Cesium Manganese Halide Nanocrystals with High Performance.","authors":"Zhipeng Xiong,Zhenyu Gao,Changhui Miao,Yanhua Fu,Xiaoling Zeng,Dandan Sun,Xingtao Chen,Lixin Yu","doi":"10.1021/acs.inorgchem.5c02240","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c02240","url":null,"abstract":"Manganese-based halide perovskites have gradually become a focus point for exploring photoluminescent materials due to their attractive electronic and photophysical properties. However, little attention has been paid to the dual-emission and thermochromic phenomena in all-inorganic Mn-based materials. In this study, Sn2+-doped Cs3MnBr3Cl2 is synthesized at room temperature, which exhibits bright yellow emission, with two broad emission peaks at 525 and 605 nm, corresponding to full width at half-maximum (fwhm) of 92 and 91 nm, respectively. The photoluminescence quantum yield (PLQY) is significantly increased from 5.3% for the absence of Sn2+ to 33.41% for the presence of Sn2+. The excitation, temperature-dependent, and time-resolved spectra indicate that the dual emissions originate from the spin-forbidden transition (4T1 → 6A1) of Mn2+ and the self-trapped exciton emission induced by Sn2+ doping. The introduction of Sn2+ modifies the crystal field environment and symmetry around Mn2+, intensifying the electron-phonon coupling, thereby causing the emergence of a new emission peak and significant broadening of the fwhm. Furthermore, due to the different temperature sensitivities of the two emission peaks, the emitted color is transitioned from yellow to orange-red as the temperature is increased. Combined with its enhanced stability, this material demonstrates promising application potential in the optoelectronic field.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"20 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144693199","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

Rationalizing Spin-Crossover Properties of Substituted Fe (II) Complexes. 取代铁（II）配合物自旋交叉性质的理性化。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-23 DOI: 10.1021/acs.inorgchem.5c01523

Gerard Comas-Vilà,Pedro Salvador

{"title":"Rationalizing Spin-Crossover Properties of Substituted Fe (II) Complexes.","authors":"Gerard Comas-Vilà,Pedro Salvador","doi":"10.1021/acs.inorgchem.5c01523","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01523","url":null,"abstract":"We investigate spin-state transitions in a series of 24 [FeII(bppX)2]2+ spin-crossover (SCO) complexes using density functional theory (DFT). The TPSSh/def2-TZVP approach demonstrates reasonable accuracy in predicting spin-state energetics compared to other functionals, though significant deviations persist in transition temperature (T1/2) estimates. Temperature-dependent and quasi-harmonic corrections for low-frequency vibrational contributions to enthalpic and entropic terms yielded only marginal improvements. To improve T1/2 prediction accuracy, we develop electronic descriptors based on effective fragment orbitals (EFOs) and their occupations, quantifying ligand σ-donation and π-acceptor characteristics that govern ligand field strength. Additionally, we introduce a resonance descriptor (R) derived solely from the effective atomic orbitals (eff-AOs) of isolated ligands. Our analysis reveals that electron-donating groups (EDGs) enhance π-electron density in the ligands while simultaneously reducing both σ-donor and π-acceptor capabilities, ultimately lowering the T1/2 value. These descriptors perform reasonably well also for a set of 12 [FeII(pyboxX)2]2+ SCO complexes. This new methodology provides a computationally efficient framework for modulating spin-state properties in transition metal complexes, enabling rational design of SCO materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"98 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684327","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

Gauging the Intramolecular CAr-I Activation from Two Parallel Sets of MCl (M = Cu, Ag, Au) Adducts of an Iodobenzyl CAAC and Its NHC Variant. 用两组平行MCl （M = Cu, Ag, Au）加合物测定碘苄基CAAC及其NHC变体的分子内CAr-I活化

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-23 DOI: 10.1021/acs.inorgchem.5c01527

Sudip Baguli,Subham Sarkar,Soumajit Nath,Dibyendu Mallick,Debabrata Mukherjee

{"title":"Gauging the Intramolecular CAr-I Activation from Two Parallel Sets of MCl (M = Cu, Ag, Au) Adducts of an Iodobenzyl CAAC and Its NHC Variant.","authors":"Sudip Baguli,Subham Sarkar,Soumajit Nath,Dibyendu Mallick,Debabrata Mukherjee","doi":"10.1021/acs.inorgchem.5c01527","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01527","url":null,"abstract":"A cyclic(alkyl)(amino)carbene (CAAC; 1) with an iodobenzyl side arm and an analogous N-heterocyclic carbene (NHC; 2) are isolated by deprotonating their corresponding pyrrolinium and imidazolium salt precursors [1H]Br and [2H]Br, respectively. Two parallel series of MCl (M = Cu, Ag, Au) complexes of 1 and 2 are then considered for the potential intramolecular CAr-I oxidative addition (OA) at the metal center. CuCl not only carries out the OA with both the carbenes but also further undergoes a CAr-Ccarbene coupling by reductive elimination (RE) to give the fused tricyclic pyrrolinium (3) and imidazolium (9) cations, respectively, with [ICuCl]- as the counteranion. Though the Cu(III) intermediate is not detected in either case, a starting 2-CuCl adduct (6) is isolated by its insolubility in THF. In contrast, AgCl and AuCl do not proceed beyond the carbene adducts (1-AgCl (4); 1-AuCl (5); 2-AgCl (7); and 2-AuCl (8)). The experimental observations agree well with DFT analyses, which also show the transformation to be more facile in the NHC case than the CAAC due to a higher conformational flexibility offered by the former. Lastly, an intramolecular CAr-Br bond also follows a similar pathway as the CAr-I with both the carbene types and CuCl.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"20 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684059","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

Incorporation of Tellurium into a NNN Pincer Ligand Framework and Consequences on Coordination Behavior. 碲在NNN钳形配体框架中的加入及其对配位行为的影响。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-23 DOI: 10.1021/acs.inorgchem.5c01741

Anthony L Amaya,Mehrnaz Abbasichaleshtori,Lina M Delgado,Bailey S Bouley,Hadi D Arman,Anthony F Cozzolino,Zachary J Tonzetich

{"title":"Incorporation of Tellurium into a NNN Pincer Ligand Framework and Consequences on Coordination Behavior.","authors":"Anthony L Amaya,Mehrnaz Abbasichaleshtori,Lina M Delgado,Bailey S Bouley,Hadi D Arman,Anthony F Cozzolino,Zachary J Tonzetich","doi":"10.1021/acs.inorgchem.5c01741","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01741","url":null,"abstract":"Secondary bonding interactions such as hydrogen-bonding have emerged as beneficial design elements in the construction of molecular catalysts. Here we examine the incorporation of chalcogen-bonding units in the form of benzotellurazole moieties into an NNN chelating framework. A series of substituted 2,6-bis(benzotellurazole)pyridines (NNNR, R = H, tBu, CF3, and Me) have been synthesized through double deoxygenative cyclization of pyridine diamide precursors. The new NNNR species are fully characterized in solution and the solid state and demonstrate planar structures consistent with related pyridine-bis(benzoxazole) chelates. Coordination complexes of Fe and Mn have been identified and structurally characterized demonstrating intermolecular chalcogen bonding between Te and Cl. Despite this promise, the compounds display very low solubility in common solvents and are found to readily demetalate in the presence of coordinating solvents. To investigate the factors contributing to the weak metal binding, density functional theory calculations are performed. The calculations demonstrate unfavorable energetics associated with the planar syn,syn conformation required for metal binding, which is a consequence of steric interactions between the pyridine unit and the large Te atoms of the benzotellurazole.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"32 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144693437","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

Organozinc Reagents in Solution: Insights from Ab Initio Molecular Dynamics and X-ray Absorption Spectroscopy. 溶液中的有机锌试剂：从头算分子动力学和x射线吸收光谱的见解。

IF 4.3 2区化学

Inorganic Chemistry Pub Date : 2025-07-23 DOI: 10.1021/acs.inorgchem.5c02580

Jordan Rio, Quentin Pessemesse, Michele Cascella, Pierre-Adrien Payard, Marie-Eve L Perrin

{"title":"Organozinc Reagents in Solution: Insights from Ab Initio Molecular Dynamics and X-ray Absorption Spectroscopy.","authors":"Jordan Rio, Quentin Pessemesse, Michele Cascella, Pierre-Adrien Payard, Marie-Eve L Perrin","doi":"10.1021/acs.inorgchem.5c02580","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c02580","url":null,"abstract":"Organozinc reagents are widely used in synthesis; however, their solution-phase structures and the resulting effects on reactivity remain insufficiently understood. Here, we present a computational workflow, validated by X-ray absorption spectroscopy, to characterize the solvation dynamics of ZnCl2, ZnMeCl, and ZnMe2 in tetrahydrofuran (THF) solution. Ab initio molecular dynamics (metadynamics and Blue Moon sampling) in explicit solvent cage reveal a distribution of solvation states at room temperature, resolving the long-standing ambiguity surrounding the solvation environment of ZnMe2. Spectral signatures derived from molecular dynamic trajectories and time-dependent DFT closely match the experimental XANES and IR data collected from the literature. We apply this framework to evaluate the effects of solvation on the transmetalation between ZnMe2 and PdMeCl(PPh2Me)2. Although THF coordination to ZnMe2 has a limited influence on activation barriers, changes in solvation state along the reaction coordinate emerge as key thermodynamic drivers. These findings underscore the need to account for solvation equilibria when modeling organozinc-mediated catalytic processes.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":""},"PeriodicalIF":4.3,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144688349","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

Homoleptic Iridium(III) Carbene Complexes with gem-Dimethyl-1,2,4-triazolo[4,3-a]indole Chelates for Blue Organic Light-Emitting Diodes. 蓝色有机发光二极管与宝石-二甲基-1,2,4-三唑[4,3-a]吲哚螯合物的同感铱（III）卡宾配合物

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-22 DOI: 10.1021/acs.inorgchem.5c01038

Zhen Zhang,Hongyang Zhang,Peng Tao,Yingjie Sun,Jibiao Jin,Jie Zhang,Xiaokang Zheng,Dou Luo,Jiming Wang,Wei Tang,Shuming Chen,Wai-Yeung Wong

{"title":"Homoleptic Iridium(III) Carbene Complexes with gem-Dimethyl-1,2,4-triazolo[4,3-a]indole Chelates for Blue Organic Light-Emitting Diodes.","authors":"Zhen Zhang,Hongyang Zhang,Peng Tao,Yingjie Sun,Jibiao Jin,Jie Zhang,Xiaokang Zheng,Dou Luo,Jiming Wang,Wei Tang,Shuming Chen,Wai-Yeung Wong","doi":"10.1021/acs.inorgchem.5c01038","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01038","url":null,"abstract":"Iridium(III) carbene complexes represent the advanced structure of efficient blue phosphorescent emitters to date, yet the refinement of the carbene group is not easy to realize in a large-scale synthesis route. In this study, we develop a series of deep-blue emissive homoleptic Ir(III) carbene complexes bearing the novel gem-dimethyl-1,2,4-triazolo[4,3-a]indole ligand. The carbene ligand can be produced on a large scale without purification by column chromatography, and the cyclometalation can be completed in a high yield without the use of Ag2O. The gem-dimethyl and fused-ring in this unconventional carbene ligand endow Ir(III) complexes with the insensitivity to dopant concentration and high rigidity. The inclusion of a large steric electron-donating tert-butyl group in these phosphors promotes the radiative transition rates and increases their photoluminescence quantum yields (PLQYs). As a result, these complexes exhibit great promise as deep-blue phosphors with the emission maxima at ∼435 nm. We successfully fabricated phosphorescent organic light-emitting diodes (OLEDs) based on these blue emitters, in which a tert-butyl-functionalized mer-Ir(III) phosphor (mer-TzDm-t)-based device achieves a maximum external quantum efficiency (EQE) up to 11.75% and Commission Internationale de I'Eclairage (CIEx,y) coordinates of (0.161, 0.117).","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"15 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684063","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

From Oxidized PrNi0.9Al0.1O3 to Reduced PrNi0.9Al0.1O2+δ Perovskite Nickelates: Stabilization of Infinite-Layer Specimens with Monovalent Ni in the Bulk Polycrystalline Form. 从氧化PrNi0.9Al0.1O3到还原PrNi0.9Al0.1O2+δ钙钛矿镍酸盐：一价镍在块状多晶形式下的无限层试样的稳定性

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-22 DOI: 10.1021/acs.inorgchem.5c02051

Javier Gainza,Carlos A López,Romualdo S Silva,João Elias F S Rodrigues,Federico Serrano-Sánchez,Alina Skorynina,Norbert M Nemes,María T Fernández-Díaz,José Luis Martínez,José Antonio Alonso

{"title":"From Oxidized PrNi0.9Al0.1O3 to Reduced PrNi0.9Al0.1O2+δ Perovskite Nickelates: Stabilization of Infinite-Layer Specimens with Monovalent Ni in the Bulk Polycrystalline Form.","authors":"Javier Gainza,Carlos A López,Romualdo S Silva,João Elias F S Rodrigues,Federico Serrano-Sánchez,Alina Skorynina,Norbert M Nemes,María T Fernández-Díaz,José Luis Martínez,José Antonio Alonso","doi":"10.1021/acs.inorgchem.5c02051","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c02051","url":null,"abstract":"Recently, a new class of high-temperature superconductors, RNiO2 (where R represents rare-earth elements) with infinite-layer (IL) structure, has been identified. They possess the same structural framework as the renowned high-Tc cuprates but with nickel replacing copper as the central element. In this study, we successfully synthesized infinite-layer samples of PrNi0.9Al0.1O2+δ in the bulk polycrystalline form through topotactic reduction of the PrNi0.9Al0.1O3 orthorhombic perovskite, via treatment with CaH2. The incorporation of aluminum at the octahedral sites promotes the stabilization of bulk derivatives of the infinite-layer structure since unreduced [AlO6] octahedra keep the layers together and prevent their decomposition. The lack of superconductivity in bulk samples has been a subject of intense debate in recent literature. One major theoretical question concerns whether hydrogen becomes incorporated into the structure during the reduction from RNiO3 to RNiO2─as suggested by theory. Here, we present neutron powder diffraction data demonstrating that hydride ions indeed reside within the IL lattice in samples of stoichiometry PrNi0.9Al0.1O2.10H0.16. Additional crystallographic analyses were carried out using temperature-dependent synchrotron X-ray diffraction on both reduced and oxidized phases. Furthermore, spectroscopic analysis via XAS and magnetometry confirms the reduction of Ni3+ to the Ni+ oxidation state, aligning with the crystallochemical evidence.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"143 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684064","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

Confining Engineered FeS Nanoparticles in Mesoporous Silica for Enhancing Mercury Sequestration and Methylation Suppression. 在介孔二氧化硅中限制工程FeS纳米颗粒以增强汞固存和甲基化抑制。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-22 DOI: 10.1021/acs.inorgchem.5c02329

Lei Yang,Yunyun Ji,Daoming Zhou,Xinyi Guo,Sheng-Li Hou,Wei Chen,Tong Zhang

{"title":"Confining Engineered FeS Nanoparticles in Mesoporous Silica for Enhancing Mercury Sequestration and Methylation Suppression.","authors":"Lei Yang,Yunyun Ji,Daoming Zhou,Xinyi Guo,Sheng-Li Hou,Wei Chen,Tong Zhang","doi":"10.1021/acs.inorgchem.5c02329","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c02329","url":null,"abstract":"Addressing mercury (Hg) contamination is an urgent priority due to its severe threats to human health. However, conventional approaches pose risks of generating highly toxic methylmercury (MeHg), highlighting the need for advanced strategies to reduce Hg bioavailability in remediation. To address this challenge, we developed a nanoconfinement strategy utilizing mesoporous silica nanoparticles (MSNs) as carriers to anchor highly dispersed mackinawite (FeS) nanoparticles within the pores for Hg(II) immobilization. Compared to FeS synthesized via homogeneous coprecipitation, the synthesized nanoconfined FeS (FeS@MSNs) exhibited enhanced adsorption kinetics with a pseudo-second-order adsorption rate constant of 5.50 × 10-5 g FeS/(mg·min) and a maximum adsorption capacity of 1815.95 mg/g FeS, and improved resistance to environmental interference. Importantly, the size confinement effect of the pores prevented methylating bacteria from accessing immobilized Hg, thereby inhibiting MeHg generation by 97%. With a combination of spectroscopic and microscopic evidence, FeS@MSNs preferentially removed Hg(II) by forming mercury sulfide (HgS) precipitates within the pores rather than via surface adsorption or bulk precipitation. This study provides valuable insights into how nanoconfinement enhances nanomaterial performance and reduces the long-term bioavailability of heavy metals, demonstrating potential for diverse heavy metal remediation applications.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"281 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684122","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

Visible Light-Activatable Organoboron Complexes Featuring Salicylaldehyde Azine Ligands for Rapid Cationic Polymerization and Mechanism Studies. 以水杨醛-嗪为配体的可见光可活化有机硼配合物的快速阳离子聚合及其机理研究。

IF 4.3 2区化学

Inorganic Chemistry Pub Date : 2025-07-21 Epub Date: 2025-07-04 DOI: 10.1021/acs.inorgchem.5c00783

Yingzhu Sun, Lei Wang, Changjiang Yu, Zihao Wang, Jinsong Shao, Xinsheng Xu, Yaxiong Wei, Yangyang Xu, Lijuan Jiao, Erhong Hao

{"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":"10.1021/acs.inorgchem.5c00783","url":null,"abstract":"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.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":"14162-14171"},"PeriodicalIF":4.3,"publicationDate":"2025-07-21","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}

引用次数: 0