Inorganic Chemistry最新文献

Theoretical Analysis of Photochemical and Electrochemical Properties of Substituted Cobalt Bipyridine Complexes: Redox Mediators in Dye-Sensitized Solar Cells as a Case Study. 取代钴联吡啶配合物的光化学和电化学性质的理论分析：染料敏化太阳能电池氧化还原介质的案例研究。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-08 DOI: 10.1021/acs.inorgchem.5c01156

Arshak A Tsaturyan,Ginevra Giobbio,Matteo Bonomo,Andrea Fin,Nadia Barbero,Raffaele Borrelli,Claudia Barolo

{"title":"Theoretical Analysis of Photochemical and Electrochemical Properties of Substituted Cobalt Bipyridine Complexes: Redox Mediators in Dye-Sensitized Solar Cells as a Case Study.","authors":"Arshak A Tsaturyan,Ginevra Giobbio,Matteo Bonomo,Andrea Fin,Nadia Barbero,Raffaele Borrelli,Claudia Barolo","doi":"10.1021/acs.inorgchem.5c01156","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01156","url":null,"abstract":"This study presents a comprehensive theoretical investigation into the photophysical and electrochemical properties of substituted cobalt bipyridine complexes, evaluated as potential redox mediators in dye-sensitized solar cells. Utilizing a variety of computational methods, including density functional theory and multireference electron correlation techniques, we examine the influence of various substituents on the electronic structure and stability of cobalt complexes. Our findings reveal that strong electron-withdrawing groups enhance the formal redox potential, while electron-donating groups decrease it, illustrating the delicate balance between electronic effects on the complex stability. The simulated properties were compared with the available experimental measurements, demonstrating good correlation and validating the computational approaches used. Analysis of the spin states indicates that cobalt(II) complexes predominantly exist in a high-spin state with low-spin configurations favored in cobalt(III). The reorganization energy for these complexes was calculated, highlighting the role of the inner and outer-shell contributions in determining electron transfer kinetics.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"4 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144578553","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

Permeable Layered Tin Sulfide Ion Exchanger for Rapid Elimination of Cs+ and Sr2. 快速去除Cs+和Sr2的可渗透层状硫化锡离子交换剂。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-08 DOI: 10.1021/acs.inorgchem.5c01997

Yu-Jie Zhang,Lin Cheng,Ze-Yu Wang,Ze-Jia Shen,Fei-Fei Wang,Jun-Zheng Wang,Zi-Xin Qiu,Shuaihua Wang,Kai-Yao Wang,Cheng Wang

{"title":"Permeable Layered Tin Sulfide Ion Exchanger for Rapid Elimination of Cs+ and Sr2.","authors":"Yu-Jie Zhang,Lin Cheng,Ze-Yu Wang,Ze-Jia Shen,Fei-Fei Wang,Jun-Zheng Wang,Zi-Xin Qiu,Shuaihua Wang,Kai-Yao Wang,Cheng Wang","doi":"10.1021/acs.inorgchem.5c01997","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01997","url":null,"abstract":"A porous layered tin sulfide material, [(CH3)2NH2]2Sn3S7·0.4H2O (SnS-1), is developed for rapid Cs+ and Sr2+ removal from aqueous solutions. The alignment of hexagonal windows (8.3 × 8.3 Å2 in cross-section) across the stacked layers forms straight pseudochannels that enables effective ion diffusion and accommodation. SnS-1 exhibits outstanding ion exchange kinetics (k2Cs = 0.256 g mg-1 min-1; k2Sr = 0.272 g mg-1 min-1) and capacities (qmCs = 417.24 mg g-1; qmSr = 116.18 mg g-1), exceeding most chalcogenide-based exchangers. It exhibits acid-base resistance across a broad pH range (0-11) and remarkable selectivity for Cs+ and Sr2+ over various competing ions. Dynamic column filtration confirms the separation applicability of SnS-1, featuring sustained Sr2+ removal (RSr = 94.45-99.51%) against Cs+ (RCs = -20 ± 5%). The SnS-1/PTFE composite membrane can efficiently remove Cs+ and Sr2+ from continuous flow (2.0 mL min-1 cm-2), with removal efficiencies exceeding 91.71 and 98.91%, respectively. Moreover, the adsorbed Cs+ and Sr2+ ions can be readily eluted from the spent column and membrane using a 2 M NaCl solution. Combined with simple synthesis, radiolytic stability, and superior performance, microporous SnS-1 emerges as a promising candidate for nuclear wastewater remediation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"153 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144578554","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

Spectroscopic Properties of Americium(III) in Mineral Acid Media. 无机酸介质中镅（III）的光谱特性。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-08 DOI: 10.1021/acs.inorgchem.5c00781

David Schnable,Erik D Reinhart,José M Veleta,Ana Arteaga,Robert G Surbella Iii

{"title":"Spectroscopic Properties of Americium(III) in Mineral Acid Media.","authors":"David Schnable,Erik D Reinhart,José M Veleta,Ana Arteaga,Robert G Surbella Iii","doi":"10.1021/acs.inorgchem.5c00781","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00781","url":null,"abstract":"We report the preparation and optical characterization of three solutions of Am(III) in common aqueous (aq.) mineral acids (HCl, HNO3, and HBr), including absorption, emission, and Raman vibrational analyses. To our knowledge, this study provides the first detailed absorption spectra of Am(III) spanning the entire UV/vis/NIR region in these mineral acids reported since the 1960s. Using this high-resolution absorption data, provided in an open access format for the broader field, we build on prior work by Carnall and others to provide detailed optical analysis including all transition assignments. This work also includes the first reported absorption spectrum of Am(III) in aq. HBr. Characteristic Am(III) luminescence could be detected from all three samples. These are the first reports of emission from Am(III) in these acid systems, which build on prior emission reports collected from aq. HClO4 solutions. The acquired emission spectra display anion-dependent shifting of the visible-region transitions by up to 21 nm from their predicted positions, akin to the nephelauxetic effect. The shift magnitude trends linearly according to acid pKa and more generally according to the transition metal spectrochemical series. These ligand field effects, coupled with luminescence lifetime experiments, indicate that weak Am-X interactions persist in solution.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"34 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144578555","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

Unveiling Unusual Reactivity of SO2 and Unusual Type of S-X Long Bonds. 揭示SO2的异常反应性和S-X长键的异常类型。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-08 DOI: 10.1021/acs.inorgchem.5c02435

Shuai Ma,Longfei Li,Xiaofeng Xie,Peng Wang,He Bai,Kan Yang,Xueqing Song,Henry F Schaefer

{"title":"Unveiling Unusual Reactivity of SO2 and Unusual Type of S-X Long Bonds.","authors":"Shuai Ma,Longfei Li,Xiaofeng Xie,Peng Wang,He Bai,Kan Yang,Xueqing Song,Henry F Schaefer","doi":"10.1021/acs.inorgchem.5c02435","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c02435","url":null,"abstract":"A new reactivity of SO2 to form unusual stable M-X-SO2 (X = F, Cl, H) complexes is unveiled in this study. Moreover, a new type of S-X long bonds, which are significantly longer than traditional S-X covalent bonds, has been discovered. The P,N-ligated Ni-F complex model 1A can bind a SO2 molecule through the new F-S long bond (2.207 Å), and a stable Ni-F-SO2 complex 1B is generated, being exergonic by 2.2 kcal/mol. According to natural localized molecular orbital analysis, the new S-F long bond has a unique p(F) → π*(O═S═O) bonding interaction, which is shown to arise from the long S-F length. In comparison, the strength of the new F-S long bond (-2.2 kcal/mol) is found to be significantly stronger than common noncovalent interactions such as the hydrogen and halogen bond. The substituent modulations suggest that the electron-donating groups can increase the strength of new F-S bonds and enhance binding free energies ΔGbind. The scope of possible M-X complexes was explored, and various metals and X (F, Cl, and H) ligands were found to form stable M-X-SO2 complexes. Specifically, the anionic M-X complexes display much higher ΔGbind values, ranging from -8 to -10 kcal/mol. The study paves the way for a green, recyclable, and adjustable SO2 absorption method.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"3 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144578552","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

Emission Properties of [Au(CN)2]- Oligomers in Crystals with One-Dimensional Au Chain Structures. 一维金链结构晶体中[Au(CN)2]-低聚物的发射特性

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-08 DOI: 10.1021/acs.inorgchem.5c00625

Munetaka Iwamura,Kaho Takebayashi,Daisuke Naruse,Ryo Wakabayashi,Kiyoshi Tsuge,Koichi Nozaki

{"title":"Emission Properties of [Au(CN)2]- Oligomers in Crystals with One-Dimensional Au Chain Structures.","authors":"Munetaka Iwamura,Kaho Takebayashi,Daisuke Naruse,Ryo Wakabayashi,Kiyoshi Tsuge,Koichi Nozaki","doi":"10.1021/acs.inorgchem.5c00625","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00625","url":null,"abstract":"The crystal structures of (Me4N)3[Au(CN)2]2Cl (Me4N: tetra-methylammonium, 1) and Et4N[Au(CN)2] (Et4N: tetra-ethylammonium, 2) were found to include 1-dimensional Au chain structures, where the Au···Au distance is as short as 3.3 Å in 1 and 3.6 Å in 2. Because the structures of the ground state oligomers have linear staggered structures, the photoexcited oligomers generated in these crystals are also expected to have linear staggered structures. The crystals exhibit emission, in which the dominant emission bands are located at 430 nm in 1 and 400 nm in 2 at 77 K with emission quantum yields of unity. These emission bands at 77 K were assignable to the phosphorescence of the tetramer and trimer of linear-staggered structures because they resemble the phosphorescence of the trimer and tetramer in aqueous solutions. The radiative lifetimes of the T1 trimer and T1 tetramer were estimated as 0.9 and 1.6 μs, respectively, from their quantum yields and lifetimes. The emission lifetime of 2 was observed in the temperature region of 4-110 K to estimate the zero-field splitting of the lowest triplet state of the trimer as 36 cm-1 (EI-II) and 64 cm-1 (EI-III) and the radiative rate constants of the three states as 1.43 × 103 s-1 (kI), 2.0 × 104 s-1 (kII), 4.8 × 106 s-1 (kIII).","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"5 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144578556","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

IF 4.3 2区化学