Inorganic Chemistry最新文献_第2页

DFT Calculation Screening of Transition Metal (TM) Doped MgO Catalyzed Dry Reforming of Methane Reaction and Related Experimental Verification. 过渡金属掺杂MgO催化甲烷干重整反应的DFT计算筛选及实验验证

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-24 DOI: 10.1021/acs.inorgchem.5c01653

Lianyang Zhang,Zhiling Huang,Dongxia Zhang,Shengjie Xia

{"title":"DFT Calculation Screening of Transition Metal (TM) Doped MgO Catalyzed Dry Reforming of Methane Reaction and Related Experimental Verification.","authors":"Lianyang Zhang,Zhiling Huang,Dongxia Zhang,Shengjie Xia","doi":"10.1021/acs.inorgchem.5c01653","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01653","url":null,"abstract":"Theoretical calculations can quickly screen for effective catalyst systems, and experimental verification is also essential. This paper uses density functional theory (DFT) to construct a transition metal (TM)-doped MgO structure. By studying the effects of TM doping on key steps in dry reforming of methane (DRM) reaction, including CO2 adsorption and catalytic CO2 dissociation, a comprehensive screening of 30 TMs was conducted. It indicates that TM atoms can promote the adsorption of CO2 by MgO due to the presence of electron deficient d orbitals, and TM can also serve as main adsorption site to attract CO2. After stability analysis of TM/MgO, calculation of CO2 adsorption and dissociation, and comprehensive consideration of adsorption energy (Eads) and energy barrier (Ea), it was screened from 30 systems that Mo/MgO had the lowest catalytic reaction Ea, Zr/MgO had the best Eads, and Fe/MgO had the most balanced comprehensive properties. Based on theoretical calculations, Fe/MgO, Zr/MgO, and Mo/MgO were synthesized, characterized, and applied to catalyze DRM reaction. The reaction mechanism of TM/MgO(TM = Fe, Zr, Mo) catalyzing DRM was analyzed and compared from the perspectives of catalytic activity, stability, and types and quantities of carbon deposits, achieving the goal of theoretical calculations guiding experimental synthesis.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"17 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144693527","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

Balance Control of Capacity and Stability of the Bimetallic Prussian Blue Cathode for High-Performance Sodium-Ion Batteries. 高性能钠离子电池双金属普鲁士蓝阴极容量与稳定性的平衡控制。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-24 DOI: 10.1021/acs.inorgchem.5c01143

Beibei Kuang,Wanchang Feng,Yuxin Shi,Liang Chen,Zilin Yang,Qian Li,Wenting Li,Shengxu Wei,Yiwen Liu,Zheng Liu,Huan Pang

{"title":"Balance Control of Capacity and Stability of the Bimetallic Prussian Blue Cathode for High-Performance Sodium-Ion Batteries.","authors":"Beibei Kuang,Wanchang Feng,Yuxin Shi,Liang Chen,Zilin Yang,Qian Li,Wenting Li,Shengxu Wei,Yiwen Liu,Zheng Liu,Huan Pang","doi":"10.1021/acs.inorgchem.5c01143","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01143","url":null,"abstract":"Prussian blue analogs (PBAs) are one of the most promising cathode materials for sodium-ion batteries (SIBs) due to their open three-dimensional backbone structure and well-developed sodium-ion diffusion channels. However, the practical application of PBAs still faces great challenges, such as a high content of anionic vacancies and poor structural stability. In this work, we synthesized nickel-manganese bimetallic PBAs by a simple coprecipitation method, and adjusting the ratio of nickel (electrochemically inert element) and manganese (electrochemically active element) can effectively control the charging and discharging depth of the battery. By precisely optimizing the ratio between the two, the charging and discharging performances can be reasonably adjusted, thus improving the overall efficiency and stability of the battery. As the cathode material of SIBs, bimetallic PBA shows excellent specific capacity, outstanding multiplicity performance, and long-term cycle stability. Especially, the capacity retention of the Ni0.1Mn1.9HCF electrode can be maintained as high as 70.5% (∼55.4 mAh g-1) after 100 cycles at a higher current density of 500 mA g-1. In addition, the cycling stability of all materials was further significantly improved in eutectic electrolytes. A novel and simple strategy can provide an effective method for the balance control of capacity and cycling stability of the PBA cathode for SIBs.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"27 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144701053","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

A Layered, Piedfort-Aggregated Cu(I) Isocyanide Coordination Network Derived from an Encumbering Tritopic Linker. 由累赘三位连接体衍生的层状、桩堡聚集铜(I)异氰化物配位网络。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-24 DOI: 10.1021/acs.inorgchem.5c02312

Adam M Grippo,Ritchie E Hernandez,Milan Gembicky,Joshua S Figueroa

{"title":"A Layered, Piedfort-Aggregated Cu(I) Isocyanide Coordination Network Derived from an Encumbering Tritopic Linker.","authors":"Adam M Grippo,Ritchie E Hernandez,Milan Gembicky,Joshua S Figueroa","doi":"10.1021/acs.inorgchem.5c02312","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c02312","url":null,"abstract":"Isocyanide coordination networks (ISOCNs) are emerging as a distinct class of framework materials capable of organizing low-valent metal centers into metal-organic framework (MOF)-type structural building units (SBUs). To date, most of the reported ISOCN materials have employed linear ditopic diisocyanide linkers. In an effort to expand linker architectures associated with ISOCN formation, reported here is the synthesis of the encumbering tritopic isocyanide linker (CNArDipp2)3Ar3 (ArDipp2 = 2,6-(2,6-(i-Pr)2C6H3)2C6H2; Ar3 = 1,3,5-(C6H4)3C6H3) and its ability to produce network materials with Cu(I) centers. Treatment of (CNArDipp2)3Ar3 with [Cu(NCMe)4]PF6 in THF under solvothermal conditions produced single crystals of the new network, CuISOCN-6, which possesses cationic [Cu(THF)(CNArDipp2)3]+ SBUs linked by a triphenylbenzene core. The lattice structure of CuISOCN-6 revealed a noninterpenetrated two-dimensional honeycomb sheet corresponding to an hcb (6,3) net. The honeycomb sheets of CuISOCN-6 are stacked in an offset, six-layer repeating pattern that possess distinct piedfort aggregates assembled via noncovalent π-π stacking interactions between the triphenylbenzene core of the (CNArDipp2)3Ar3 linker. The piedfort aggregate structural elements compress the lattice structure of CuISOCN-6 such that it is dense packed and nonporous, as determined via gas sorption measurements. However, CuISOCN-6 possesses considerable thermal and chemical stability on account of interlayer piedfort association.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"17 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144693200","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

A Photoluminescent Uranyl Complex for Dual-Platform X-ray Dose Detection. 用于双平台x射线剂量检测的光致发光铀酰配合物。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-24 DOI: 10.1021/acs.inorgchem.5c02631

Cong Li,Jian Xie,Baowei Hu,Heyao Zhang,Huangjie Lu

引用次数: 0

Ligand-Nuclei Effects on Spin Relaxation in V(IV) Complexes. 配体-核对V（IV）配合物自旋弛豫的影响。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-24 DOI: 10.1021/acs.inorgchem.5c01930

Roxanna Martinez,Ökten Üngör,Cassidy E Jackson,Firoz S T Khan,Johan van Tol,Joseph M Zadrozny

{"title":"Ligand-Nuclei Effects on Spin Relaxation in V(IV) Complexes.","authors":"Roxanna Martinez,Ökten Üngör,Cassidy E Jackson,Firoz S T Khan,Johan van Tol,Joseph M Zadrozny","doi":"10.1021/acs.inorgchem.5c01930","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01930","url":null,"abstract":"Understanding how magnetic nuclei affect spin relaxation is vital for designing robust spin coherence in magnetic materials and molecules. A key question is the extent that magnetic nuclei close to a spin (e.g., in the ligand shell of a metal complex) influence relaxation and how it varies over different classes of nuclei. Herein, we apply high-field EPR, X-band EPR, and ac magnetic susceptibility techniques to a family of five V(IV) complexes of the type [V(C6X4O2)3]2-, featuring five different sets of 12 nuclear spins on the ligand shell: X = 1H (1), 2H (2), 19F (3), 35/37Cl (4), and 79/81Br (5). We found several unanticipated results in these studies. For example, at high-field/-frequency, we found that compound 1, with the highest-magnetic-moment ligand nuclear spins, exhibits the longest phase memory relaxation times of the series. Furthermore, at lower fields, we found that the spin-lattice relaxation time and its field dependence were ligand-dependent, despite no obvious change in electronic structure across the five species. Based on this data, structural comparisons, and Raman spectroscopic data, we tentatively conclude that the spin-lattice relaxation properties of 1-5 stem from fine-tuning of the local magnetic environment with changing identity of the X atoms.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"115 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144701059","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

Planar and Nonplanar Polymorphic Forms of Ni(II)-Porphyrin: Photophysical, Photocatalysis, and DFT Study. Ni(II)-卟啉的平面和非平面多晶形式：光物理、光催化和DFT研究。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-24 DOI: 10.1021/acs.inorgchem.4c04221

Swati Dhamija,Rafia Siddiqui,Ritam Das,Suman Majee,Devalina Ray,Hatem M Titi,Ranjan Patra

{"title":"Planar and Nonplanar Polymorphic Forms of Ni(II)-Porphyrin: Photophysical, Photocatalysis, and DFT Study.","authors":"Swati Dhamija,Rafia Siddiqui,Ritam Das,Suman Majee,Devalina Ray,Hatem M Titi,Ranjan Patra","doi":"10.1021/acs.inorgchem.4c04221","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04221","url":null,"abstract":"Herein, we report the polymorphic forms of Ni(II)-tetra(4-bromo-2,6-difluorophenyl) porphyrin (1), which have applications in the photocatalytic conversion of indoline to indole under blue light. X-ray diffraction studies reveal that one polymorphic form of 1 (namely, 1α) stabilizes in the monoclinic system and has a planar geometry, while the other form (namely, 1β) has a nonplanar geometry and crystallizes in the tetragonal system. Due to their different conformations (planar and nonplanar), these polymorphs exhibit distinct solid-state properties. For instance, the solid-state absorption spectrum of 1β shows a broad absorption Soret band compared to 1α. Complementary theoretical studies show that compound 1α is energetically more stable than compound 1β by 16.5 kcal mol-1. In addition, electrostatic potential isosurfaces clearly reveal the presence of σ-holes on the bromine atom, indicative of halogen bond interactions in the crystalline state. The electronic structures of porphyrins directly influence the photophysical properties through two major effects: (a) porphyrin core geometry and (b) heavy atom effect (HAE). The photocatalytic study demonstrates the efficient conversion of indoline to indole using compound 1 in the presence of blue light.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"120 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144693198","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

Synthesis and Reactivity of an Yttrium Hydride Complex Supported by an Arene-Anchored Bis(phosphinomethylamido) Palladium (0) Metalloligand. 芳烃锚定双（磷甲基胺）钯金属配体负载的氢化钇配合物的合成及反应性。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-24 DOI: 10.1021/acs.inorgchem.5c01897

Hang Shen,Cunyu Song,Dongjing Hong,Peng Cui

引用次数: 0

One-Pot Isomer-Pure Synthesis of 1,4-Diorgano[60]fullerene Complexes via Tetrafluoropyridine Regulated Site-Selective Coordination of Platinum/Palladium on the 1,4-Unsymmetric C60 Core. 四氟吡啶调控铂/钯在1,4-不对称C60核上的位点选择性配位一锅纯异构体合成1,4-二有机[60]富勒烯配合物

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-24 DOI: 10.1021/acs.inorgchem.5c01723

Jin-Ying Liu,Yi-Long Li,Zheng-Chun Yin,Jun Xuan,Hong-Ping Zhou,Fei Li

引用次数: 0

Triel-Defined Helicity in One-Dimensional III-VI-VII van der Waals Crystals. 一维III-VI-VII范德华晶体的三定义螺旋度。

IF 4.3 2区化学

Inorganic Chemistry Pub Date : 2025-07-24 DOI: 10.1021/acs.inorgchem.5c01731

Kaitlyn G Dold, Dmitri Leo Mesoza Cordova, Thanh N Huynh, Griffin M Milligan, Simon J Teat, Maxx Q Arguilla

{"title":"Triel-Defined Helicity in One-Dimensional III-VI-VII van der Waals Crystals.","authors":"Kaitlyn G Dold, Dmitri Leo Mesoza Cordova, Thanh N Huynh, Griffin M Milligan, Simon J Teat, Maxx Q Arguilla","doi":"10.1021/acs.inorgchem.5c01731","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01731","url":null,"abstract":"<p><p>Inorganic extended lattice solids that bear complex helical motifs manifest unusual physical and quantum states that arise due to their noncentrosymmetric or chiral nature. However, the systematic understanding of how elemental composition influences the structure and physical properties in helical inorganic crystals has been precluded by the rarity of these materials and the lack of modular phases that display such motifs. Here, we report the synthesis of AlSeI single crystals, the first aluminum-containing helical crystal in the III-VI-VII 1D van der Waals class. AlSeI completes the experimentally accessible triel series in the helical selene iodides alongside InSeI and GaSeI. Using the Al, Ga, and In triel series in this selene iodide class, we experimentally demonstrate the evolution of the local quasi-tetrahedral building unit geometry, chain packing, helical parameters, and band gaps based primarily on the identity of the triel atom. Our results underscore the chemical modularity of these phases, the broad range of helical parameters, and the spectrum of electronic states from the visible to the ultraviolet range in this emergent class of 1D, exfoliable, and helical extended lattice solids.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":""},"PeriodicalIF":4.3,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144705768","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

Detecting Coordination-Induced Spin-State Switching in Coumarin-Tagged Nickel(II) Complexes via the Fluorescence Quenching Method. 利用荧光猝灭法检测香豆素标记镍（II）配合物中配位诱导的自旋态开关。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-24 DOI: 10.1021/acs.inorgchem.5c01832

Shufang Xue,Tengli Wang,Jintao Zhu,Shanshan Deng,Yanying Zhao,Lifei Zou,Yunnan Guo

{"title":"Detecting Coordination-Induced Spin-State Switching in Coumarin-Tagged Nickel(II) Complexes via the Fluorescence Quenching Method.","authors":"Shufang Xue,Tengli Wang,Jintao Zhu,Shanshan Deng,Yanying Zhao,Lifei Zou,Yunnan Guo","doi":"10.1021/acs.inorgchem.5c01832","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01832","url":null,"abstract":"In this study, coumarin-functionalized Ni(II) complex 3 has been demonstrated to act as a fluorescent probe for the quantification of coordination-induced spin-state switching (CISSS) behavior via fluorescence quenching. Upon coordination with pyridine, the Ni(II) center undergoes a spin-state transition from a diamagnetic to a paramagnetic form, leading to the observable changes in fluorescence intensity. Deconvolution of quenching contributions based on three distinct models─CISSS quenching, sphere of action, and dynamic (collisional) quenching─reveals that static quenching mechanisms (involving CISSS quenching and sphere of action) dominate throughout the titration process, with CISSS quenching contributing up to 28% maximally. Theoretical analysis further confirms that the elevation of the highest occupied molecular orbital (HOMO) energy level in the ligand upon coordination with nickel(II) ions facilitates the photoinduced electron transfer (PET) process. Nickel(II) complexes in diamagnetic and paramagnetic states exhibit distinct PET rates (kPET-dia = 0.37(1) ns-1 for diamagnetic species; kPET-para = 0.48(2) ns-1 for paramagnetic species), which, in turn, induces detectable CISSS-dependent fluorescence quenching. This work demonstrates the feasibility of using fluorescence quenching as a visual tool to monitor CISSS behavior in coordination complexes, offering new insights into spin-state-responsive molecular sensing.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"699 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144693194","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