Inorganic Chemistry最新文献_第3页

Mitochondria-Localized and Aggregation-Induced Near-Infrared Emission Iridium(III) Complexes for Photodynamic Therapy. 线粒体定位和聚集诱导的近红外发射铱（III）配合物用于光动力治疗。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-02 DOI: 10.1021/acs.inorgchem.5c01814

Weibin Chen,Qianghui Zheng,Wanqing Zhang,Fengfu Fu,Mei-Jin Li

{"title":"Mitochondria-Localized and Aggregation-Induced Near-Infrared Emission Iridium(III) Complexes for Photodynamic Therapy.","authors":"Weibin Chen,Qianghui Zheng,Wanqing Zhang,Fengfu Fu,Mei-Jin Li","doi":"10.1021/acs.inorgchem.5c01814","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01814","url":null,"abstract":"In recent years, the optical functional materials of iridium(III) complexes have attracted much attention due to their excellent photophysical properties and potential biomedical applications. Among them, aggregation-induced emission (AIE) properties have shown significant advantages in photodynamic therapy (PDT). In this work, three new iridium(III) complexes with near-infrared emission were designed and synthesized, and their crystal structures were determined. All complexes exhibited significant AIE phenomena. Especially, Ir-1 containing an -NH2 functional group exhibited a unique hollow nanoparticle morphology, excellent mitochondrial targeting ability, and high reactive oxygen species (ROS) efficiency, which is expected to play an important role as a new type of nanoprobe in the field of PDT. The complex has the ability to generate both type I and type II ROS, which makes it a potent photosensitizer for the efficient phototherapy of hypoxic tumors. What is more, the complex has dual functions of PDT and chemotherapy, and their synergistic effect greatly enhances the antineoplastic effects of the reagent.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"33 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533434","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

Ambient Synthesis for Fe(II) Polypyridyl Complexes with an Order of Magnitude Increase in Charge-Transfer Excited-State Lifetimes over [Fe(bpy)3]2. 与[Fe(bpy)3]相比，Fe（II）多吡啶配合物的电荷转移激发态寿命增加了一个数量级

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-01 DOI: 10.1021/acs.inorgchem.5c01300

Matthew T Baldwin,Nicholas A Zosel,Aaron H Shoemaker,Michael W Mara,Tyler N Haddock,Lin X Chen,Bryan M Hunter

{"title":"Ambient Synthesis for Fe(II) Polypyridyl Complexes with an Order of Magnitude Increase in Charge-Transfer Excited-State Lifetimes over [Fe(bpy)3]2.","authors":"Matthew T Baldwin,Nicholas A Zosel,Aaron H Shoemaker,Michael W Mara,Tyler N Haddock,Lin X Chen,Bryan M Hunter","doi":"10.1021/acs.inorgchem.5c01300","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01300","url":null,"abstract":"Replacing precious metals with abundant metals is an important research focus in photochemical energy conversion and storage to meet global energy demands. However, transition metal complexes (TMCs) based on abundant 3d metals typically possess photochemical disadvantages─such as short charge-transfer excited-state lifetimes─and molecular modifications have focused on optimizing the interplay of structure, dynamics, and energetics to overcome their limitations. One strategy to do so is the use of bespoke ligands that can extend the lifetimes of chemically useful excited states. Here, we report the synthesis and characterization of novel Fe(II) complexes featuring lengthy polypyridyl ligands that can be readily synthesized. Steady-state and transient absorption spectroscopies indicate that these complexes have desirable properties and their excited metal-to-ligand charge-transfer states live an order of magnitude longer than in the benchmark [Fe(bpy)3]2+. This lifetime is largely preserved in the heteroleptic complexes, thereby enabling the preparation of asymmetric complexes. Additionally, we apply nonradiative transition theory to explain the long-time decay kinetics. In light of their ease of preparation and reasonable excited-state lifetimes, we suggest the use of these complexes in Fe(II) dye-sensitized solar cells, where the rate of charge injection would be competitive with increased lifetime.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"70 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533484","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 Promising Short-Wave UV NLO Crystal with an Optimized KBBF-like Structure and Well-Balanced Properties Achieved via a Chemical Substitution Strategy. 一种有前途的短波紫外NLO晶体，具有优化的kbbf样结构和通过化学取代策略获得的良好平衡性能。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-01 DOI: 10.1021/acs.inorgchem.5c02281

Shuaifeng Li,Mengru Liu,Peng Zhao,Huijian Zhao,Ning Ye,Zhanggui Hu,Conggang Li

{"title":"A Promising Short-Wave UV NLO Crystal with an Optimized KBBF-like Structure and Well-Balanced Properties Achieved via a Chemical Substitution Strategy.","authors":"Shuaifeng Li,Mengru Liu,Peng Zhao,Huijian Zhao,Ning Ye,Zhanggui Hu,Conggang Li","doi":"10.1021/acs.inorgchem.5c02281","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c02281","url":null,"abstract":"Balancing a short ultraviolet (UV) cutoff edge, a sufficient birefringence, and a strong second-harmonic generation (SHG) response is crucial yet challenging in the quest for beryllium-free deep-UV nonlinear optical (NLO) crystals. Herein, we present the synthesis of an optimized KBe2BO3F2 (KBBF)-like fluorinated borate crystal, Rb3Sr3Li2Al4B6O20F (RSLABOF), through a chemical substitution strategy achieved by substituting Be2+ cations in the KBBF structure with Al3+ and Li+ cations. RSALBOF crystallizes in R32 (No. 155), inheriting the structural merits of KBBF and achieving a well-balanced property, including a strong SHG efficiency equivalent to 1.4 times that of KDP, a short UV absorption cutoff edge (<200 nm), and a favorable birefringence value of 0.064 at 1064 nm. Moreover, the layered structure of RSLABOF features a reinforced interlayer bonding facilitated by Sr-O bonds, which is approximately 4.7 times stronger than that in KBBF, alleviating the propensity for layering growth. Theoretical calculations revealed that the significant SHG intensity primarily originates from the in-layer uniformly aligned [BO3] groups in RSLABOF. These observations highlight the potential of RSLABOF crystals as beryllium-free short-wave UV NLO crystals.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"3 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533438","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

Dinitrogen Binding and Silylation by Bis(ketimino)carbazolide Complexes of Iron and Cobalt. 铁和钴的双（酮胺）咔唑烷配合物的二氮结合和硅基化。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-01 DOI: 10.1021/acs.inorgchem.5c02069

Jack H Lin,Alexis K Bauer,Samuel T Hugie,Michael L Neidig,Datong Song

引用次数: 0

Radical Elaboration of a Ligand-to-Ligand Charge Transfer Chromophore Yields Emissive Excited State Decay. 配体-配体电荷转移发色团的自由基精化产生发射激发态衰变。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-01 DOI: 10.1021/acs.inorgchem.5c01319

Christopher R Tichnell,Patrick Hewitt,Anil Reddy Marri,David A Shultz,Martin L Kirk

引用次数: 0

Electrocatalytic Ammonia Oxidation with Coordinatively Saturated Ruthenium Catalyst. 配位饱和钌催化剂电催化氨氧化研究。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-01 DOI: 10.1021/acs.inorgchem.5c02418

Chuan-Pin Chen,Oluwafemi Abubakar,Xiaoyin Zhang,Thomas W Hamann

引用次数: 0

Catalytic Ring-Opening Homopolymerization and Copolymerization of rac-Lactide and δ-Valerolactone Utilizing Rare-Earth Metal Complexes with Indol-2-yl-Based Ligands in Tridentate and Tetradentate Bonding Modes. 稀土金属配合物与吲哚-2基配体在三齿和四齿键模式下催化开环均聚和共聚rac-丙交酯和δ-戊内酯

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-01 DOI: 10.1021/acs.inorgchem.5c00790

Zeming Huang,Xinlei Yi,Rui Pan,Hua Huang,Chencheng Liu,Li Chen,Fenhua Wang,Shaowu Wang

{"title":"Catalytic Ring-Opening Homopolymerization and Copolymerization of rac-Lactide and δ-Valerolactone Utilizing Rare-Earth Metal Complexes with Indol-2-yl-Based Ligands in Tridentate and Tetradentate Bonding Modes.","authors":"Zeming Huang,Xinlei Yi,Rui Pan,Hua Huang,Chencheng Liu,Li Chen,Fenhua Wang,Shaowu Wang","doi":"10.1021/acs.inorgchem.5c00790","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00790","url":null,"abstract":"The copolymers of rac-lactide (rac-LA) and δ-valerolactone (δ-VL) can improve the properties of the individual polymers in terms of variable mechanical, thermal, permeability, and degradation properties. However, copolymerization of these two monomers catalyzed by metal catalysts faces challenges due to different activities of the intermediates in the propagation processes and lack of understanding the catalytic procedures to realize the copolymerization. Here, a series of novel indol-2-yl-based NNC pincer-type rare-earth metal dialkyl complexes (κ3NNC-L)RE(CH2SiMe3)2 (RE = Lu(1a), Yb(1b), Er(1c), Y(1d), Dy(1e)) (L = 1-(Me2NCH2CH2)-3-((Me2NCH2CH2)MeNCH2)-C8H4N) and carboryne-based rare-earth metallacycles (κ4NNCN-L)RE(η2-C2B10H10) (RE = Lu(2a), Yb(2b), Er(2c), Y(2d), Dy(2e)) were synthesized in good yields. These complexes exhibited high activity in homopolymerization of rac-LA and δ-VL. Notably, highly efficient block copolymerization procedures for the copolymerization of δ-VL and rac-LA initiated by metal complexes were for the first time described by controlling the sequence of feeding the two monomers in the presence of complexes 1 and 2, while the random copolymerization of δ-VL and rac-LA can also be realized by utilization of complexes 1 and 2 as catalysts.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"22 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533479","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

Structures and Properties of the C6v Symmetric Mn2Ge12 Cluster and Its One-Dimensional Nanostructure. C6v对称Mn2Ge12簇及其一维纳米结构的结构与性质

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-01 DOI: 10.1021/acs.inorgchem.5c00382

Li-Juan Zhao,Xi-Ling Xu,Wei-Jun Zheng,Hong-Guang Xu

引用次数: 0

Axial Nitrogen Coordination Engineering of Fe Single-Atom Catalyst for Enhanced Peroxidase-like Activity. 增强过氧化物酶类活性的铁单原子催化剂轴向氮配位工程。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-01 DOI: 10.1021/acs.inorgchem.5c02515

Xu Liu,Jianping Guan,Nianhui Zhou,Jinhua Hu,Tianyu Tao,Yi Zhang,Tao Gan,Shibin Wang,Yu Xiong

{"title":"Axial Nitrogen Coordination Engineering of Fe Single-Atom Catalyst for Enhanced Peroxidase-like Activity.","authors":"Xu Liu,Jianping Guan,Nianhui Zhou,Jinhua Hu,Tianyu Tao,Yi Zhang,Tao Gan,Shibin Wang,Yu Xiong","doi":"10.1021/acs.inorgchem.5c02515","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c02515","url":null,"abstract":"Mimicking the hierarchical structure as well as the asymmetric Fe-N5 sites in natural horseradish peroxidase (HRP) is of great importance in developing Fe1/CN with high peroxidase-like (POD-like) activity. In this work, Fe1/CN with an asymmetric FeN5 moiety and ordered porous structure (FeN5/CN) is fabricated by an ammonia-assisted redispersion strategy, which shows high structural similarity with HRP. Therefore, FeN5/CN shows an excellent catalytic efficiency (specific activity = 117.9 U/mg, kcat/Km = 2185 mM-1 s-1) and selectivity (Km = 0.059 mM) in a POD-like reaction. Based on the high catalytic properties of FeN5/CN, a sensor for the detection of carbosulfan with a low limit of detection of 3.1 nM is assembled. Interestingly, FeN5/CN activates H2O2 via a superoxide pathway, while ·OH, 1O2, and ·O2- can all be detected in the FeN4/CN involved catalytic system. Mechanistic study by density functional theory calculations combined with experimental results illustrates that Fe-N5 sites provide moderate adsorption of *OH, enlarging and decreasing the reaction energy to form ·OH and ·O2-, respectively, while Fe-N4 sites exhibited higher affinity toward the OH* intermediate, resulting in the facile O-O bond cleavage from H2O2 molecule and prohibited the process of *OH desorption to ·OH.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"19 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533383","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

Structure and Bond Dissociation Variations in Dialumenes: A Comparative DFT Study on N,P- versus N,N-Bidentate Ligand Effects. 二铝烯的结构和键解离变化：N，P-与N，N-双齿配体效应的比较DFT研究。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-07-01 DOI: 10.1021/acs.inorgchem.5c02012

Weiyi Li,Cai-Qin Li,Ying-Kun Yan,Lei Sun,Wang Guan

{"title":"Structure and Bond Dissociation Variations in Dialumenes: A Comparative DFT Study on N,P- versus N,N-Bidentate Ligand Effects.","authors":"Weiyi Li,Cai-Qin Li,Ying-Kun Yan,Lei Sun,Wang Guan","doi":"10.1021/acs.inorgchem.5c02012","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c02012","url":null,"abstract":"Herein, we report a comprehensive density functional theory (DFT) calculation to investigate the distinct dissociation behaviors of dialumenes supported by amidophosphine, amidinate, and β-diketiminate (BDI) ligands. Calculations reveal that amidophosphine and amidinate ligands stabilize the Al═Al double bond via a dynamic equilibrium with their aluminyl monomers. Conversely, the BDI ligand preferentially stabilizes mononuclear Al(I) species over dimerization. According to energy decomposition analysis (EDA) and charge decomposition analysis (CDA), this distinct behavior is attributed to the enhanced Pauli's repulsion and diminished orbital interaction between the BDI-stabilized aluminyl fragments. Notably, despite the constrained N-Al-N bite angle imposed by the amidinate ligand, the enhanced stability of the Al═Al bond emerges through limited aluminyl monomer deformation and effective ligand-metal conjugation. A systematic comparison with the hydrogenated amidophosphine ligand systems further demonstrates that the ligand-metal conjugation critically modulates Al═Al bond dissociation, primarily through steric repulsion between the amino lone pairs and Al-Al cores. These key ligand parameters derived from specific ligand systems in this study provide a theoretical foundation for future dialumene design.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"11 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533478","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