Inorganic Chemistry Frontiers最新文献

{"title":"Step-wise assembly of a dysprosium-viologen framework with photoswitchable slow magnetic relaxation under zero dc field","authors":"Hao-Ling Sun, Zhen-Na Huang, Lei Zhang","doi":"10.1039/d4qi02771j","DOIUrl":"https://doi.org/10.1039/d4qi02771j","url":null,"abstract":"Lanthanide molecular nanomagnets featuring reversible photoresponsive characteristic and photomediated magnetic behavior are highly appealing for developing next-generation optics and memory devices though the rational assembly of such materials remains elusive. Herein, we demonstrate a step-wise approach, which employs a photochromic dysprosium-viologen compound {[Dy(ipbp)<small>₂</small>(H<small>₂</small>O)<small>₃</small>].NO<small>₃</small>.2H<small>₂</small>O}n (<strong>1</strong>) (H<small>₂</small>ipbp.Cl = (1-(3,5-dicarboxyphenyl)-4,4ʹ-bipyridinium chloride) as the building block and 2,5-pyrazinedicarboxylate dianions (2,5-pzdc<small>^2-</small>) as bridges, giving rise to a new framework {[Dy(ipbp)<small>₂</small>(2,5-pzdc)<small>_0.5</small>(H<small>₂</small>O)].5H<small>₂</small>O}n (<strong>2</strong>) exhibiting photochromic effect and slow magnetic relaxation under zero dc field. This finding is notable and exciting, as the starting compound <strong>1</strong> shows no magnetic relaxation on its own. The ab initio calculations demonstrate that replacing water molecule at the equatorial plane in <strong>1</strong> with the 2,5-pzdc<small>^2-</small> bridge, the longer Dy-N bond length and the less charged pyrazine nitrogen atom result in a weaker equatorial field strength, and the coordination geometry around Dy<small>³⁺</small> ion in <strong>2</strong> is thus closer to the ideal triangular dodecahedral than in <strong>1</strong>, leading to stronger axial magnetic anisotropy of Dy<small>³⁺</small> ion and switch-on of slow magnetic relaxation under zero dc field. Further magnetic analysis of compound <strong>2</strong> before and after UV light irradiation reveal the weak ferromagnetic coupling between the photogenerated radicals and Dy<small>³⁺</small> ions, a slight inhibition of quantum tunnelling of magnetization, as well as a modest enhancement of energy barrier for the slow magnetic relaxation, highlight the photomodulation of the dynamic magnetic behavior.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"21 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797199","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Surficial-enriched Ru on octahedral CeO2 with strong electronic interactions as an efficient electrocatalyst for hydrogen generation in alkaline freshwater/seawater","authors":"Jing Li, Ruotong Guo, Xingchao Zang, Yue Wang, Hongdong Li, Weiping Xiao, Liantao Xin, Yingxia Zong, Guangying Fu, Zexing Wu, Lei Wang","doi":"10.1039/d4qi02552k","DOIUrl":"https://doi.org/10.1039/d4qi02552k","url":null,"abstract":"Developing high-performance and cost-effective electrocatalysts for the hydrogen evolution reaction (HER) is highly essential for the large-scale application of water splitting. In this work, surficial-enriched ruthenium (Ru) catalyst was developed on octahedral cerium dioxide (CeO<small>₂</small>) through a combination of hydrothermal synthesis and ultrafast (60 s) wet impregnation approaches, utilizing H<small>₂</small>O<small>₂</small> as a facilitator (Ru/CeO<small>₂</small>–H<small>₂</small>O<small>₂</small>). Experimental characterization and density functional theory (DFT) calculation demonstrate that the created oxygen vacancy (Ov) and strong electronic interactions play crucial roles in improving catalytic activity and stability. In particular, the specific octahedral morphology and surficial-enriched Ru enhance the exposure of abundant active sites, thereby accelerating the reaction kinetics. The as-synthesized Ru/CeO<small>₂</small>–H<small>₂</small>O<small>₂</small> demonstrated commendable catalytic performance in both 1 M KOH and 1 M KOH + seawater with small overpotentials of 37 and 47 mV, respectively, to attain a current density of 10 mA cm<small>⁻²</small>. Furthermore, it exhibited remarkable long-term stability at both 10 mA cm<small>⁻²</small> and 500 mA cm<small>⁻²</small>, and demonstrated the ability to drive overall water splitting when coupled with sustainable energy sources. Therefore, this study presents a promising approach for constructing high noble-metal utilization efficiency with a specific support, offering potential for enhanced sustainable energy applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"28 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797193","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Flexibility index: a general descriptor of polarization ability in crystalline materials","authors":"Qin Chen, Xingxing Jiang, Zheshuai Lin","doi":"10.1039/d4qi02749c","DOIUrl":"https://doi.org/10.1039/d4qi02749c","url":null,"abstract":"Although optical phenomena in crystalline materials are different, they are all generated from polarization processes of microscopic structural units under photoelectric field. To develop the simple and effective model that is able to evaluate the polarization ability is crucial to the steps of structural screening and mechanism analysis in the research of optical materials. Here, we applied “flexibility (F) index”, a model previously used to investigate the structural origin of second-order nonlinear optical responses, to unitary and binary diamond-like materials, and demonstrated that this index has a negative correlation to band gap and a positive correlation to first- and second-order polarizabilities. Remarkably, the first-order polarizabilities have a linear-function correlation with F-index, while second-order polarizability have a cube-function correlation with “projected-flexibility (Fp) index”. These polarizability-order-dependent correlation validate the feasibility of the F-index in characterizing specific optical properties.The result of study proves the universality of F-index to describe the optical polarization, which provides a quick and efficient tool to evaluate the optical response in crystalline materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"20 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797157","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis, Oxidation and Unusual Coordination Chemistry of the Diphosphete Complex [(Cp'''Co)2(μ,η4:4-((CH3)CP)2)]","authors":"Eva-Maria Rummel, Mehdi El Sayed Moussa, Maria Parzefall, Eugenia V. Peresypkina, Christoph Riesinger, Alexey Timoshkin, Gabor Balazs, Piero Mastrorilli, Stefano Todisco, Manfred Scheer","doi":"10.1039/d4qi02643h","DOIUrl":"https://doi.org/10.1039/d4qi02643h","url":null,"abstract":"Notwithstanding four decades of active research, very rare examples of diphosphabutadiene complexes arising from dimerisation of the phosphaalkyne CH3–C≡P have been reported. Herein, we show that methyl phosphaalkyne dimerises in the coordination sphere of Cp'''Co fragments to yield the unprecedented diphosphete complex [Cp'''Co(η4-P2C2Me2)] (1) and the triple-decker complex [{Cp'''Co}2(μ,η4:η4 P2C2Me2)] (2). Compound 2 can be oxidised with Ag[Al{OC(CF3)3}4] (Ag[TEF]) to give [{Cp'''Co}2(μ,η4:η4 P2C2Me2)][TEF] (3). Additionally, it shows an unusual coordination behaviour towards copper halides and [W(CO)4(nbd)] (nbd = norbornadiene). Its reaction with CuCl leads to the formation of the 1D polymer [{Cp'''Co}2(μ,η4:η2:η1:η1-P2C2Me2){Cu(µ-Cl)}2]n (6) while its reaction with CuBr, CuI and [W(CO)4(nbd)] results in the metallacyclic compounds [(Cp'''Co){μ3,η4:η1:η1-P2C2Me2}(CH3CN){Cu(μ-X)}2]2 (X = Br (7a), I (7b)) and [Cp'''Co{μ3,η4:η1:η1-P2C2Me2}{W(CO)4}]3 (8). In 6, an isomerisation of the diphosphete ring to a diphosphacyclopentadienyl ring occurs. In 7 and 8, the loss of Cp'''Co moieties from the former compound 2 is observed. The formation of 1,3-diphosphete rings in 1 and 2 instead of the more thermodynamically favoured 1,2-diphosphete rings are explained by DFT computations.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"117 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797154","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A high-performance dysprosium single-ion magnet with local pseudo cubic geometry","authors":"Yanbo Shi, Chennan Zhang, Mingyue Shi, Yang Zhou, Hong Li, Rui Liu, Shaojun Zheng, Aihua Yuan, Lei Chen, Shu-Yang Chen, Bing Yin, Zhao-Bo Hu","doi":"10.1039/d4qi02851a","DOIUrl":"https://doi.org/10.1039/d4qi02851a","url":null,"abstract":"The syntheses and magnetic characterizations of two eight-coordinate isostructural mononuclear complexes, [Ln(BPPA)2]BPh4∙2CH2Cl2 (Ln = Dy, 1-Dy and Tb, 2-Tb; HBPPA = N-(3,5-di-tert-butyl-2-hydroxybenzyl)-N,N-bis(2-pyridylmethyl)amine), were reported. The eight-coordinate Ln(III) ions have a local pseudo cubic geometry, where two O atoms of the phenol groups in opposite sides with the short Ln(III)−O bonds and the O−Ln(III)−O angel of 180o. This geometrical feature results in a strong axial crystal field along the O−Ln(III)−O direction. Complex 1-Dy exhibits zero-field slow relaxation of magnetization with the peaks of out-of-phase susceptibilities (χM'') up to 46 K. On applying 1000 Oe dc field, the energy barrier to magnetic reversal for 1-Dy reaches 678(50) K, which even surpasses those of most of the reported square antiprism Dy(III) complexes. However, 2-Tb only shows weak χM'' signals without maxima under the extra dc field. It is worth noting that complex 1-Dy represents the first observation of zero-field slow relaxation behavior in the Ln(III) complexes with local cubic geometry. Ab initio computations, carried out on both of them, substantiate the different of the magnetic properties in both complexes, which also reveal that the high energy barrier for 1-Dy was mainly caused by the axial short Dy−O distances.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"12 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797155","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Anion-mediated properties of a metal complex in a hexameric resorcin[4]arene cage: chirality induction, kinetics and reactivity","authors":"Hichem Ichou, Kevin Telliez, Sonia Lajnef, Fabienne Peyrot, Benjamin Doistau, Laurence Leherte, Benoit Colasson","doi":"10.1039/d4qi02896a","DOIUrl":"https://doi.org/10.1039/d4qi02896a","url":null,"abstract":"The influence of anions associated with a metal complex on host-guest assembly properties within a hexameric resorcinarene cage was investigated by UV-vis, EPR and electronic circular dichroism spectroscopies and by molecular dynamics (MD) simulations. Upon encapsulation, the metal complex has a restricted mobility but conserves its reactivity towards ligand exchange at the metal centre. Only under light irradiation, the behavior of the metal complex is altered by its encapsulation. Also, the counter-ion strongly affects the encapsulation kinetics. MD simulations suggest that this effect can be triggered when the exchange of a structuring water molecule by the anion within the cage wall is possible. Finally, a double chirality induction is observed from a chiral counter-ion to the capsule and to the encapsulated cationic complex moiety itself.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"239 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142805239","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Sr8MgSc(PO4)7:Eu2+ phosphor: d–f transition driven applications for solid-state lighting and extreme environment multimode sensing investigations","authors":"Baofeng Zheng, Jiahao Yan, Jingyao Li, Yixuan Wang, Xinyi Yang, Wenze Li","doi":"10.1039/d4qi02664k","DOIUrl":"https://doi.org/10.1039/d4qi02664k","url":null,"abstract":"Materials with multiple modes for measuring extreme environmental indicators are urgently required. Herein, a kind of bright yellow-green emitting phosphor Sr<small>₈</small>MgSc(PO<small>₄</small>)<small>₇</small>:Eu<small>²⁺</small> with applications in solid-state luminescence and multi-mode sensing in extreme environments has been synthesized. The assembled warm white LED device has a higher color rendering index (<em>R</em><small>_a</small> = 93.2), a lower correlated color temperature (CCT = 4718 K) and appropriate chromaticity coordinates (0.3509, 0.3397). Furthermore, from room temperature (RT, 298 K) to 78 K, the emission color rapidly changes from yellow-green to orange. The maximum relative sensitivity and absolute sensitivity were calculated as <em>S</em><small>_a</small> (max) = 6.36 × 10<small>⁻²</small> K<small>⁻¹</small> and <em>S</em><small>_r</small> (max) = 1.8% K<small>⁻¹</small>, respectively. In the process of applying pressure, the phosphor withstands a pressure of up to 21.5 GPa. The calculation method of its pressure sensitivity is developed by using three strategies. The sensitivity obtained by the LIR method is the largest, which is <em>S</em><small>_pr</small> (max) = 116.22% GPa<small>⁻¹</small>. In conclusion, the bright yellow-green phosphor Sr<small>₈</small>MgSc(PO<small>₄</small>)<small>₇</small>:Eu<small>²⁺</small>, showing a rapid and sensitive temperature and pressure response, has considerable potential for application in solid state lighting, low temperature sensing, and pressure sensing.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"26 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793687","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Probing the Interaction of Cisplatin with Calmodulin and its Effect upon Binding to Myosin Light-Chain Kinase","authors":"Siming Yuan, Shenghu Wang, Kaiming Cao, Yu Wang, Hongze Hu, Liqin Tang, Aizong Shen, Fabio Arnesano, Giovanni Natile, Yangzhong Liu","doi":"10.1039/d4qi02844a","DOIUrl":"https://doi.org/10.1039/d4qi02844a","url":null,"abstract":"Despite the successful clinical application of cisplatin, its mechanism of action and adverse effects remain poorly understood. To elucidate the complex pharmacology of this drug, research has focused on its interaction with proteins. Herein, we examined the interaction of cisplatin with calmodulin (CaM), a pivotal protein in signal transduction, and its effect upon binding to the MLCK kinase. Selective labeling of the proteins, including 13CH3-methionine- and 15N-labeled CaM, as well as 19F-tryptophan-labeled MLCK, enabled effective detection of protein folding and interactions using multiple NMR techniques. Results revealed that cisplatin readily reacts with CaM, leading to mobilization of bound Ca2+ ions and inhibition of CaM/MLCK complex formation. The preformed CaM/MLCK complex exhibited greater resilience to cisplatin, as compared to free CaM, due to more embedded methionine residues within the CaM/MLCK complex. Although the complex survived to platination, some destabilization occurred, as evidenced by the mobilization of some Ca2+ ions and collapse of the complex under chromatographic conditions. Analogous reactions occur in a cellular setting. These results imply that the platination of CaM could underlie the mechanism of cisplatin-induced neurotoxicity.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"28 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142782960","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Novel Antimony-Based Mixed Halides Exhibiting Excellent SHG Response and Broad Transmission Range","authors":"Luli Wang, Han Luo, Siyu Chen, Ling Huang, Liling Cao, Xuehua Dong, Guohong Zou","doi":"10.1039/d4qi02757d","DOIUrl":"https://doi.org/10.1039/d4qi02757d","url":null,"abstract":"In this study, we successfully synthesized two novel non-centrosymmetric (NCS) antimony halide compounds, RbSbF3Cl and Rb3Sb4F14Cl. These compounds were formed by combining Sb3+ cations, which possess stereochemically active lone pairs (SCALP), with halogen atoms (fluorine and chlorine). The introduction of mixed halogen atoms enables Sb atoms to adopt multiple coordination modes, which in turn promotes the development of both compounds towards NCS structures. Notably, Rb3Sb4F14Cl demonstrated a large second harmonic generation (SHG) response, approximately three times greater than that of KH2PO4 (KDP), along with a wide transparency range from 0.27 to 13.3 μm and a high laser damage threshold (LDT) of 223 MW/cm2. These exceptional properties indicate that Rb3Sb4F14Cl is a highly promising nonlinear optical (NLO) crystal with excellent overall performance, making it suitable for potential applications spanning the short-wave ultraviolet (UV) to mid-infrared (IR) spectral regions. In contrast, RbSbF3Cl exhibits a large birefringence of 0.31 at 546 nm as a uniaxial crystal, suggesting its practicability as a birefringent material.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"16 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777042","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Ni–N–C catalyst for CO2 electroreduction based on the MOF@MOF configuration exhibiting wide active reaction sites","authors":"Chul Hyun Jun, Chandan Chandru Gudal, Sampath Prabhakaran, Anki Reddy Mule, Pil J. Yoo, Do Hwan Kim, Chan-Hwa Chung","doi":"10.1039/d4qi02293a","DOIUrl":"https://doi.org/10.1039/d4qi02293a","url":null,"abstract":"CO production, which is known for its efficient use of fewer electrons, has garnered significant attention owing to its potential applications in downstream industries. This study introduces a novel method for synthesizing the Ni–N–C structure with Ni, using a porous metal–organic framework (MOF) and a zeolitic imidazolate framework (ZIF), which is a type of material under MOFs, with the structural configuration of MOF@MOF. Decoupling the inner electron-transfer paths from the outer active sites makes it possible to obtain a high partial current for CO while minimizing the content of Ni. In addition, the pyrolyzed host MOF has superhydrophobic properties, making the inner space of Ni–N–C-748 a favorable environment for CO<small>₂</small> that prevents the hydrogen evolution reaction. Consequently, Ni–N–C-748 exhibited a faradaic efficiency for CO greater than 95% over a wide potential range. Furthermore, a potential of 2.1 V was obtained at 100 mA cm<small>⁻²</small> using a membrane electrode assembly cell.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"79 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777041","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}