Inorganic Chemistry Frontiers最新文献

{"title":"Magneto-optical response and luminescence properties of lanthanide–titanium–oxo clusters Eu2Ti7 and Sm2Ti7†","authors":"Wei-Dong Liu, Han Xu, Chong-Yang Li, La-Sheng Long, Lan-Sun Zheng and Xiang-Jian Kong","doi":"10.1039/D4QI02645D","DOIUrl":"10.1039/D4QI02645D","url":null,"abstract":"<p >The study of magneto-optical effects based on the f–f emission and absorption of lanthanide ions has attracted considerable interest. In this work, we present a series of isostructural lanthanide–titanium–oxo clusters (LTOCs) <strong>Ln<small>₂</small>Ti<small>₇</small></strong> (Ln = La, Sm, Eu) using 3,5-di-<em>tert</em>-butylbenzoic acid as the ligand. A detailed comparison of the luminescence properties of <strong>Sm<small>₂</small>Ti<small>₇</small></strong> and <strong>Eu<small>₂</small>Ti<small>₇</small></strong> shows that <strong>Eu<small>₂</small>Ti<small>₇</small></strong> displays superior luminescence intensity, higher color purity red light, longer lifetime, and significantly higher quantum yield. These properties, along with its high stability in solution, make <strong>Eu<small>₂</small>Ti<small>₇</small></strong> an excellent candidate for magnetic circularly polarized luminescence (MCPL) studies. Under an external magnetic field, <strong>Eu<small>₂</small>Ti<small>₇</small></strong> exhibited strong MCPL signals, with the maximum |<em>g</em><small>_MCPL</small>| value being 0.04 T<small>⁻¹</small> from the <small>⁵</small>D<small>₀</small> → <small>⁷</small>F<small>₄</small> transition. In contrast, the weaker luminescence of <strong>Sm<small>₂</small>Ti<small>₇</small></strong> rendered MCPL analysis ineffective; however, its strong near-infrared absorption allowed for magnetic circular dichroism (MCD) studies. The MCD spectra of Sm<small>₂</small>Ti<small>₇</small> revealed significant signals corresponding to f–f transitions in the 900–1600 nm range, with the maximum |<em>g</em><small>_MCD</small>| value observed at 1102 nm. This work provides valuable insights into the magneto-optical properties of Ln-based clusters, emphasizing the role of energy-level analysis for further research into their potential applications in magneto-optical devices.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":" 1","pages":" 253-260"},"PeriodicalIF":6.1,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678744","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":"Designing Different Carbon Capping Amorphous MoO2 to Enhance Electrochemical Performance in Lithium-Ion Batteries","authors":"Yali Cao, Gaoyuan Liu, Xinxin Yin, Jing Xie, Jindou Hu, Aize Hao, Zhenjiang Lu","doi":"10.1039/d4qi02198c","DOIUrl":"https://doi.org/10.1039/d4qi02198c","url":null,"abstract":"Transition metal oxides (TMOs) are considered a showing potential anode material for the lithium-ion batteries (LIBs) because of its high theoretical capacity. However, their use in LIBs is limited by factors such as low initial coulombic efficiency, substantial volume changes, and low electrical conductivity. Here, the amorphous MoO2 capped with different carbon is ingeniously designed by controlling the calcination temperature and different carbon sources. Electrochemical kinetic and material characterization show that the amorphous structure not only enhances its electronic conductivity, but also optimizes the lithium-ion (Li+) migration mode, thus improving its rate performance. Furthermore, the pore sizes produced by different carbon sources were found to have different effects on the performance of LIBs. Meanwhile, the Li+ storage mechanism of the amorphous MoO2-x@C was revealed by in-situ XRD analysis. As expected, the amorphous MoO2-x@C exhibits an excellent cycling stability, maintaining a discharge specific capacity of 601.4 mAh g−1 at 5.0 A g−1 for 800 cycles. Particularly, the MoO2-x@C||LiCoO2 full cell still possesses a capacity of 109.8 mAh g−1 at 0.2 C for 80 cycles. This endeavor will provide an experimental idea for the molybdenum-based oxide high-performance anode materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"63 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678683","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 dual-purpose copper(i) coordination polymer for the construction of self-driven photoinduced C–H arylation systems†","authors":"Yue Zhang, Ying-Ying Zhang, Shuo Li, Fei Wang, Yuanmeng Tao, Jiaxing Cui, Chao Huang and Liwei Mi","doi":"10.1039/D4QI02381A","DOIUrl":"10.1039/D4QI02381A","url":null,"abstract":"<p >The simultaneous exploitation of the dual or multiple physical and chemical properties of a material is a promising strategy for developing high-tech intelligent complex systems. In this study, a copper(<small>I</small>) coordination polymer (<strong>Cu<small>^I</small>-CP</strong>, <strong>2</strong>) was synthesized and utilized as a dual-purpose material to construct a self-powered photocatalytic system capable of significantly improving the power generation capabilities of triboelectric generators (TEGs) as a triboelectric layer and efficiently catalyzing the C–H arylation reaction as a photocatalyst. Compound <strong>2</strong> was achieved <em>via</em> a solvothermal method in the presence of ammonia and ethylenediamine. In contrast, only mixed-valence copper salts ([Cu<small>^II</small>(H<small>₂</small>O)<small>₅</small>][Cu<small>^I</small><small>₃</small>(CN)<small>₅</small>]·H<small>₂</small>O, <strong>1</strong>) were obtained without ammonia and ethylenediamine. Comparative analysis revealed that the TEG based on <strong>2</strong> (<strong>2</strong>-TEG) showcased superior output performance compared to <strong>1</strong>-TEG owing to the exceptional electron-donating ability of <strong>2</strong>. Furthermore, under light-emitting diode (LED) irradiation powered by <strong>2</strong>-TEG, <strong>2</strong> demonstrated remarkable catalytic activity and selectivity in the photoinduced C–H arylation of benzothiazole, far exceeding the performance of <strong>1</strong>. This research highlights the potential of bifunctional material <strong>2</strong> with a distinctive structure, renowned for its outstanding energy harvesting and conversion capabilities as well as excellent photocatalytic performance, thereby facilitating the design objectives of multitasking in self-driven complex systems.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":" 1","pages":" 301-310"},"PeriodicalIF":6.1,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678739","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":"High-performance Rh@MgO catalysts for complete dehydrogenation of hydrazine borane: a comparative study†","authors":"Ahmet Bulut, Mustafa Erkartal, Mehmet Yurderi, Tuba Top and Mehmet Zahmakiran","doi":"10.1039/D4QI02575J","DOIUrl":"10.1039/D4QI02575J","url":null,"abstract":"<p >Hydrazine borane (HB) has great potential as a safe and convenient hydrogen carrier material due to its high hydrogen capacity (15.4 wt%) and good stability under ambient conditions. However, efficient hydrogen production through complete decomposition of hydrazine borane at low temperatures (&lt;373 K) constitutes a major challenge. Herein, we report the successful immobilization of monodisperse Rh nanoparticles on MgO solid support, leading to the formation of the Rh@MgO catalyst. This developed catalyst exhibits outstanding catalytic performance in the dehydrogenation of HB, achieving a remarkable turnover frequency (TOF) of 2005.34 h<small>⁻¹</small> at 50 °C with 100% H<small>₂</small> selectivity, despite containing only 2 wt% Rh. Comparative experiments with Rh on various metal–oxide nanoparticles, other transition metal catalysts on MgO, and Ni grown on MgO in both single-phase and bimetallic forms reveal that Rh@MgO consistently outperforms these alternatives. The exceptional catalytic activity is attributed to the synergistic interaction between Rh and MgO, which involves several key factors: the homogeneous dispersion of ultrafine, monodisperse Rh particles enhances catalytic efficiency; the proximity of the work functions of Rh and MgO results in a low-energy Schottky barrier that facilitates electron transfer; and the localization of electrons in surface defects of MgO aligns with the Fermi level of Rh, further promoting electron transfer through Fermi level pinning (FLP). The combination of low Rh content and cost-effective MgO support presents a promising pathway for both laboratory-scale research and practical industrial applications, highlighting the potential of the Rh@MgO catalyst as an efficient and economically viable solution for catalytic processes.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":" 1","pages":" 342-354"},"PeriodicalIF":6.1,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/qi/d4qi02575j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678738","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Interchain interactions raised the photo-induced [LS] → [HS*] transition temperature to 78 K in a cyanide-bridged [FeIII2CoII] chain†","authors":"Wen-Jing Jiang, Yin-Shan Meng, Han-Han Lu, Hai-Lang Zhu, Qiang Liu, Chunying Duan, Hiroki Oshio and Tao Liu","doi":"10.1039/D4QI02428A","DOIUrl":"10.1039/D4QI02428A","url":null,"abstract":"<p >Bistable mixed valence compounds have thermodynamically accessible phases at certain temperatures, and the electron transfer switches the electronic configurations by applying external stimuli like heat and light. Thermally induced phase transition temperatures range widely, while the photo-induced state conversions need irradiation at very low temperatures, such as below 30 K, and the photo-induced metastable state relaxes rapidly at low temperatures. We prepared new mixed-valence compounds of [Fe(bipy)(CN)<small>₄</small>]<small>₂</small>[CoL<small>₂</small>] (L = 4-[(1<em>E</em>)-2-phenyldiazenyl]pyridine for <strong>1-papy</strong> and 4-(2-phenylethynyl)pyridine for <strong>1-pepy</strong>) in which cyanide-bridged squared cores form corner-shared chains with substantial interchain π–π contacts. Mössbauser spectra revealed that <strong>1-papy</strong> and <strong>1-pepy</strong> are in the high-spin (HS) state [(Fe<small>^III</small><small>_LS</small>)<small>₂</small>Co<small>^II</small><small>_HS</small>] at 300 K and the low-spin (LS) state [Fe<small>^II</small><small>_LS</small>Fe<small>^III</small><small>_LS</small>Co<small>^III</small><small>_LS</small>] at 78 K, confirming the occurrence of the electron transfer coupled spin transition (ETCST). Magnetic susceptibility measurements suggested their <em>T</em><small>_c</small> values of 231 and 260 K, respectively. Photoirradiation (808 nm) for <strong>1-papy</strong> and <strong>1-pepy</strong> at 10 K induced the state conversion from the [LS] to the [HS*] state, and the metastable [HS]* state relaxed to the thermodynamically stable [LS] states at temperatures (<em>T</em><small>_relax</small>) of 130 and 90 K, respectively. Furthermore, the [LS] states in <strong>1-papy</strong> and <strong>1-pepy</strong> were fully converted to the [HS*] states by light irradiation at 78 and 50 K, respectively. The X-ray structural analyses showed characteristic coordination bond lengths for the metal ions in each electronic state before and after light irradiation, but shortened intrachain π<small>_L</small>⋯π<small>_L</small> contact distances, from 3.726(4) to 3.688(4) Å, were observed for <strong>1-papy</strong> upon the state conversion from the [LS] to the [HS*] state, despite the swollen cell volumes from 2479 to 2566 Å<small>³</small>, respectively. Photomagneto and structural studies suggest that the intermolecular interactions increase the light-induced state conversion and relaxation temperatures.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":" 1","pages":" 131-137"},"PeriodicalIF":6.1,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673643","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":"Heterogeneous interface engineering to enhance oxygen electrocatalytic activity for rechargeable zinc–air batteries†","authors":"Tao-Tao Li, Yu-Rui Ji, Yi-Meng Wu, Peng-Fei Wang, Zong-Lin Liu, Jie Shu and Ting-Feng Yi","doi":"10.1039/D4QI02213K","DOIUrl":"10.1039/D4QI02213K","url":null,"abstract":"<p >The electrocatalytic activity of catalysts can be significantly enhanced through the utilization of heterogeneous structures. Nevertheless, the optimization of both catalytic activity and durability <em>via</em> heterojunction engineering remains a considerable challenge. In this work, we fabricated electrocatalysts of Co/CoO heterojunctions on a highly porous hollow carbon material. The formation of heterojunctions increases the abundance of accessible active sites and optimizes the electrocatalytic reaction kinetics and reactivity. Thus, the prepared catalysts (Co/CoO@N–C-40) deliver robust and stable bifunctional oxygen electrocatalytic activity during the oxygen reduction/evolution reaction (ORR/OER) process. The performance of rechargeable zinc–air batteries (ZABs) greatly depends on bifunctional oxygen electrocatalysts, which are crucial for efficient charging and discharging processes. Consequently, the Co/CoO@N–C-40-based ZABs have superior cycling stability (750 h) and show a stable energy efficiency of 55.10% at 10 mA cm<small>⁻²</small> (53.46% after 555 h). This work offers a high-quality oxygen electrocatalyst for ZABs and extends the application of heterogeneous interfacial catalysts in various energy storage and conversion devices.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":" 1","pages":" 205-216"},"PeriodicalIF":6.1,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673668","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":"Purification of octafluoropropane from hexafluoropropylene /octafluoropropane mixtures with a metal-organic framework exhibiting high productivity","authors":"Yuan-Qin Feng, Hui-Fang Ma, Shuai Luo, Hui-Ping Xiao, Qing-Yan Liu, Yu-Ling Wang","doi":"10.1039/d4qi02562h","DOIUrl":"https://doi.org/10.1039/d4qi02562h","url":null,"abstract":"Octafluoropropane (C3F8) electronic specialty gas is widely used in the process of etching and cleaning in semiconductor manufacturing industry. Removal of hexafluoropropylene (C3F6) impurities from C3F6/C3F8 mixtures thus is highly important but a formidable challenge since C3F6 and C3F8 possess similar physicochemical properties and molecular sizes. Herein we present a cobalt metal-organic framework (MOF) (termed as JXNU-21) constructed of 3-chloroisonicotinic ligands, featuring dangling 3-chloroisonicotinic ligands in the one-dimensional channels. Due to the rotation flexibility of the aromatic rings of the dangling 3-chloroisonicotinate ligands with uncoordinated nitrogen sites, the step-wise adsorption isotherms for the large-sized C3F8 were observed for JXNU-21. The high adsorption selectivity of 15.6 for C3F6/C3F8 (10:90) mixture and high C3F6 storage density (5.8 mmol g–1) under ambient conditions endow JXNU-21 with high potential for C3F6/C3F8 separation. The results of the breakthrough experiments show high-purity (99.999%) C3F8 gas can be achieved from a C3F6/C3F8 (10:90) mixture in one step. Additionally, the benchmark C3F8 productivity of 173.8 cm3 g–1 was obtained from the breakthrough experiments under ambient conditions, outperforming all other reported porous materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"250 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671071","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":"Modulation of halogens in organic manganese halides for high-resolution and large-area flexible X-ray imaging†","authors":"Ying Sun, Qian Ma, Dongheng Zhao, Pan Gao, Qi Wang, Zeyu Guo and Xiaomei Jiang","doi":"10.1039/D4QI02522A","DOIUrl":"10.1039/D4QI02522A","url":null,"abstract":"<p >Manganese-based organic metal halides, due to their excellent optoelectronic properties and stable chemical nature, have been widely used in optoelectronic devices and sensors. In this study, through rational modulation of halogens, three novel zero-dimensional organic manganese halides [(C<small>₆</small>H<small>₈</small>N)<small>₂</small>MnX<small>₄</small> (X = Cl, Br, and I)] were obtained by changing the halogen atom <em>via</em> the solvent evaporation method. Due to the d–d electronic transition of Mn<small>²⁺</small> in the tetrahedrally coordinated [MnX<small>₄</small>]<small>²⁻</small> polyhedron, all samples exhibit strong green emission. Notably,(C<small>₆</small>H<small>₈</small>N)<small>₂</small>MnBr<small>₄</small> exhibited a remarkable light yield of 18 224 photons per MeV and a low detection limit of 1.9 μGy s<small>⁻¹</small>, which is below the X-ray diagnostic limit and even superior to that of commercial BGO scintillators. Moreover, a 9 cm × 9 cm flexible scintillator film was successfully fabricated by mixing (C<small>₆</small>H<small>₈</small>N)<small>₂</small>MnBr<small>₄</small> crystalline powder with polymethyl methacrylate, and this film manifested superior radiation stability and an X-ray imaging resolution of 12.1 lp mm<small>⁻¹</small>. Notably, the X-ray images captured by the flexible film demonstrate distinguished clarity when adhered perfectly to curved metal sheets. The combination of excellent performance and facile solution processing opens new opportunities for low-cost, high-performance organic metal halide-based large-area flexible scintillators for X-ray detection and imaging.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":" 1","pages":" 291-300"},"PeriodicalIF":6.1,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671069","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":"Tailoring electronic structure to enhance the ammonium-ion storage properties of VO2 by molybdenum doping toward highly efficient aqueous ammonium-ion batteries†","authors":"Yifu Zhang, Zhenhua Zhou, Xianfang Tan, Yanyan Liu, Fangfang Zhang, Changgong Meng and Xiaoming Zhu","doi":"10.1039/D4QI01910E","DOIUrl":"10.1039/D4QI01910E","url":null,"abstract":"<p >Recently, research on ammonium-ion storage has gained widespread interest, and it is still a major problem and a popular research area to produce high-performance electrode materials for aqueous ammonium ion batteries (AAIBs). Herein, the electronic structure of tunnel-like vanadium dioxide (VO<small>₂</small>) is tailored by molybdenum doping (denoted as VO<small>₂</small>-Mo) to enhance ammonium-ion storage properties toward highly efficient AAIBs. VO<small>₂</small>-Mo with a unique nanobelt structure is designed and synthesized by adjusting the content of Mo <em>via</em> a facile hydrothermal method. Density functional theory (DFT) simulations and experimental data both demonstrate that molybdenum atoms in the VO<small>₂</small> structure can improve mass transfer, speed up ion transport, and accelerate kinetics, showing boosted NH<small>₄</small><small>⁺</small>-storage properties. With 2% Mo doping, at 0.1 A g<small>⁻¹</small>, VO<small>₂</small>-Mo exhibits a specific discharge capacity of around 370 mA h g<small>⁻¹</small>, surpassing VO<small>₂</small> (232 mA h g<small>⁻¹</small>) and the vanadium oxide-based materials that have been reported for NH<small>₄</small><small>⁺</small>-storage. After approximately 6000 successive charging and discharging cycles at 2 A g<small>⁻¹</small>, it essentially maintains the specific capacity of 140 mA h g<small>⁻¹</small>. Using VO<small>₂</small>-Mo, polyaniline (PANI) and 1 M (NH<small>₄</small>)<small>₂</small>SO<small>₄</small> as the anode, cathode, and electrolyte, respectively, a VO<small>₂</small>-Mo//PANI full battery was further built, and at 0.2 A g<small>⁻¹</small>, it reached a specific discharge capacity of up to 232 mA h g<small>⁻¹</small>, surpassing the performances of the most state-of-the-art AAIBs. At 89 W kg<small>⁻¹</small>, the VO<small>₂</small>-Mo//PANI battery can achieve an energy density (<em>E</em>) up to 133 W h kg<small>⁻¹</small>. This study provides new ideas for tailoring electrode materials with enhanced NH<small>₄</small><small>⁺</small>-storage for AAIBs.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":" 1","pages":" 355-368"},"PeriodicalIF":6.1,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673676","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":"Multispin superatoms: seven-nuclear rhenium clusters with unusual magnetic properties†","authors":"Aleksei S. Pronin, Yakov M. Gaifulin, Taisiya S. Sukhikh, Alexander N. Lavrov and Yuri V. Mironov","doi":"10.1039/D4QI02353F","DOIUrl":"10.1039/D4QI02353F","url":null,"abstract":"<p >Obtaining nanosized, solution-processable molecules and ions with switchable magnetic moments is crucial for the development of storage devices. In this work, two seven-nuclear rhenium cluster complexes Cs<small>₇</small>[{Re<small>₃</small>S<small>₄</small>(CN)<small>₉</small>}{Re<small>₄</small>S<small>₄</small>}(CN)<small>₉</small>]·10H<small>₂</small>O (<strong>1</strong>) and K<small>₇</small>[{Re<small>₃</small>Se<small>₄</small>(CN)<small>₉</small>}{Re<small>₄</small>Se<small>₄</small>}(CN)<small>₉</small>]·15H<small>₂</small>O (<strong>2</strong>) were prepared and comprehensively characterized. The obtained clusters with an even number of cluster valence electrons (CVE) are found to consist of triangular and tetrahedral fragments strongly bonded together by bridging inner ligands and constitute a new structural type. Magnetochemical analysis of complexes has revealed the presence of non-magnetic singlet (<em>M</em><small>_<em>S</em></small> = 0) and magnetic doublet (<em>M</em><small>_<em>S</em></small> = ±1) states with a temperature-dependent population. These states, according to DFT calculations, may originate from the zero-field splitted <em>S</em> = 1 ground state, which is quite surprising given that clusters with an even number of CVE usually possess low-spin states (<em>S</em> = 0) due to the delocalized nature of the frontier molecular orbitals (MOs) and the effective removal of MO degeneracy by Jahn–Teller spatial distortion of the clusters. We have also succeeded in controlling one-electron oxidation of the clusters, which results in an odd number of CVE and drives the compound into a conventional paramagnetic <em>S</em> = 1/2 state.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":" 24","pages":" 8945-8952"},"PeriodicalIF":6.1,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671068","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}