Pub Date : 2026-03-19DOI: 10.1021/acs.inorgchem.5c06057
Akbar Mohammadi Zardkhoshoui, Faezeh Hashemi, Mohammad Ali Saghafizadeh, Saied Saeed Hosseiny Davarani
Bridging the energy-power gap in energy storage demands battery-type electrodes that overcome the intrinsic trade-offs between capacity, rate capability, and cycling stability. Herein, we introduce a dual-engineering strategy that integrates a conductive heterostructured nanocomposite of manganese–iron–cobalt tellurides (MnFeCoTe) with a precisely controlled hollow hierarchical architecture. The material is synthesized through a templated hydrothermal transformation, where well-defined MnFe-Prussian blue analogue (MnFe-PBA) nanocubes are converted into hollow MnFeCoTe nanocomposite nanocubes uniformly sheathed with interconnected nanosheets. This distinctive morphological evolution is driven by a Kirkendall effect during the simultaneous tellurization and cobalt incorporation, creating a hollow core for strain accommodation and a conductive, high-surface-area shell for rapid ion/electron transport. We optimized the tellurization temperature, finding that 180 °C yields the optimal hierarchical architecture, denoted as MnFeCoTe-180, which balances complete phase conversion with structural integrity. The heterostructured nanocomposite system, comprised of intimately mixed binary telluride phases (MnTe, FeTe, and CoTe), provides intrinsic metallicity and rich multielectron redox activity through synergistic interfacial effects, while the architecture ensures full electrolyte accessibility and mechanical robustness. The resulting MnFeCoTe-180 electrode delivers a high specific capacity of 1455 C g–1 at 1 A g–1, exceptional rate performance (80.25% capacity retention at 45 A g–1), and outstanding long-term cyclability (97.22% retention after 10,000 cycles). In a full asymmetric hybrid supercapacitor, the device achieves a high energy density of 65 Wh kg–1 at 802.46 W kg–1 and maintains 48.1 Wh kg–1 at 37 kW kg–1, with 90.25% capacity retention over 10,000 cycles. This work demonstrates a holistic design paradigm, where targeted nanocomposite composition and rational nanoarchitecture are combined to unlock transformative electrochemical performance, setting a new benchmark for next-generation faradaic electrodes.
弥合能量存储中的能量-功率差距要求电池型电极克服容量、速率能力和循环稳定性之间的内在权衡。在此，我们引入了一种双工程策略，将导电的锰铁钴碲化物异质结构纳米复合材料（MnFeCoTe）与精确控制的空心分层结构集成在一起。该材料是通过模板水热转化合成的，其中定义明确的mnfe -普鲁士蓝类似物（MnFe-PBA）纳米立方体被转化为中空的MnFeCoTe纳米复合纳米立方体，均匀地包裹着相互连接的纳米片。这种独特的形态演变是由同时碲化和钴结合过程中的Kirkendall效应驱动的，形成了一个用于应变调节的中空核心和一个用于快速离子/电子传输的导电高表面积壳。我们优化了碲化温度，发现180°C产生最优的分层结构，表示为MnFeCoTe-180，它平衡了完全相变和结构完整性。该异质结构纳米复合体系由密切混合的二元碲化物相（MnTe、FeTe和CoTe）组成，通过协同界面效应提供了固有的金属丰度和丰富的多电子氧化还原活性，同时该体系结构确保了完全的电解质可及性和机械稳稳性。由此产生的MnFeCoTe-180电极在1 a g-1时具有1455 C g-1的高比容量，卓越的倍率性能（45 a g-1时容量保持率为80.25%），以及出色的长期可循环性（10,000次循环后保持率为97.22%）。在全不对称混合超级电容器中，该器件在802.46 W kg-1时实现65 Wh kg-1的高能量密度，在37 kW kg-1时保持48.1 Wh kg-1，在10,000次循环中保持90.25%的容量。这项工作展示了一种整体设计范式，其中有针对性的纳米复合材料组成和合理的纳米结构相结合，以解锁变革性的电化学性能，为下一代法拉第电极设定了新的基准。
{"title":"Manganese–Iron–Cobalt Telluride Nanocomposite Hollow Nanocubes Armored with Interconnected Porous Nanosheets: A Holistic Design for High-Performance Battery-Type Electrodes","authors":"Akbar Mohammadi Zardkhoshoui, Faezeh Hashemi, Mohammad Ali Saghafizadeh, Saied Saeed Hosseiny Davarani","doi":"10.1021/acs.inorgchem.5c06057","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c06057","url":null,"abstract":"Bridging the energy-power gap in energy storage demands battery-type electrodes that overcome the intrinsic trade-offs between capacity, rate capability, and cycling stability. Herein, we introduce a dual-engineering strategy that integrates a conductive heterostructured nanocomposite of manganese–iron–cobalt tellurides (MnFeCoTe) with a precisely controlled hollow hierarchical architecture. The material is synthesized through a templated hydrothermal transformation, where well-defined MnFe-Prussian blue analogue (MnFe-PBA) nanocubes are converted into hollow MnFeCoTe nanocomposite nanocubes uniformly sheathed with interconnected nanosheets. This distinctive morphological evolution is driven by a Kirkendall effect during the simultaneous tellurization and cobalt incorporation, creating a hollow core for strain accommodation and a conductive, high-surface-area shell for rapid ion/electron transport. We optimized the tellurization temperature, finding that 180 °C yields the optimal hierarchical architecture, denoted as MnFeCoTe-180, which balances complete phase conversion with structural integrity. The heterostructured nanocomposite system, comprised of intimately mixed binary telluride phases (MnTe, FeTe, and CoTe), provides intrinsic metallicity and rich multielectron redox activity through synergistic interfacial effects, while the architecture ensures full electrolyte accessibility and mechanical robustness. The resulting MnFeCoTe-180 electrode delivers a high specific capacity of 1455 C g<sup>–1</sup> at 1 A g<sup>–1</sup>, exceptional rate performance (80.25% capacity retention at 45 A g<sup>–1</sup>), and outstanding long-term cyclability (97.22% retention after 10,000 cycles). In a full asymmetric hybrid supercapacitor, the device achieves a high energy density of 65 Wh kg<sup>–1</sup> at 802.46 W kg<sup>–1</sup> and maintains 48.1 Wh kg<sup>–1</sup> at 37 kW kg<sup>–1</sup>, with 90.25% capacity retention over 10,000 cycles. This work demonstrates a holistic design paradigm, where targeted nanocomposite composition and rational nanoarchitecture are combined to unlock transformative electrochemical performance, setting a new benchmark for next-generation faradaic electrodes.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478572","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}
Pub Date : 2026-03-19DOI: 10.1021/acs.inorgchem.6c00191
Jie Qin, Yanghua Lan, Jingqian Wang, Zhijin Xu, Xin Dong, Yaru Geng, Junhua Luo, Lina Li
A pressing challenge in environmental, biomedical, and infrared sensing is the creation of versatile detectors capable of operating across wide wavelengths. Due to the fundamental limitations imposed by intrinsic bandgap structures, the operational scope of most existing photoactive materials remains predominantly confined to the ultraviolet and visible regions, thereby impeding the development of effective broadband detection systems. In this study, we have designed a lead-free polar perovskite [2-(4-aminobutyl)guanidine]BiBr5 (1). Importantly, the built-in electric field associated with the intrinsic symmetry breaking in 1 induces bulk photovoltaic effect under illumination. Furthermore, 1 exhibits a distinctive photopyroelectric (PPE) effect, which broadens the detection wavelength and breaks the limitation of the optical absorption bandgap, covering the range of the 266–980 nm spectral region and exceeding the optical absorption bandgap.
{"title":"Self-Powered Broadband Photodetection in Hybrid Perovskite Enabled by Photovoltaic Effect","authors":"Jie Qin, Yanghua Lan, Jingqian Wang, Zhijin Xu, Xin Dong, Yaru Geng, Junhua Luo, Lina Li","doi":"10.1021/acs.inorgchem.6c00191","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00191","url":null,"abstract":"A pressing challenge in environmental, biomedical, and infrared sensing is the creation of versatile detectors capable of operating across wide wavelengths. Due to the fundamental limitations imposed by intrinsic bandgap structures, the operational scope of most existing photoactive materials remains predominantly confined to the ultraviolet and visible regions, thereby impeding the development of effective broadband detection systems. In this study, we have designed a lead-free polar perovskite [2-(4-aminobutyl)guanidine]BiBr<sub>5</sub> (<b>1</b>). Importantly, the built-in electric field associated with the intrinsic symmetry breaking in <b>1</b> induces bulk photovoltaic effect under illumination. Furthermore, <b>1</b> exhibits a distinctive photopyroelectric (PPE) effect, which broadens the detection wavelength and breaks the limitation of the optical absorption bandgap, covering the range of the 266–980 nm spectral region and exceeding the optical absorption bandgap.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"11 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478573","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}
We report a systematic study of phenanthroline-Pd(II) complexes featuring electronically tuned amide substituents (alkyl: L1; carboxylic: L2/L3) for the transfer hydrogenation (TH) of trans-cinnamic acid (trans-CA) to hydrocinnamic acid (HCA) in imidazolium-based ionic liquids (ILs). The electronic effects of ligand substituents, hydrogen source (FA/TEA mixtures vs ammonium formate), and solvent environment on catalytic activity were evaluated. Alkylamide-substituted [Pd(L1)Cl2] displayed superior performance with FA/TEA via solution-phase hydride transfer, whereas electron-deficient [Pd(L2-L3)Cl2] were more effective with ammonium formate under a mixed homogeneous/heterogeneous regime. Ionic liquids significantly enhanced catalyst performance compared to the conventional organic solvent DMF, with minor changes in IL cations or anion causing substantial variations in conversion. Mechanistic studies, including MS, UV-Vis, NMR, electrochemistry (using Pt(II) analogues), and gas-evolution analyses, revealed that monoformate Pd intermediates and their evolution depend on the electronic properties of the ligands and the hydrogen donor, directing productive or unproductive pathways. This work highlights the delicate interplay between ligand design, hydrogen source, and ionic liquid microenvironment in controlling Pd-catalyzed transfer hydrogenation and provides a platform for designing efficient, tunable Pd-based TH systems.
{"title":"Tuning Pd Catalyst Performance in Transfer Hydrogenation Reactions: Ligand Electronic Properties, Hydrogen Source and Ionic Liquid-Mediated-Effects.","authors":"Milica Kolaković Marković,Alicja Franke,Ina Kellner,Laura Senft,Peter Mayer,Philipp Maier,Ivana Ivanović-Burmazović","doi":"10.1021/acs.inorgchem.5c05855","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05855","url":null,"abstract":"We report a systematic study of phenanthroline-Pd(II) complexes featuring electronically tuned amide substituents (alkyl: L1; carboxylic: L2/L3) for the transfer hydrogenation (TH) of trans-cinnamic acid (trans-CA) to hydrocinnamic acid (HCA) in imidazolium-based ionic liquids (ILs). The electronic effects of ligand substituents, hydrogen source (FA/TEA mixtures vs ammonium formate), and solvent environment on catalytic activity were evaluated. Alkylamide-substituted [Pd(L1)Cl2] displayed superior performance with FA/TEA via solution-phase hydride transfer, whereas electron-deficient [Pd(L2-L3)Cl2] were more effective with ammonium formate under a mixed homogeneous/heterogeneous regime. Ionic liquids significantly enhanced catalyst performance compared to the conventional organic solvent DMF, with minor changes in IL cations or anion causing substantial variations in conversion. Mechanistic studies, including MS, UV-Vis, NMR, electrochemistry (using Pt(II) analogues), and gas-evolution analyses, revealed that monoformate Pd intermediates and their evolution depend on the electronic properties of the ligands and the hydrogen donor, directing productive or unproductive pathways. This work highlights the delicate interplay between ligand design, hydrogen source, and ionic liquid microenvironment in controlling Pd-catalyzed transfer hydrogenation and provides a platform for designing efficient, tunable Pd-based TH systems.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"57 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147483683","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}
Atmospheric water harvesting (AWH) is an effective strategy to address water scarcity in arid regions, but the key challenge lies in developing adsorbents that can efficiently capture water at low relative humidity, while enabling facile release with minimal energy input. Herein, three mixed-ligand MOFs, Zn-mfa-atz-1, Zn-mfa-atz-2, and Zn-mfa-tz, were synthesized using low-cost ligands, itaconic acid (H2ic) and 3-amino-1,2,4-triazole (Hatz) or 1H-1,2,4-triazole (Htz). During the syntheses, H2ic underwent in situ isomerization into (E)-2-methylfumaric acid (H2mfa). The MOFs are all 3D framework structures, and Zn-mfa-atz-2 and Zn-mfa-tz are isostructural. Zn-mfa-atz-1 and Zn-mfa-atz-2 exhibit permanent porosity (BET surface areas of 353 and 379 m2g–1, respectively) and high stability in liquid water at room temperature for 1 week. Their water vapor adsorption isotherms are reversible, with moderate uptakes at P/P0 < 40% and relatively low adsorption heats (38 to 54 kJ mo–1). Under a low H2O partial pressure of 1.7 kPa, the two MOFs deliver stable water harvesting capacities of 0.08 and 0.11 g g–1 at an adsorption temperature of 32 °C (RH = 35.7%) and a desorption temperature of 60 °C (RH = 8.5%). While the working capacities are not high, the MOFs offer an advantage in terms of material cost.
{"title":"Hydrolytically Stable Zinc-triazole-dicarboxylates for Atmospheric Water Harvesting Formed by In Situ Isomerization of Itaconic Acid","authors":"Zhe Liu, Ya-Nan Wang, Wen-Liang Li, Yu Qin, Xiao-Min Liu, Rui-Chao Zhao, Jian-Rong Li, Lin-Hua Xie","doi":"10.1021/acs.inorgchem.5c06014","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c06014","url":null,"abstract":"Atmospheric water harvesting (AWH) is an effective strategy to address water scarcity in arid regions, but the key challenge lies in developing adsorbents that can efficiently capture water at low relative humidity, while enabling facile release with minimal energy input. Herein, three mixed-ligand MOFs, <b>Zn-mfa-atz-1</b>, <b>Zn-mfa-atz-2</b>, and <b>Zn-mfa-tz</b>, were synthesized using low-cost ligands, itaconic acid (H<sub>2</sub>ic) and 3-amino-1,2,4-triazole (Hatz) or 1<i>H</i>-1,2,4-triazole (Htz). During the syntheses, H<sub>2</sub>ic underwent <i>in situ</i> isomerization into (<i>E</i>)-2-methylfumaric acid (H<sub>2</sub>mfa). The MOFs are all 3D framework structures, and <b>Zn-mfa-atz-2</b> and <b>Zn-mfa-tz</b> are isostructural. <b>Zn-mfa-atz-1</b> and <b>Zn-mfa-atz-2</b> exhibit permanent porosity (BET surface areas of 353 and 379 m<sup>2</sup>g<sup>–1</sup>, respectively) and high stability in liquid water at room temperature for 1 week. Their water vapor adsorption isotherms are reversible, with moderate uptakes at <i>P</i>/<i>P</i><sub>0</sub> < 40% and relatively low adsorption heats (38 to 54 kJ mo<sup>–1</sup>). Under a low H<sub>2</sub>O partial pressure of 1.7 kPa, the two MOFs deliver stable water harvesting capacities of 0.08 and 0.11 g g<sup>–1</sup> at an adsorption temperature of 32 °C (RH = 35.7%) and a desorption temperature of 60 °C (RH = 8.5%). While the working capacities are not high, the MOFs offer an advantage in terms of material cost.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"143 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478615","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}
Molybdenum(II) iodide (Mo6I12) serves as a versatile precursor to phosphorescent octahedral molybdenum cluster complexes that exhibit properties relevant to energy, environmental, and biomedical applications. Despite its straightforward synthesis, stability, and extended visible-light absorption, the photophysical and photocatalytic properties of Mo6I12 have remained unexplored, because the compound has historically been available only as an insoluble bulk material. Herein, we report the top-down preparation of Mo6I12 nanocrystals via ultrasonic treatment, yielding stable colloidal suspensions in acetone and water. The nanocrystals exhibited broad visible-light absorption extending up to ∼700 nm and weak red to near-infrared photoluminescence intensifying at low temperatures. These features indicate an indirect semiconducting nature, which was confirmed by density functional calculations. Upon blue-light illumination, the nanocrystals generate reactive oxygen species, including the hydroxyl radical via a photocatalytic mechanism that operates even under anaerobic conditions. Their photocatalytic potential in the context of water disinfection was validated through bacterial photodynamic inactivation, demonstrating effective inactivation (up to >4 log reduction) of clinically relevant strains of Gram-positive bacteria under visible-light irradiation. The low toxicity of the nanocrystals on HeLa cells highlighted their favorable safety profile for water disinfection. This work reveals the unique light-induced properties of Mo6I12 nanocrystals and establishes them as promising materials for photocatalytic and photodynamic applications.
{"title":"Downsizing Mo6I12 to Nanocrystals Unveils Visible-Light Photocatalytic Antibacterial Activity.","authors":"Michaela Kubáňová,Martin Št'astný,Eric Bourhis,Petr Bezdička,Jakub Tolasz,Aimin Yao,Jean-François Halet,Mouna Ben Yahia,Régis Gautier,Jaroslav Zelenka,Kamil Lang,Régis Guégan,Kaplan Kirakci","doi":"10.1021/acs.inorgchem.5c05876","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05876","url":null,"abstract":"Molybdenum(II) iodide (Mo6I12) serves as a versatile precursor to phosphorescent octahedral molybdenum cluster complexes that exhibit properties relevant to energy, environmental, and biomedical applications. Despite its straightforward synthesis, stability, and extended visible-light absorption, the photophysical and photocatalytic properties of Mo6I12 have remained unexplored, because the compound has historically been available only as an insoluble bulk material. Herein, we report the top-down preparation of Mo6I12 nanocrystals via ultrasonic treatment, yielding stable colloidal suspensions in acetone and water. The nanocrystals exhibited broad visible-light absorption extending up to ∼700 nm and weak red to near-infrared photoluminescence intensifying at low temperatures. These features indicate an indirect semiconducting nature, which was confirmed by density functional calculations. Upon blue-light illumination, the nanocrystals generate reactive oxygen species, including the hydroxyl radical via a photocatalytic mechanism that operates even under anaerobic conditions. Their photocatalytic potential in the context of water disinfection was validated through bacterial photodynamic inactivation, demonstrating effective inactivation (up to >4 log reduction) of clinically relevant strains of Gram-positive bacteria under visible-light irradiation. The low toxicity of the nanocrystals on HeLa cells highlighted their favorable safety profile for water disinfection. This work reveals the unique light-induced properties of Mo6I12 nanocrystals and establishes them as promising materials for photocatalytic and photodynamic applications.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"146 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471704","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}
Quasi-2D (q-2D) perovskite materials can construct a distribution of multiple n phases by incorporating spacer organic cation additives and thus have been widely applied in blue perovskite light-emitting diodes (PeLEDs). However, the lack of research on the regulation of low-n-value q-2D phases by different additives has hindered the development of pure-blue PeLEDs. Herein, by investigating a series of organic cation additives, we identified the key factors governing the assembly of n phases: the additive’s steric hindrance and amino group flexibility. Additives with high steric hindrance can effectively segment the 3D perovskite lattice, facilitating the formation of low-n phases. However, increased flexibility of the amino groups in additives that coordinate with the perovskite lattice induces the further assembly of low-n phases into high-n phases during crystallization, whereas low flexibility can anchor low-n phase components and inhibit their further assembly. By utilizing additives with different steric hindrance and flexibility, we achieved the regulation of electroluminescence spectra of all-bromide q-2D perovskites from green (517 nm) to deep blue (449 nm). It was confirmed that the p-F-PEABr additive, featuring high steric hindrance and low amino group flexibility, can effectively control the uniform distribution of low-n phases. Thus, the corresponding q-2D PeLEDs achieved high-quality pure blue electroluminescence at 468 nm with an external quantum efficiency (EQE) of 2.72%, and no obvious spectral shift was observed. This work uncovers the mechanism underlying the effect of spacer additives’ steric hindrance and amino group flexibility on the precise regulation of q-2D phase distribution, paving the way for the development of pure blue PeLEDs.
{"title":"Synergistic Regulation of Additive’s Steric Hindrance and Amino Group Flexibility Enables All-Bromide Pure Blue Perovskite Light-Emitting Diodes","authors":"Xingle Shang, Likuan Zhou, Yuanyuan Zhang, Kun Zhang, Yifei Wang, Xinrui Chen, Wenjun Yuan, Haoqi Li, Haikun Liu, Hengyang Xiang, Haibo Zeng","doi":"10.1021/acs.inorgchem.6c00280","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00280","url":null,"abstract":"Quasi-2D (q-2D) perovskite materials can construct a distribution of multiple n phases by incorporating spacer organic cation additives and thus have been widely applied in blue perovskite light-emitting diodes (PeLEDs). However, the lack of research on the regulation of low-<i>n</i>-value q-2D phases by different additives has hindered the development of pure-blue PeLEDs. Herein, by investigating a series of organic cation additives, we identified the key factors governing the assembly of n phases: the additive’s steric hindrance and amino group flexibility. Additives with high steric hindrance can effectively segment the 3D perovskite lattice, facilitating the formation of low-<i>n</i> phases. However, increased flexibility of the amino groups in additives that coordinate with the perovskite lattice induces the further assembly of low-<i>n</i> phases into high-<i>n</i> phases during crystallization, whereas low flexibility can anchor low-<i>n</i> phase components and inhibit their further assembly. By utilizing additives with different steric hindrance and flexibility, we achieved the regulation of electroluminescence spectra of all-bromide q-2D perovskites from green (517 nm) to deep blue (449 nm). It was confirmed that the p-F-PEABr additive, featuring high steric hindrance and low amino group flexibility, can effectively control the uniform distribution of low-<i>n</i> phases. Thus, the corresponding q-2D PeLEDs achieved high-quality pure blue electroluminescence at 468 nm with an external quantum efficiency (EQE) of 2.72%, and no obvious spectral shift was observed. This work uncovers the mechanism underlying the effect of spacer additives’ steric hindrance and amino group flexibility on the precise regulation of q-2D phase distribution, paving the way for the development of pure blue PeLEDs.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"231 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478157","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}
A novel hexameric thorium-antimony-tungstate compound, [NH2(CH3)2]16Na10-{[(SbW9O32)(OH)(SbW9O31)(OH)2(SbW9O33)(Th2WSb9O13)(OH)4(H2O)]2}·57H2O (Th4Sb24), has been synthesized. It represents the first tetranuclear thorium-containing polyoxometalates (POMs) cluster, consisting of a [{(Th2WSb9O29)(OH)5(H2O)}2]22- ({Th4Sb18W2}) heterometallic cluster and six {SbW9} units, and it exhibits the highest Th and Sb nuclearity in POM chemistry. Th4Sb24 serves as an efficient heterogeneous catalyst for the Knoevenagel condensation under mild conditions, achieving 93% yield, a turnover number (TON) of 1860, and a turnover frequency (TOF) of 3720 h-1, while showing good recyclability and scalability. Mechanistic studies indicate a synergistic effect where the Lewis-acidic Th centers activate benzaldehyde, while the {SbW9} units facilitate proton abstraction. This work offers a viable strategy for designing high-nuclearity actinide POMs with practical catalytic utility.
{"title":"A Tetranuclear Thorium-Containing Hexameric Antimonotungstate: Synthesis, Structure, and Catalysis of the Knoevenagel Condensation.","authors":"Minghui Xiong,Xiaoyue Wang,Shudi Ji,Yanan Liu,Hanning Zhao,Zixin Gong,Haiying Wang,Jingyang Niu,Dongdi Zhang","doi":"10.1021/acs.inorgchem.6c00156","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00156","url":null,"abstract":"A novel hexameric thorium-antimony-tungstate compound, [NH2(CH3)2]16Na10-{[(SbW9O32)(OH)(SbW9O31)(OH)2(SbW9O33)(Th2WSb9O13)(OH)4(H2O)]2}·57H2O (Th4Sb24), has been synthesized. It represents the first tetranuclear thorium-containing polyoxometalates (POMs) cluster, consisting of a [{(Th2WSb9O29)(OH)5(H2O)}2]22- ({Th4Sb18W2}) heterometallic cluster and six {SbW9} units, and it exhibits the highest Th and Sb nuclearity in POM chemistry. Th4Sb24 serves as an efficient heterogeneous catalyst for the Knoevenagel condensation under mild conditions, achieving 93% yield, a turnover number (TON) of 1860, and a turnover frequency (TOF) of 3720 h-1, while showing good recyclability and scalability. Mechanistic studies indicate a synergistic effect where the Lewis-acidic Th centers activate benzaldehyde, while the {SbW9} units facilitate proton abstraction. This work offers a viable strategy for designing high-nuclearity actinide POMs with practical catalytic utility.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"5 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471709","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}
Pub Date : 2026-03-18DOI: 10.1021/acs.inorgchem.6c00122
Kalyankumar S Morla,Tushar Balasaheb Deshmukh,Subuhan Ahamed,Rajulal Sahu,Lakita Khidtta,Kartik Chandra Mondal,Babasaheb R Sankapal,Abhishek Banerjee
The versatile redox and coordination chemistry of vanadium make oxo-vanadates promising for electrochemical energy storage studies, especially when stabilized by diphosphonate ligands. Herein, we report a series of newly designed 3d-3d mixed-metal hybrid oxovanadates, viz., (NH4)4[H4{CoII(H2O)4}(VV2O5)2(VIVO2){O3P-C(O)(CH2-3-C5NH4)-PO3}2]·5H2O (CoV-a), (NH4)4[H4{NiII(H2O)4}(VV2O5)2(VIVO2){O3P-C(O)(CH2-3-C5NH4)-PO3}2]·7H2O (NiV-a), (NH4)6[H3{CuII(H2O)2(CH3COO)}(VV2O5)2(VIVO2){O3P-C(O)(CH2-3-C5NH4)-PO3}2]·3H2O (CuV-a), (NH4)5[H4{ZnII(H2O)2(CH3COO)}(VV2O5)2(VIVO2){O3P-C(O)(CH2-3-C5NH4)-PO3}2]·4H2O (ZnV-a), incorporating Co, Ni, Cu, and Zn, respectively, with pyridyl-based diphosphonate ligands. Single-crystal X-ray diffraction reveals that all compounds crystallize in the orthorhombic Pnna space group with an isoreticular sinusoidal wave-like structure. Metal oxidation states were confirmed by bond-valence-sum calculations and multiple spectroscopic studies. Electochemical energy storage studies were performed with binder-free electrodes, fabricated via direct growth of crystalline phases on MWCNT-coated stainless-steel substrates and extensively characterized using powder X-ray diffraction, photoelectron spectroscopy, electron microscopy, and surface area analysis. Electrochemical evaluation through cyclic voltammetry, charge-discharge, stability, and impedance studies demonstrated the superior performance of the vanadocuprate derivative compared to the cobalt, nickel, and zinc analogues. The optimized vanadocuprate electrode was thus employed to prepare a symmetric prototype device, which delivered a high energy density of 12 Wh kg-1 and power density of 2957 W kg-1. Practical applicability was demonstrated by successfully powering LEDs, highlighting the potential of these hybrid oxovanadates as efficient energy storage materials.
{"title":"Electrochemical Energy Storage Studies in 3d-3d Mixed-Metal Diphosphonate Oxovanadates: Structure-Property Correlation and Superior Performance of a Copper-Vanadium Electrode in Symmetric Supercapacitors.","authors":"Kalyankumar S Morla,Tushar Balasaheb Deshmukh,Subuhan Ahamed,Rajulal Sahu,Lakita Khidtta,Kartik Chandra Mondal,Babasaheb R Sankapal,Abhishek Banerjee","doi":"10.1021/acs.inorgchem.6c00122","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00122","url":null,"abstract":"The versatile redox and coordination chemistry of vanadium make oxo-vanadates promising for electrochemical energy storage studies, especially when stabilized by diphosphonate ligands. Herein, we report a series of newly designed 3d-3d mixed-metal hybrid oxovanadates, viz., (NH4)4[H4{CoII(H2O)4}(VV2O5)2(VIVO2){O3P-C(O)(CH2-3-C5NH4)-PO3}2]·5H2O (CoV-a), (NH4)4[H4{NiII(H2O)4}(VV2O5)2(VIVO2){O3P-C(O)(CH2-3-C5NH4)-PO3}2]·7H2O (NiV-a), (NH4)6[H3{CuII(H2O)2(CH3COO)}(VV2O5)2(VIVO2){O3P-C(O)(CH2-3-C5NH4)-PO3}2]·3H2O (CuV-a), (NH4)5[H4{ZnII(H2O)2(CH3COO)}(VV2O5)2(VIVO2){O3P-C(O)(CH2-3-C5NH4)-PO3}2]·4H2O (ZnV-a), incorporating Co, Ni, Cu, and Zn, respectively, with pyridyl-based diphosphonate ligands. Single-crystal X-ray diffraction reveals that all compounds crystallize in the orthorhombic Pnna space group with an isoreticular sinusoidal wave-like structure. Metal oxidation states were confirmed by bond-valence-sum calculations and multiple spectroscopic studies. Electochemical energy storage studies were performed with binder-free electrodes, fabricated via direct growth of crystalline phases on MWCNT-coated stainless-steel substrates and extensively characterized using powder X-ray diffraction, photoelectron spectroscopy, electron microscopy, and surface area analysis. Electrochemical evaluation through cyclic voltammetry, charge-discharge, stability, and impedance studies demonstrated the superior performance of the vanadocuprate derivative compared to the cobalt, nickel, and zinc analogues. The optimized vanadocuprate electrode was thus employed to prepare a symmetric prototype device, which delivered a high energy density of 12 Wh kg-1 and power density of 2957 W kg-1. Practical applicability was demonstrated by successfully powering LEDs, highlighting the potential of these hybrid oxovanadates as efficient energy storage materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"70 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471758","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}
Pub Date : 2026-03-18DOI: 10.1021/acs.inorgchem.5c05371
Sougata Sarkar,Tarak Nath Das,Arijit Chakraborty,Shreemoy De
Nanodimensional metallohydrogels with fascinating supramolecular architectures showing potential enzyme-mimicking behavior are a key concern in current research. Here, we have addressed a wet chemistry approach for the synthesis of an Fe(III) metallohydrogel employing the sodium salt of 5-sulfoisophthalic acid. At the outset, the metallogelation results in an opaque gel. Both metal-ligand coordination and solvent-assisted hydrogen bonding interactions are responsible for gel formation. Here, the most intriguing feature was the spontaneous transformation of the as-synthesized opaque gel to a completely transparent gel under ambient conditions over time. The kinetic modulation of this transformation was clearly reflected in differences in the microanalytical results between the opaque and transparent gel materials. Herein, the opaque gel is assigned as a kinetically controlled product (KCP), while the transparent gel is identified as a thermodynamically controlled product (TCP). A mechanism encompassing a delicate balance between KCP and TCP is proposed to elucidate the complex pathway. The nanoscale metallohydrogel was then successfully employed as a heterogeneous catalyst in enzyme mimetic reactions and oxidase and peroxidase mimicking. A simple method for low-level detection of glutathione (GSH) was also reported. Thus, this nanoscale Fe(III) metallohydrogel is illustrated as an efficient dual-purpose artificial enzyme mimic, i.e., nanozyme, showing its application potential in biomimetic research.
{"title":"Gel-to-Gel Transformation in an Fe(III) Metallohydrogel: Kinetic Modulation, Mechanistic Insights, and Dual-Responsive Intrinsic Nanozyme Activity.","authors":"Sougata Sarkar,Tarak Nath Das,Arijit Chakraborty,Shreemoy De","doi":"10.1021/acs.inorgchem.5c05371","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05371","url":null,"abstract":"Nanodimensional metallohydrogels with fascinating supramolecular architectures showing potential enzyme-mimicking behavior are a key concern in current research. Here, we have addressed a wet chemistry approach for the synthesis of an Fe(III) metallohydrogel employing the sodium salt of 5-sulfoisophthalic acid. At the outset, the metallogelation results in an opaque gel. Both metal-ligand coordination and solvent-assisted hydrogen bonding interactions are responsible for gel formation. Here, the most intriguing feature was the spontaneous transformation of the as-synthesized opaque gel to a completely transparent gel under ambient conditions over time. The kinetic modulation of this transformation was clearly reflected in differences in the microanalytical results between the opaque and transparent gel materials. Herein, the opaque gel is assigned as a kinetically controlled product (KCP), while the transparent gel is identified as a thermodynamically controlled product (TCP). A mechanism encompassing a delicate balance between KCP and TCP is proposed to elucidate the complex pathway. The nanoscale metallohydrogel was then successfully employed as a heterogeneous catalyst in enzyme mimetic reactions and oxidase and peroxidase mimicking. A simple method for low-level detection of glutathione (GSH) was also reported. Thus, this nanoscale Fe(III) metallohydrogel is illustrated as an efficient dual-purpose artificial enzyme mimic, i.e., nanozyme, showing its application potential in biomimetic research.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"33 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471705","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}
Pub Date : 2026-03-18DOI: 10.1021/acs.inorgchem.5c06046
Ali S. Mougharbel, Saurav Bhattacharya, Anupam Sarkar, Anton-Jan Bons, Tom D’hondt, Helge Jaensch, Ulrich Kortz
We report on the synthesis, characterization, and catalysis of organorhodium- and iridium-containing derivatives of the 48-tungsto-8-phosphate wheel, [{Rh(Cp*)(H2O)}4P8W48O184]32– (1) and [{Ir(Cp*)(H2O)}4P8W48O184]32– (2). The novel polyanions 1 and 2 were synthesized by the reaction of (MCp*Cl2)2 (M = RhIII, IrIII) with the mixed potassium–lithium salt of the cyclic P8W48 precursor in an aqueous medium using mild one-pot conditions, and four organometallic moieties are covalently bound to the central cavity of the P8W48 wheel via two M-O(W) oxygen bridges. Both polyanions were structurally characterized in the solid state by single-crystal X-ray diffraction, FT-IR spectroscopy, and thermogravimetric analysis, as well as in solution by 31P and 13C NMR spectroscopy. The hydrogenation of olefins was investigated after supporting polyanions 1 and 2 on mesoporous SBA15. The supported catalysts exhibited high activity in the selective hydrogenation of o-xylene with very little cracking products, even under high temperature and pressure conditions.
本文报道了48-钨-8-磷酸轮的含有机铑和含铱衍生物[{Rh(Cp*)(H2O)}4P8W48O184]32 -(1)和[{Ir(Cp*)(H2O)}4P8W48O184]32 -(2)的合成、表征和催化作用。采用（MCp*Cl2）2 （M = RhIII, IrIII）与环P8W48前驱体的混合钾锂盐在水介质中温和的一锅条件下反应合成了新型多阴离子1和2，并通过两个M- o (W)氧桥将4个有机金属基团共价结合到P8W48轮毂的中心腔上。通过单晶x射线衍射、FT-IR光谱和热重分析，以及溶液中的31P和13C NMR光谱，对两种聚阴离子进行了结构表征。研究了在介孔SBA15上负载聚阴离子1和2后烯烃的加氢反应。在高温高压条件下，负载型催化剂对邻二甲苯的选择性加氢反应表现出较高的活性，裂解产物很少。
{"title":"Organorhodium and Iridium-Containing Derivatives of the 48-Tungsto-8-phosphate Wheel: Synthesis, Characterization, and Catalytic Activity","authors":"Ali S. Mougharbel, Saurav Bhattacharya, Anupam Sarkar, Anton-Jan Bons, Tom D’hondt, Helge Jaensch, Ulrich Kortz","doi":"10.1021/acs.inorgchem.5c06046","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c06046","url":null,"abstract":"We report on the synthesis, characterization, and catalysis of organorhodium- and iridium-containing derivatives of the 48-tungsto-8-phosphate wheel, [{Rh(Cp*)(H<sub>2</sub>O)}<sub>4</sub>P<sub>8</sub>W<sub>48</sub>O<sub>184</sub>]<sup>32–</sup> (<b>1</b>) and [{Ir(Cp*)(H<sub>2</sub>O)}<sub>4</sub>P<sub>8</sub>W<sub>48</sub>O<sub>184</sub>]<sup>32–</sup> (<b>2</b>). The novel polyanions <b>1</b> and <b>2</b> were synthesized by the reaction of (MCp*Cl<sub>2</sub>)<sub>2</sub> (M = Rh<sup>III</sup>, Ir<sup>III</sup>) with the mixed potassium–lithium salt of the cyclic P<sub>8</sub>W<sub>48</sub> precursor in an aqueous medium using mild one-pot conditions, and four organometallic moieties are covalently bound to the central cavity of the P<sub>8</sub>W<sub>48</sub> wheel via two M-O(W) oxygen bridges. Both polyanions were structurally characterized in the solid state by single-crystal X-ray diffraction, FT-IR spectroscopy, and thermogravimetric analysis, as well as in solution by <sup>31</sup>P and <sup>13</sup>C NMR spectroscopy. The hydrogenation of olefins was investigated after supporting polyanions <b>1</b> and <b>2</b> on mesoporous SBA15. The supported catalysts exhibited high activity in the selective hydrogenation of o-xylene with very little cracking products, even under high temperature and pressure conditions.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"28 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478737","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}
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