It is urgent and significant to design and fabricate long-range ordered crystalline proton-conductive materials and study their proton conduction mechanisms. Two new polyoxometalate-based coordination polymers, named CUST-963 and CUST-964, have been constructed by combining Keggin-type H4SiW12O40 (SiW12), nitrogen-rich ligand 2,5-di(1H-imidazole-1-yl)terephthalic acid (H2DTA), and transition metal ions under hydrothermal conditions. X-ray diffraction analysis revealed that there are more uncoordinated nitrogen sites within CUST-963, which can collaboratively form a denser and continuous hydrogen-bonding network with surface oxygen atoms of SiW12 and water molecules and act as proton hopping sites. The alternating current impedance tests suggested CUST-963 achieves a lower activation energy (0.14 eV) and a higher proton conductivity (1.88 × 10–2 S cm–1) than that of CUST-964 under 95 °C and 98% relative humidity. This work provided an effective strategy for designing high-performance proton-conductive materials.
设计和制备远程有序晶体质子导电材料并研究其质子传导机理具有迫切而重要的意义。在水热条件下，将keggin型H4SiW12O40 （SiW12）与富氮配体2,5-二（1h -咪唑-1-酰基）对苯二甲酸（H2DTA）和过渡金属离子结合，构建了两种新型多金属氧酸盐基配位聚合物，命名为ust -963和ust -964。x射线衍射分析表明，CUST-963中存在更多的非配位氮位点，这些位点可以与SiW12表面氧原子和水分子协同形成更密集、连续的氢键网络，并充当质子跳跃位点。交流阻抗测试表明，在95℃、98%相对湿度条件下，CUST-963比CUST-964具有更低的活化能（0.14 eV）和更高的质子电导率（1.88 × 10-2 S cm-1）。这项工作为设计高性能质子导电材料提供了一种有效的策略。
{"title":"Constructing Denser Hydrogen-Bonding Networks in Polyoxometalate-Based Coordination Polymers for Enhancing Proton Conduction","authors":"Xin Zheng, Xue-Song Wu, Hong-Yan Li, Xingqi Han, Yu Tian, Xinlong Wang, Zonghang Li, Zhong-Min Su","doi":"10.1021/acs.inorgchem.5c05341","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05341","url":null,"abstract":"It is urgent and significant to design and fabricate long-range ordered crystalline proton-conductive materials and study their proton conduction mechanisms. Two new polyoxometalate-based coordination polymers, named CUST-963 and CUST-964, have been constructed by combining Keggin-type H<sub>4</sub>SiW<sub>12</sub>O<sub>40</sub> (SiW<sub>12</sub>), nitrogen-rich ligand 2,5-di(1<i>H</i>-imidazole-1-yl)terephthalic acid (H<sub>2</sub>DTA), and transition metal ions under hydrothermal conditions. X-ray diffraction analysis revealed that there are more uncoordinated nitrogen sites within CUST-963, which can collaboratively form a denser and continuous hydrogen-bonding network with surface oxygen atoms of SiW<sub>12</sub> and water molecules and act as proton hopping sites. The alternating current impedance tests suggested CUST-963 achieves a lower activation energy (0.14 eV) and a higher proton conductivity (1.88 × 10<sup>–2</sup> S cm<sup>–1</sup>) than that of CUST-964 under 95 °C and 98% relative humidity. This work provided an effective strategy for designing high-performance proton-conductive materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"19 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116131","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 : 2026-02-05DOI: 10.1021/acs.inorgchem.6c00202
Xuemei Wen, Qinglan Zhong, Guohong Zou, Jing Li, Zhien Lin
Transparent crystals of Zn(SCN)2(l-C6H9N3O2) (1) and Zn(SCN)(l-C5H8NO2)(H2O) (2) were obtained using natural amino acids as linkers. The two compounds have one-dimensional structures that combine molecular and helical chiralities. They exhibit significant nonlinear optical responses that are phase matchable under 1064 nm laser irradiation. Notably, the second-harmonic generation efficiency of compound 2 (3.8 × KH2PO4) surpasses those of previously reported metal thiocyanates functionalized with natural amino acids.
{"title":"Nonlinear Optical Responses in One-Dimensional Zinc Thiocyanates Functionalized with Natural Amino Acids","authors":"Xuemei Wen, Qinglan Zhong, Guohong Zou, Jing Li, Zhien Lin","doi":"10.1021/acs.inorgchem.6c00202","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00202","url":null,"abstract":"Transparent crystals of Zn(SCN)<sub>2</sub>(<span>l</span>-C<sub>6</sub>H<sub>9</sub>N<sub>3</sub>O<sub>2</sub>) (<b>1</b>) and Zn(SCN)(<span>l</span>-C<sub>5</sub>H<sub>8</sub>NO<sub>2</sub>)(H<sub>2</sub>O) (<b>2</b>) were obtained using natural amino acids as linkers. The two compounds have one-dimensional structures that combine molecular and helical chiralities. They exhibit significant nonlinear optical responses that are phase matchable under 1064 nm laser irradiation. Notably, the second-harmonic generation efficiency of compound <b>2</b> (3.8 × KH<sub>2</sub>PO<sub>4</sub>) surpasses those of previously reported metal thiocyanates functionalized with natural amino acids.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"23 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122346","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}
The interplay between electrical conduction and magnetism offers a powerful means to elucidate emergent mechanisms and control properties; however, realizing this in Ni(dmit)2 crystals has been challenging due to undesirable reactions among their components. Mn1.83([18]crown-6)3[Ni(dmit)2]11(H2O)7.33(CH3CN)2 (1) is prepared in the present study, integrating one-dimensional [18]crown-6 ion channels hosting mixed-valence Mn2+/Mn3+ with conducting [Ni(dmit)2] layers. Subsequently, a structure-driven mechanism of conductivity is clarified. In the crystal, [Ni(dmit)2] forms one-dimensional dimer–dimer–trimer–dimer–dimer stacks; weak interchain contacts generate two-dimensional sheets alternating with supramolecular channel layers. Mn ions occupy two partially populated sites and adopt seven-coordinate environments with two axial aqua ligands and five equatorial crown-ether oxygen. Magnetometry indicates Mn moments are effectively decoupled from the conducting [Ni(dmit)2] sublattice: the Mn sublattice follows Curie–Weiss behavior with an exceptionally small Weiss temperature, while the [Ni(dmit)2] stacks form S = 1/2 one-dimensional Heisenberg antiferromagnetic chains. Compound 1 exhibits high conductivity at 300 K and one-dimensional variable-range hopping, attributable to thermal fluctuations of the supramolecular channels that modulate intracolumn transfer integrals and promote carrier localization. To our knowledge, 1 is the first system combining transition-metal-ion [18]crown-6 channels with conducting [Ni(dmit)2] layers, establishing a supramolecular route to tune spin–charge coexistence via host design.
{"title":"Supramolecular Ion-Channel Engineering of Spin–Charge Coexistence in a [Ni(dmit)2] Conductor Hosting Mixed-Valence Mn Cations","authors":"Daisuke Ishikawa, Jun Manabe, Masato Haneda, Kiyonori Takahashi, Takayoshi Nakamura, Sadafumi Nishihara","doi":"10.1021/acs.inorgchem.6c00118","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00118","url":null,"abstract":"The interplay between electrical conduction and magnetism offers a powerful means to elucidate emergent mechanisms and control properties; however, realizing this in Ni(dmit)<sub>2</sub> crystals has been challenging due to undesirable reactions among their components. Mn<sub>1.83</sub>([18]crown-6)<sub>3</sub>[Ni(dmit)<sub>2</sub>]<sub>11</sub>(H<sub>2</sub>O)<sub>7.33</sub>(CH<sub>3</sub>CN)<sub>2</sub> (<b>1</b>) is prepared in the present study, integrating one-dimensional [18]crown-6 ion channels hosting mixed-valence Mn<sup>2+</sup>/Mn<sup>3+</sup> with conducting [Ni(dmit)<sub>2</sub>] layers. Subsequently, a structure-driven mechanism of conductivity is clarified. In the crystal, [Ni(dmit)<sub>2</sub>] forms one-dimensional dimer–dimer–trimer–dimer–dimer stacks; weak interchain contacts generate two-dimensional sheets alternating with supramolecular channel layers. Mn ions occupy two partially populated sites and adopt seven-coordinate environments with two axial aqua ligands and five equatorial crown-ether oxygen. Magnetometry indicates Mn moments are effectively decoupled from the conducting [Ni(dmit)<sub>2</sub>] sublattice: the Mn sublattice follows Curie–Weiss behavior with an exceptionally small Weiss temperature, while the [Ni(dmit)<sub>2</sub>] stacks form <i>S</i> = 1/2 one-dimensional Heisenberg antiferromagnetic chains. Compound <b>1</b> exhibits high conductivity at 300 K and one-dimensional variable-range hopping, attributable to thermal fluctuations of the supramolecular channels that modulate intracolumn transfer integrals and promote carrier localization. To our knowledge, <b>1</b> is the first system combining transition-metal-ion [18]crown-6 channels with conducting [Ni(dmit)<sub>2</sub>] layers, establishing a supramolecular route to tune spin–charge coexistence via host design.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"23 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116059","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}
Birefringent crystals have become increasingly appealing for versatile polarization devices owing to their ability to modulate the polarized light. However, the efficient synthesis of material with sufficient birefringent value and wide transparency range is still a significant challenge. Herein, a new rare-earth borate birefringent crystal, Li6Lu(BO3)3 (LLBO), was successfully synthesized and comprehensively characterized. LLBO crystallizes in the monoclinic system with space group P21/c, featuring a robust three-dimensional framework constructed from distorted [LuO6] octahedra and planar [BO3] triangles. LLBO exhibits excellent thermal stability up to 1200 °C. Notably, LLBO displays a remarkably short ultraviolet (UV) cutoff edge at 204 nm supplemented by a wide optical band gap of 5.48 eV, demonstrating its excellent transparency in the near-UV regions. The experimentally measured birefringence (Δn = 0.057) displays a good agreement with the theoretical value (Δn = 0.056@1064 nm), confirming that LLBO exhibits pronounced optical anisotropy. The optical characteristics of LLBO derived from theoretical calculations are mainly reliant on the essential structural groups [LuO6] polyhedra and [BO3] triangles. Above results reveal the potential application of LLBO for light polarization modulation and provide novel insights for fabricating short-wave ultraviolet birefringent materials.
{"title":"Li6Lu(BO3)3: A Rare-Earth Borate Crystal Exhibiting Large Birefringence and Broad UV Transparency","authors":"Mingyue Gu, Xianchao Zhu, Zhanggui Hu, Yicheng Wu, Yongmin Guo","doi":"10.1021/acs.inorgchem.5c05985","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05985","url":null,"abstract":"Birefringent crystals have become increasingly appealing for versatile polarization devices owing to their ability to modulate the polarized light. However, the efficient synthesis of material with sufficient birefringent value and wide transparency range is still a significant challenge. Herein, a new rare-earth borate birefringent crystal, Li<sub>6</sub>Lu(BO<sub>3</sub>)<sub>3</sub> (LLBO), was successfully synthesized and comprehensively characterized. LLBO crystallizes in the monoclinic system with space group <i>P</i>2<sub>1</sub>/<i>c</i>, featuring a robust three-dimensional framework constructed from distorted [LuO<sub>6</sub>] octahedra and planar [BO<sub>3</sub>] triangles. LLBO exhibits excellent thermal stability up to 1200 °C. Notably, LLBO displays a remarkably short ultraviolet (UV) cutoff edge at 204 nm supplemented by a wide optical band gap of 5.48 eV, demonstrating its excellent transparency in the near-UV regions. The experimentally measured birefringence (Δ<i>n</i> = 0.057) displays a good agreement with the theoretical value (Δ<i>n</i> = 0.056@1064 nm), confirming that LLBO exhibits pronounced optical anisotropy. The optical characteristics of LLBO derived from theoretical calculations are mainly reliant on the essential structural groups [LuO<sub>6</sub>] polyhedra and [BO<sub>3</sub>] triangles. Above results reveal the potential application of LLBO for light polarization modulation and provide novel insights for fabricating short-wave ultraviolet birefringent materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"58 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116146","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 : 2026-02-04DOI: 10.1021/acs.inorgchem.5c04367
Yao Xiao,Dan Ni Luo,Qing Lin Guan,Yu Xian Chi,Ting Zhang,Feng Ying Bai,Yong Heng Xing
Viologen-encapsulated metal–organic frameworks (MOFs) have attracted significant interest owing to their responsiveness to multiple external stimuli, which enhances their potential applications in sensing and environmental monitoring. Here, we synthesized the novel viologen-encapsulated Ho-MOF material (pbpy)·[Ho2(NH2–BDC)4(H2O)]·3H2O (complex 1) via an in situ method using 2-aminoterephthalic acid (NH2–H2BDC) and the viologen derivative dichloro-1,1′-(1,4-benzylidene)-di(4,4′-bipyridine) (pbpy·2Cl), along with the control material [Ho4(NH2–BDC)5(DMA)2(μ3-OH)2]·3H2O (complex 2) without a viologen for comparison. Complex 1 exhibited dual detection capability for Th(IV) and nitroaromatic compounds (NACs), demonstrating significant advantages in sensing performance compared to complex 2. These results highlight the critical role of viologen incorporation in improving sensor functionality. Moreover, we prepared a MOF-based PVDF composite film material capable of rapidly detecting Th(IV) and NACs, demonstrating potential for practical sensing applications. In addition, thanks to the presence of a viologen inside the channels, complex 1 could achieve rapid and visual detection of N2H4·H2O. EPR results indicate that the color change is due to the generation of viologen radicals. These properties make the material a promising candidate for multianalyte detection, advancing the development of multistimulus responsive materials.
{"title":"NH2–BDC-Pillared Ho-MOFs with/without Viologen Encapsulation: Fluorescence Sensing, Multistimulus Response, and PVDF Composite Film","authors":"Yao Xiao,Dan Ni Luo,Qing Lin Guan,Yu Xian Chi,Ting Zhang,Feng Ying Bai,Yong Heng Xing","doi":"10.1021/acs.inorgchem.5c04367","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c04367","url":null,"abstract":"Viologen-encapsulated metal–organic frameworks (MOFs) have attracted significant interest owing to their responsiveness to multiple external stimuli, which enhances their potential applications in sensing and environmental monitoring. Here, we synthesized the novel viologen-encapsulated Ho-MOF material (pbpy)·[Ho2(NH2–BDC)4(H2O)]·3H2O (complex 1) via an in situ method using 2-aminoterephthalic acid (NH2–H2BDC) and the viologen derivative dichloro-1,1′-(1,4-benzylidene)-di(4,4′-bipyridine) (pbpy·2Cl), along with the control material [Ho4(NH2–BDC)5(DMA)2(μ3-OH)2]·3H2O (complex 2) without a viologen for comparison. Complex 1 exhibited dual detection capability for Th(IV) and nitroaromatic compounds (NACs), demonstrating significant advantages in sensing performance compared to complex 2. These results highlight the critical role of viologen incorporation in improving sensor functionality. Moreover, we prepared a MOF-based PVDF composite film material capable of rapidly detecting Th(IV) and NACs, demonstrating potential for practical sensing applications. In addition, thanks to the presence of a viologen inside the channels, complex 1 could achieve rapid and visual detection of N2H4·H2O. EPR results indicate that the color change is due to the generation of viologen radicals. These properties make the material a promising candidate for multianalyte detection, advancing the development of multistimulus responsive materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"3 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111237","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 : 2026-02-04DOI: 10.1021/acs.inorgchem.5c05109
Parveen K. Verma,Arunasis Bhattacharyya,Prasanta K. Mohapatra
The oxidation of Am3+ and stabilization of its higher oxidation states are critical for Am/Cm separations and for understanding its fundamental chemistry. While most researchers focused on Am oxidation in HNO3. Other reports indicate stabilization of AmO22+ and AmO2+ in H3PO4 and HCl media, respectively, using NaBiO3. However, the formation and stabilization of Am higher oxidation states in these ternary heterogeneous systems (NaBiO3(s) + mineral acid(aq) + Am(aq)) remain unclear. In the present work, we investigated the behavior of NaBiO3 in different acidic solutions (binary system) and extended it to a ternary system (NaBiO3 + Am3+ in HCl). Although different mineral acids react uniquely with NaBiO3, an increase in the initial pH after NaBiO3 contact was observed in all cases, but to a different extent. The variations in the equilibrium pH and mineralogy of acid-treated NaBiO3 suggest that H+ ions plays key role in Bi5+ → Bi3+ conversion. Additionaly the specific anion of the mineral acid appears to dictate the formation of additional mineral phases. Our findings suggest that the higher stability of AmO2+ in HCl is primarily due to its elevated pH following NaBiO3 contact, which prevents its reduction/disproportionation. Conversely, H3PO4, being a polyprotic acid, behaves differently and stabilizes AmO22+ mainly through phosphate complexation.
{"title":"Understanding the Stability of the Unusual Oxidation States of Americium in Different Mineral Acids","authors":"Parveen K. Verma,Arunasis Bhattacharyya,Prasanta K. Mohapatra","doi":"10.1021/acs.inorgchem.5c05109","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05109","url":null,"abstract":"The oxidation of Am3+ and stabilization of its higher oxidation states are critical for Am/Cm separations and for understanding its fundamental chemistry. While most researchers focused on Am oxidation in HNO3. Other reports indicate stabilization of AmO22+ and AmO2+ in H3PO4 and HCl media, respectively, using NaBiO3. However, the formation and stabilization of Am higher oxidation states in these ternary heterogeneous systems (NaBiO3(s) + mineral acid(aq) + Am(aq)) remain unclear. In the present work, we investigated the behavior of NaBiO3 in different acidic solutions (binary system) and extended it to a ternary system (NaBiO3 + Am3+ in HCl). Although different mineral acids react uniquely with NaBiO3, an increase in the initial pH after NaBiO3 contact was observed in all cases, but to a different extent. The variations in the equilibrium pH and mineralogy of acid-treated NaBiO3 suggest that H+ ions plays key role in Bi5+ → Bi3+ conversion. Additionaly the specific anion of the mineral acid appears to dictate the formation of additional mineral phases. Our findings suggest that the higher stability of AmO2+ in HCl is primarily due to its elevated pH following NaBiO3 contact, which prevents its reduction/disproportionation. Conversely, H3PO4, being a polyprotic acid, behaves differently and stabilizes AmO22+ mainly through phosphate complexation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"8 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111245","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 : 2026-02-04DOI: 10.1021/acs.inorgchem.5c03344
Ye Tian,Teng Lu,Shaoqi Guo,Chen Chen,Liaona She,Li Jin,Ray L. Withers,Yuanting Wu,Wanyin Ge,Xiaoyong Wei,Haixue Yan,Yun Liu
It is common that the as-sintered bulk ceramics or powders undergo mechanical and/or heat treatment for further investigating the structure or properties. However, if their structures change during these procedures, it would mislead their structure–properties relation and subsequently lead to the wrong design of the desired ceramic products. In this work, we reported the mechanical/heat treatment effect on the structures of AgNbO3-based antiferroelectric/ferroelectric (AFE/FE) materials. The results revealed that the structure of AgNbO3-based systems with chemical compositions close to/in the AFE/FE phase boundary strongly depends on the history of polishing/grinding and/or annealing processing. Manual polishing/grinding (or milling) ceramic bulk/powders can induce a phase transition from AFE(Pbcm) to FE(R3c), and the transition can be reversed via the heat treatment, which is intimately related to a temperature-driven phase transformation having a metastable AFE phase. Our finding thus provides new insight into phase transitions in AgNbO3-based systems, suggesting that the proper parameters of processing need to be considered to enable the development of an understanding of structure–property relationships in ceramic materials.
{"title":"Susceptible Antiferroelectric/Ferroelectric Transitions in Silver Niobate-Based Ceramics Induced by Manual Mechanical Processing","authors":"Ye Tian,Teng Lu,Shaoqi Guo,Chen Chen,Liaona She,Li Jin,Ray L. Withers,Yuanting Wu,Wanyin Ge,Xiaoyong Wei,Haixue Yan,Yun Liu","doi":"10.1021/acs.inorgchem.5c03344","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c03344","url":null,"abstract":"It is common that the as-sintered bulk ceramics or powders undergo mechanical and/or heat treatment for further investigating the structure or properties. However, if their structures change during these procedures, it would mislead their structure–properties relation and subsequently lead to the wrong design of the desired ceramic products. In this work, we reported the mechanical/heat treatment effect on the structures of AgNbO3-based antiferroelectric/ferroelectric (AFE/FE) materials. The results revealed that the structure of AgNbO3-based systems with chemical compositions close to/in the AFE/FE phase boundary strongly depends on the history of polishing/grinding and/or annealing processing. Manual polishing/grinding (or milling) ceramic bulk/powders can induce a phase transition from AFE(Pbcm) to FE(R3c), and the transition can be reversed via the heat treatment, which is intimately related to a temperature-driven phase transformation having a metastable AFE phase. Our finding thus provides new insight into phase transitions in AgNbO3-based systems, suggesting that the proper parameters of processing need to be considered to enable the development of an understanding of structure–property relationships in ceramic materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"68 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111235","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}
The development of novel multicomponent nanozymes with high catalytic efficiency and selectivity continues to be a focal point in contemporary research. In this work, a multilanthanide-containing phospho(III)tungstate [H2N(CH3)2]8Na12H16[La4(H2O)15W8(tart)3(H2tart)O20]2[H2P2W14O52]4·52H2O (1, H4tart = tartaric acid) was synthesized. Its polyoxoanion consists of two identical tartrate-stabilized tetra-La3+-substituted {La4(H2O)15W8(tart)3(H2tart)O20} units bridged by four multivacant Dawson-like [H2P2W14O52]12– fragments. Subsequently, 1 was subjected to ultrasonic treatment to form a nanofilm, which was then used as a guest material to coat MIL-(53)Fe (MILFe), preparing a series of core–shell heterostructured MILFe@1 composites. These MILFe@1 composites facilitate multielectron transfer and function as highly active nanozymes, significantly enhancing the catalytic oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB). Under optimized conditions, the MILFe@1–2 (1: MILFe = 1:2) composite demonstrates robust catalytic performance over a broad TMB concentration range without the need for H2O2. This work highlights the potential of integrating lanthanide-containing polyoxometalates with metal–organic frameworks to construct core–shell heterostructured nanozymes with enhanced catalytic efficiency. Concurrently, the polyoxometalate shell enables rapid electron transfer kinetics, which is crucial for enhancing the overall catalytic performance of the system.
{"title":"Core–Shell Heterostructured Composite Architected from a Multilanthanide-Included Phospho(III)tungstate and MIL-(53)Fe as a Nanozyme for Catalytic Oxidation of 3,3′,5,5′-Tetramethylbenzidine","authors":"Guoping Liu,Jun Jiang,Baoxing Zeng,Yanzhou Li,Lijuan Chen,Junwei Zhao","doi":"10.1021/acs.inorgchem.5c05706","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05706","url":null,"abstract":"The development of novel multicomponent nanozymes with high catalytic efficiency and selectivity continues to be a focal point in contemporary research. In this work, a multilanthanide-containing phospho(III)tungstate [H2N(CH3)2]8Na12H16[La4(H2O)15W8(tart)3(H2tart)O20]2[H2P2W14O52]4·52H2O (1, H4tart = tartaric acid) was synthesized. Its polyoxoanion consists of two identical tartrate-stabilized tetra-La3+-substituted {La4(H2O)15W8(tart)3(H2tart)O20} units bridged by four multivacant Dawson-like [H2P2W14O52]12– fragments. Subsequently, 1 was subjected to ultrasonic treatment to form a nanofilm, which was then used as a guest material to coat MIL-(53)Fe (MILFe), preparing a series of core–shell heterostructured MILFe@1 composites. These MILFe@1 composites facilitate multielectron transfer and function as highly active nanozymes, significantly enhancing the catalytic oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB). Under optimized conditions, the MILFe@1–2 (1: MILFe = 1:2) composite demonstrates robust catalytic performance over a broad TMB concentration range without the need for H2O2. This work highlights the potential of integrating lanthanide-containing polyoxometalates with metal–organic frameworks to construct core–shell heterostructured nanozymes with enhanced catalytic efficiency. Concurrently, the polyoxometalate shell enables rapid electron transfer kinetics, which is crucial for enhancing the overall catalytic performance of the system.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"28 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111218","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}
Metal–organic frameworks (MOFs) exhibit attractive catalytic performance, particularly for carbon dioxide (CO2) fixation. We here developed a new MOF {Cu2(Bibt)(Apta)2}n, namely CuBA, under the solvothermal process {Bibt = (4,7-bis(1H-imidazol-1-yl)benzo-[2,1,3]thiadiazole, Apta = deprotonation of 2-aminophthalic acid}. CuBA forms a paddle-wheel binuclear copper(II) Cu2(COO)4N2 unit, which is further extended to a 6-connected three-dimensional (3D) {412•63} topology. In particular, CuBA shows a high CO2/N2 selectivity at 298 K, which encourages us to apply it to catalyze CO2 fixation. The experiments demonstrate that CuBA can catalyze the carboxylative cyclization of various propargylic amines with CO2 at ambient conditions (1 atm, 25 °C) with high TON. Moreover, CuBA maintains good catalytic activities for 5 cycles, showing good recyclability. Significantly, the gram-scale reaction is performed with a good yield. Furthermore, the low-concentration CO2 (30 vol %) experiments under CuBA afford the products in moderate to good yields (25 °C, 24 h). 1H NMR studies indicate that CuBA and DBU work together to activate the propargylic amine substrate, facilitating the reaction. It is anticipated that this work will inspire the rational design of non-noble-metal-containing MOFs for efficient CO2 utilization under mild conditions.
{"title":"A Paddle-Wheel Binuclear Copper(II)-Based MOF for Cyclization of Propargylic Amines with Flue Gas CO2 at Ambient Conditions","authors":"Mengling Xu,Yan Deng,Jiuzheng Zhang,Qiu-Hong Cheng,Xiang-Yu Zhang,Kun Huang,Da-Bin Qin","doi":"10.1021/acs.inorgchem.5c05750","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05750","url":null,"abstract":"Metal–organic frameworks (MOFs) exhibit attractive catalytic performance, particularly for carbon dioxide (CO2) fixation. We here developed a new MOF {Cu2(Bibt)(Apta)2}n, namely CuBA, under the solvothermal process {Bibt = (4,7-bis(1H-imidazol-1-yl)benzo-[2,1,3]thiadiazole, Apta = deprotonation of 2-aminophthalic acid}. CuBA forms a paddle-wheel binuclear copper(II) Cu2(COO)4N2 unit, which is further extended to a 6-connected three-dimensional (3D) {412•63} topology. In particular, CuBA shows a high CO2/N2 selectivity at 298 K, which encourages us to apply it to catalyze CO2 fixation. The experiments demonstrate that CuBA can catalyze the carboxylative cyclization of various propargylic amines with CO2 at ambient conditions (1 atm, 25 °C) with high TON. Moreover, CuBA maintains good catalytic activities for 5 cycles, showing good recyclability. Significantly, the gram-scale reaction is performed with a good yield. Furthermore, the low-concentration CO2 (30 vol %) experiments under CuBA afford the products in moderate to good yields (25 °C, 24 h). 1H NMR studies indicate that CuBA and DBU work together to activate the propargylic amine substrate, facilitating the reaction. It is anticipated that this work will inspire the rational design of non-noble-metal-containing MOFs for efficient CO2 utilization under mild conditions.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"31 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111216","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}
The ligand loading-dependent ortho/meta switching regioselectivity in an Ir-catalyzed C–H borylation of an aromatic ester has been experimentally achieved recently, while the origin of switching regioselectivity still remains unclear. In this work, we performed density functional theory (DFT) calculations to reveal the reaction mechanism and the principle of the switching regioselectivity. Results show that two active species, namely, (N, B)2IrIII(Bpin) and (N, B)IrIII(Bpin)2, are generated in situ, and their concentrations are dependent on the ligand loading. When the loading of the ligand is sufficient, the concentration of (N, B)2IrIII(Bpin) is higher, which catalyzes the C(sp2)–H bond activation via an unusual N, B bidentate ligand-assisted mechanism. The unexpected meta-selective C(sp2)–H borylation is achieved because the interplay between (N, B)2IrIII(Bpin) and the aromatic ester leads to special steric effects and noncovalent interactions. When the ligand is insufficient, the concentration of tetra-coordinated (N, B)IrIII(Bpin)2 becomes higher. Ortho-selective C(sp2)–H borylation is achieved via coordination directing because the coordination of the carbonyl group stabilizes tetra-coordinated active species with two vacant sites and leads the ortho C–H bonds approaching the active center. These findings are expected to aid the development of innovative strategies for precise control of the regioselectivity in Ir-catalyzed C–H borylation.
{"title":"More is Different: Theoretical Investigation on the Origin of Ligand Loading-Dependent Switching Regioselectivity in Ir-Catalyzed C–H Borylation","authors":"Ling-Qi Meng,Xiao-Xia You,Li-Li Wang,Xin-Cheng Xu,Zhong-Min Su,Feng-Wei Gao,Rong-Lin Zhong","doi":"10.1021/acs.inorgchem.5c05218","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05218","url":null,"abstract":"The ligand loading-dependent ortho/meta switching regioselectivity in an Ir-catalyzed C–H borylation of an aromatic ester has been experimentally achieved recently, while the origin of switching regioselectivity still remains unclear. In this work, we performed density functional theory (DFT) calculations to reveal the reaction mechanism and the principle of the switching regioselectivity. Results show that two active species, namely, (N, B)2IrIII(Bpin) and (N, B)IrIII(Bpin)2, are generated in situ, and their concentrations are dependent on the ligand loading. When the loading of the ligand is sufficient, the concentration of (N, B)2IrIII(Bpin) is higher, which catalyzes the C(sp2)–H bond activation via an unusual N, B bidentate ligand-assisted mechanism. The unexpected meta-selective C(sp2)–H borylation is achieved because the interplay between (N, B)2IrIII(Bpin) and the aromatic ester leads to special steric effects and noncovalent interactions. When the ligand is insufficient, the concentration of tetra-coordinated (N, B)IrIII(Bpin)2 becomes higher. Ortho-selective C(sp2)–H borylation is achieved via coordination directing because the coordination of the carbonyl group stabilizes tetra-coordinated active species with two vacant sites and leads the ortho C–H bonds approaching the active center. These findings are expected to aid the development of innovative strategies for precise control of the regioselectivity in Ir-catalyzed C–H borylation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"91 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111246","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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