The exploration of novel metal-oxo clusters with unique composition and functionality remains an attractive goal in the field of structural chemistry and materials chemistry. By employing a triply synergistic induction strategy that combines ligand induction with structural tailoring effect of halide anions (I-) and lone pair electrons of low-valency p-block metal ions (Pb2+ and Sb3+ ions), two unprecedented organic ligand-decorated lead-antimony oxohalide cluster compounds have been successfully prepared, namely [(HTEOA)SbOPbI]4·2H2O (H3TEOA = triethanolamine) (1) and (HTEOA)3Sb3OPbI3·CH3OH (2). 1 features a sandwich configuration formed by two pairs of Sb-L (L= HTEOA) layers and a central [Pb4O4I4] unit. By contrast, 2 represents a crown configuration consisting of a [Sb3OL3] base and a [PbI3] cap. Compound 1 exhibits excellent irradiation stability and high removal capacity for UO22+ ions, with rapid kinetics response reaching removal rate (RU) of 99.89% within 5 minutes. Even in the presence of high concentrations of competing ions (e.g., Na+, Ca2+ and Mg2+) and in actual water samples, it maintains exceptional selectivity toward UO22+ with high removal efficiency (distribution coefficient (KdU) > 7.42 × 104 mL g-1, RU > 98.64%). This work not only represents a breakthrough in p-block heterometallic oxohalide cluster chemistry, but also expands the potential of antimony oxohalide clusters for radionuclide remendiation.
{"title":"Unprecedented Lead-Antimony Oxohalide Clusters with the Efficient Capture for UO22+ ions","authors":"Jia-Hua Luo, Yu-Wei Ren, Lu Yang, Jing Wang, Hao-Dan Xiao, Feng-Hua Xian, Hai-Yan Sun, Mei-Ling Feng, Bing Hu, Xiao-Ying Huang","doi":"10.1039/d5qi02583d","DOIUrl":"https://doi.org/10.1039/d5qi02583d","url":null,"abstract":"The exploration of novel metal-oxo clusters with unique composition and functionality remains an attractive goal in the field of structural chemistry and materials chemistry. By employing a triply synergistic induction strategy that combines ligand induction with structural tailoring effect of halide anions (I-) and lone pair electrons of low-valency p-block metal ions (Pb2+ and Sb3+ ions), two unprecedented organic ligand-decorated lead-antimony oxohalide cluster compounds have been successfully prepared, namely [(HTEOA)SbOPbI]4·2H2O (H3TEOA = triethanolamine) (1) and (HTEOA)3Sb3OPbI3·CH3OH (2). 1 features a sandwich configuration formed by two pairs of Sb-L (L= HTEOA) layers and a central [Pb4O4I4] unit. By contrast, 2 represents a crown configuration consisting of a [Sb3OL3] base and a [PbI3] cap. Compound 1 exhibits excellent irradiation stability and high removal capacity for UO22+ ions, with rapid kinetics response reaching removal rate (RU) of 99.89% within 5 minutes. Even in the presence of high concentrations of competing ions (e.g., Na+, Ca2+ and Mg2+) and in actual water samples, it maintains exceptional selectivity toward UO22+ with high removal efficiency (distribution coefficient (KdU) > 7.42 × 104 mL g-1, RU > 98.64%). This work not only represents a breakthrough in p-block heterometallic oxohalide cluster chemistry, but also expands the potential of antimony oxohalide clusters for radionuclide remendiation.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116060","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}
Achieving direct cleavage of CO bonds in biomass under mild conditions to generate high-value-added products via catalytic hydrogenation remains a substantial challenge. We developed a Pd–Fe bimetallic catalyst supported on oxygen vacancy (Ov)-enriched TiO2 for the direct cleavage of CO bonds, and as a result, up to 99% yield of 2-methoxy-4-methylphenol (MMP) was achieved from the conversion of vanillin (VAN) at 140 °C under atmospheric H2 pressure. This study utilizes Ov to enhance hydrogen spillover levels during the reaction process and proposes a novel reaction pathway that avoids the formation of alcohol intermediates. Mechanistic investigations reveal that surface Ov facilitates hydrogen spillover, enabling active hydrogen migration from Pd–Fe sites to TiO2 to form Ti–H species. Through synergistic Pd–Fe bimetallic effects and metal–support interfacial interactions, direct hydrodeoxygenation (HDO) of VAN is achieved, ultimately generating MMP with high selectivity. The catalyst demonstrates excellent stability and broad substrate suitability, maintaining uncompromised activity after five catalytic cycles.
{"title":"Oxygen vacancy-enhanced hydrogen spillover on a bifunctional PdFe/TiO2−x catalyst for highly selective direct hydrodeoxygenation of carbonyl compounds","authors":"Chaofan Deng, Chun Cai","doi":"10.1039/d5qi02432c","DOIUrl":"https://doi.org/10.1039/d5qi02432c","url":null,"abstract":"Achieving direct cleavage of C<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/>O bonds in biomass under mild conditions to generate high-value-added products <em>via</em> catalytic hydrogenation remains a substantial challenge. We developed a Pd–Fe bimetallic catalyst supported on oxygen vacancy (O<small><sub>v</sub></small>)-enriched TiO<small><sub>2</sub></small> for the direct cleavage of C<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/>O bonds, and as a result, up to 99% yield of 2-methoxy-4-methylphenol (MMP) was achieved from the conversion of vanillin (VAN) at 140 °C under atmospheric H<small><sub>2</sub></small> pressure. This study utilizes O<small><sub>v</sub></small> to enhance hydrogen spillover levels during the reaction process and proposes a novel reaction pathway that avoids the formation of alcohol intermediates. Mechanistic investigations reveal that surface O<small><sub>v</sub></small> facilitates hydrogen spillover, enabling active hydrogen migration from Pd–Fe sites to TiO<small><sub>2</sub></small> to form Ti–H species. Through synergistic Pd–Fe bimetallic effects and metal–support interfacial interactions, direct hydrodeoxygenation (HDO) of VAN is achieved, ultimately generating MMP with high selectivity. The catalyst demonstrates excellent stability and broad substrate suitability, maintaining uncompromised activity after five catalytic cycles.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"6 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116145","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}
The catalytic activation of CO 2 under mild conditions to form value-added heterocyclic products is of paramount interest.Copper sulfides are a large class of materials, many of which are found as minerals in nature. They often show remarkable physical properties, and further studies of their catalytic properties need to be conducted. The simple compound Cu 2 S was designed and its catalytic activities in CO 2 activation are disclosed here. Synthesized Cu 2 S is shown to be an efficient heterogeneous catalyst for the carboxylation of propargylamines under ambient temperature and pressure conditions and the carboxylation of terminal alkynes with one atm CO 2 at 80 °C. CO 2 is transformed into high-value-added chemicals with a wide range of substrates with excellent yields, and the catalyst is easily reused at least 5 times without significant activity reduction. The catalytic and recycling performances are significantly better for synthesized Cu 2 S compared to those of its commercial analogue. In summary, Cu 2 S is a new catalyst that is non-toxic, simple, self-supported, recyclable, and practical. This finding opens the general route to the catalytic properties of Cu 2 S toward, not only mild CO 2 activation applications, but also a variety of other useful reactions.
{"title":"CO 2 Conversion Efficiently Catalyzed under Ambient Conditions by Self-Supported and Recyclable Cu 2 S","authors":"Huili Wang, Tiansheng Wang, Murielle Berlande, Ahmed Subrati, Sergio Enrique Moya, Lionel Salmon, Nathalie Daro, Nathalie Audebrand, Jean-Rene Hamon, Haizhu Yu, Jean-Luc Pozzo, Didier Astruc","doi":"10.1039/d5qi02546j","DOIUrl":"https://doi.org/10.1039/d5qi02546j","url":null,"abstract":"The catalytic activation of CO 2 under mild conditions to form value-added heterocyclic products is of paramount interest.Copper sulfides are a large class of materials, many of which are found as minerals in nature. They often show remarkable physical properties, and further studies of their catalytic properties need to be conducted. The simple compound Cu 2 S was designed and its catalytic activities in CO 2 activation are disclosed here. Synthesized Cu 2 S is shown to be an efficient heterogeneous catalyst for the carboxylation of propargylamines under ambient temperature and pressure conditions and the carboxylation of terminal alkynes with one atm CO 2 at 80 °C. CO 2 is transformed into high-value-added chemicals with a wide range of substrates with excellent yields, and the catalyst is easily reused at least 5 times without significant activity reduction. The catalytic and recycling performances are significantly better for synthesized Cu 2 S compared to those of its commercial analogue. In summary, Cu 2 S is a new catalyst that is non-toxic, simple, self-supported, recyclable, and practical. This finding opens the general route to the catalytic properties of Cu 2 S toward, not only mild CO 2 activation applications, but also a variety of other useful reactions.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101496","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}
Pietro Mariani, Jacopo Orsilli, Henk Stoffel, Simone Mascotto, Damiano Monticelli, Enrico Berretti, Alessandro Lavacchi, Luca Bignardi, Cinzia Cepek, Maria Goula, Nikolaos Charisiou, Angeliki Latsiou, Silvia Mostoni, Barbara Di Credico, Roberto Scotti, Massimiliano D'Arienzo
In this work, we examine the redox behavior and exsolution kinetics of Ni and Fe in A-site-deficient Sr 0.95 Ti 1-x+y Fe x Ni y O 3±δ , combining TPR, XAS, electron microscopy and EPR to elucidate dopant-specific contributions to defect chemistry and metal nucleation. In particular, TPR data indicated that Fe predominantly governs the formation and reducibility of oxygen-vacancy-associated defects, generating reduced Fe species at comparatively low temperature, whereas Ni dictates the overall reduction extent. In fact, as assessed by XAS, Ni-only samples exhibit relatively low conversion to Ni (0), while co-doping with Fe boosts Ni exsolution. Moreover, it turned out that even a tiny Ni amount promotes iron reduction, as unveiled by EXAFS spectra. Along this line, STEM analyses confirmed the surface segregation of well-anchored Fe-Ni co-exsolved nanoparticles for co-doped perovskites, while scarce exsolution was observed for Fe-doped samples. EPR completed the picture corroborating that Fe species, incorporated in the perovskite as highly stable Fe(III) substitutional defects, are less reducible and less mobile than Ni ones, which instead appear mostly as intercalated sites. Such Fe defects become mobile and undergo surface segregation only when Ni is incorporated in the lattice. These structure-property relationships directly translate into enhanced performance in the RWGS reaction of co-doped perovskites, where Fe drives vacancy-mediated redox processes while Ni promotes H₂ dissociation. Overall, the results indicate that the methodological approach developed here can be extended to other exsolvable dopants (e.g., Co), offering a pathway toward the rational design of exsolved catalysts with tunable structures and compositions for advanced energy-conversion applications.
在这项工作中，我们研究了Ni和Fe在a位缺陷Sr 0.95 Ti 1-x+y Fe x Ni y O 3±δ中的氧化还原行为和析出动力学，结合TPR， XAS，电子显微镜和EPR来阐明掺杂剂对缺陷化学和金属成核的特异性贡献。特别是，TPR数据表明，Fe主要控制了氧空位相关缺陷的形成和还原性，在相对较低的温度下产生了还原铁，而Ni则决定了整体的还原程度。事实上，通过XAS评估，纯Ni样品向Ni(0)的转化相对较低，而与Fe共掺杂则促进了Ni的析出。此外，正如EXAFS光谱所揭示的那样，即使是微量的Ni也会促进铁的还原。沿着这条线，STEM分析证实了共掺杂钙钛矿的铁-镍共溶纳米颗粒的表面偏析，而铁掺杂样品的表面偏析很少。EPR完成了这幅图，证实了作为高度稳定的Fe（III）取代缺陷结合在钙钛矿中的Fe物种比Ni物种更不容易被还原和迁移，而Ni则主要作为插入位点出现。只有在晶格中加入Ni时，这些Fe缺陷才会移动并发生表面偏析。这些结构-性能关系直接转化为共掺杂钙钛矿在RWGS反应中的性能增强，其中Fe驱动空位介导的氧化还原过程，而Ni促进H₂解离。总的来说，结果表明，这里开发的方法方法可以扩展到其他可溶掺杂剂（例如Co），为合理设计具有可调结构和成分的可溶催化剂提供了一条途径，用于先进的能量转换应用。
{"title":"Bimetallic Fe-Ni exsolution from A site deficient SrTiO3: insight into the reciprocal role of metal active centers","authors":"Pietro Mariani, Jacopo Orsilli, Henk Stoffel, Simone Mascotto, Damiano Monticelli, Enrico Berretti, Alessandro Lavacchi, Luca Bignardi, Cinzia Cepek, Maria Goula, Nikolaos Charisiou, Angeliki Latsiou, Silvia Mostoni, Barbara Di Credico, Roberto Scotti, Massimiliano D'Arienzo","doi":"10.1039/d5qi02469b","DOIUrl":"https://doi.org/10.1039/d5qi02469b","url":null,"abstract":"In this work, we examine the redox behavior and exsolution kinetics of Ni and Fe in A-site-deficient Sr 0.95 Ti 1-x+y Fe x Ni y O 3±δ , combining TPR, XAS, electron microscopy and EPR to elucidate dopant-specific contributions to defect chemistry and metal nucleation. In particular, TPR data indicated that Fe predominantly governs the formation and reducibility of oxygen-vacancy-associated defects, generating reduced Fe species at comparatively low temperature, whereas Ni dictates the overall reduction extent. In fact, as assessed by XAS, Ni-only samples exhibit relatively low conversion to Ni (0), while co-doping with Fe boosts Ni exsolution. Moreover, it turned out that even a tiny Ni amount promotes iron reduction, as unveiled by EXAFS spectra. Along this line, STEM analyses confirmed the surface segregation of well-anchored Fe-Ni co-exsolved nanoparticles for co-doped perovskites, while scarce exsolution was observed for Fe-doped samples. EPR completed the picture corroborating that Fe species, incorporated in the perovskite as highly stable Fe(III) substitutional defects, are less reducible and less mobile than Ni ones, which instead appear mostly as intercalated sites. Such Fe defects become mobile and undergo surface segregation only when Ni is incorporated in the lattice. These structure-property relationships directly translate into enhanced performance in the RWGS reaction of co-doped perovskites, where Fe drives vacancy-mediated redox processes while Ni promotes H₂ dissociation. Overall, the results indicate that the methodological approach developed here can be extended to other exsolvable dopants (e.g., Co), offering a pathway toward the rational design of exsolved catalysts with tunable structures and compositions for advanced energy-conversion applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"280 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116122","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}
Deyue Cao, Bowen Zheng, Ningjie Xu, Xin Wang, Gen Luo
Although rare-earth-catalysed C-H addition to unsaturated hydrocarbons has emerged as a powerful and atom-economical strategy, the mechanistic principles governing selectivity in reactions involving conjugated dienes remain poorly understood. Here, density functional theory (DFT) calculations are employed to elucidate the mechanistic origins of divergent selectivity in rare-earth-catalysed pyridine C-H alkylation and aldimine annulation reactions with conjugated dienes. The results indicate that, despite producing formal 1,4-and 1,2-insertion products, respectively, both transformations proceed through a preferred 1,4-cis-insertion pathway to generate η3 -allyl intermediates. Comprehensive computational analyses reveal that the divergence arises from distinct post-insertion pathways: sterically favored protonation at the terminal carbon in pyridine alkylation, versus electronically and sterically driven cyclization at the internal carbon in aldimine annulation. These results demonstrate that product selectivity is dictated primarily by the site-selective evolution of the η3 -allyl intermediate rather than by the initial insertion event. This work establishes a unified mechanistic framework for diene-enabled rare-earthcatalysed C-H functionalization and provides theoretical insights into selectivity control through post-insertion reactivity.
{"title":"Insertion Modes and Origins of Product Selectivity in Rare-Earth-Catalysed C-H Functionalization with Conjugated Dienes","authors":"Deyue Cao, Bowen Zheng, Ningjie Xu, Xin Wang, Gen Luo","doi":"10.1039/d6qi00049e","DOIUrl":"https://doi.org/10.1039/d6qi00049e","url":null,"abstract":"Although rare-earth-catalysed C-H addition to unsaturated hydrocarbons has emerged as a powerful and atom-economical strategy, the mechanistic principles governing selectivity in reactions involving conjugated dienes remain poorly understood. Here, density functional theory (DFT) calculations are employed to elucidate the mechanistic origins of divergent selectivity in rare-earth-catalysed pyridine C-H alkylation and aldimine annulation reactions with conjugated dienes. The results indicate that, despite producing formal 1,4-and 1,2-insertion products, respectively, both transformations proceed through a preferred 1,4-cis-insertion pathway to generate η3 -allyl intermediates. Comprehensive computational analyses reveal that the divergence arises from distinct post-insertion pathways: sterically favored protonation at the terminal carbon in pyridine alkylation, versus electronically and sterically driven cyclization at the internal carbon in aldimine annulation. These results demonstrate that product selectivity is dictated primarily by the site-selective evolution of the η3 -allyl intermediate rather than by the initial insertion event. This work establishes a unified mechanistic framework for diene-enabled rare-earthcatalysed C-H functionalization and provides theoretical insights into selectivity control through post-insertion reactivity.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"236 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116123","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}
The rational design of high-performance visible-light-responsive and recyclable C-H bond activation photocatalysts represents one of the critical challenges for advancing sustainable photocatalytic chemistry. Here, we successfully obtained a novel crystalline material (CR-DT) through the self-assembly of decatungstate (DT) with Ru metalloligands, which represents the first example of the crystalline polyoxometalate@metal-organic frameworks incorporating DT with photosensitive metalloligands. CR-DT not only retains the HAT function of DT but also overcomes its limitations of effectiveness only in the ultraviolet light region and difficulty in reuse, further enhancing photocatalytic performance. When CR-DT was employed as the photocatalyst for the Baeyer-Villiger oxidation reaction, the catalytic generation of εcaprolactone was achieved in yields up to 99.5%, with TON and TOF of 995 and 678 h -1 , respectively, both of which were the highest among the photocatalysts currently used for this reaction. Remarkably, CR-DT exhibited excellent recyclability, maintained high yield even after ten cycles, providing a viable candidate for industrial applications. Recently, metal-organic frameworks (MOFs) have emerged as a distinctive class of materials with well-defined structures, large porosity, and customizable functions, which have established MOFs as a versatile platform for directional construction of high-performance photocatalysts through precise spatial organization of active sites. [23][24][25][26] Choosing a suitable secondary building unit serves as an essential strategy for achieving precise functional customization of MOFs. 27,28 The DT module with HAT
合理设计高性能可见光响应和可回收的C-H键活化光催化剂是推进可持续光催化化学的关键挑战之一。在这里，我们成功地通过十钨酸盐（DT）与Ru金属配体的自组装获得了一种新的晶体材料（CR-DT），这是将DT与光敏金属配体结合在一起的晶体polyoxometalate@metal-organic框架的第一个例子。CR-DT既保留了DT的HAT功能，又克服了其仅在紫外光区有效和难以重复使用的局限性，进一步提高了光催化性能。采用CR-DT作为Baeyer-Villiger氧化反应的光催化剂，催化生成ε己内酯的产率高达99.5%，TON和TOF分别为995和678 h -1，是目前用于该反应的光催化剂中最高的。值得注意的是，CR-DT表现出优异的可回收性，即使在10次循环后仍保持高收率，为工业应用提供了可行的候选材料。近年来，金属有机框架（mof）作为一种具有明确结构、大孔隙率和可定制功能的独特材料而出现，这使得mof成为通过精确的活性位点空间组织定向构建高性能光催化剂的通用平台。选择合适的二次建筑单元是实现mof精确功能定制的基本策略。27,28带有HAT的DT模块
{"title":"Upgraded Decatungstate: The Visible-Light-Responsive, Recyclable, and Efficient Photocatalyst Achieved via Self-Assembly","authors":"Yanan Liu, Luoning Li, Minzhen Cai, Jingping Wang, Jing Wang, Pengtao Ma, Jingyang Niu","doi":"10.1039/d5qi02558c","DOIUrl":"https://doi.org/10.1039/d5qi02558c","url":null,"abstract":"The rational design of high-performance visible-light-responsive and recyclable C-H bond activation photocatalysts represents one of the critical challenges for advancing sustainable photocatalytic chemistry. Here, we successfully obtained a novel crystalline material (CR-DT) through the self-assembly of decatungstate (DT) with Ru metalloligands, which represents the first example of the crystalline polyoxometalate@metal-organic frameworks incorporating DT with photosensitive metalloligands. CR-DT not only retains the HAT function of DT but also overcomes its limitations of effectiveness only in the ultraviolet light region and difficulty in reuse, further enhancing photocatalytic performance. When CR-DT was employed as the photocatalyst for the Baeyer-Villiger oxidation reaction, the catalytic generation of εcaprolactone was achieved in yields up to 99.5%, with TON and TOF of 995 and 678 h -1 , respectively, both of which were the highest among the photocatalysts currently used for this reaction. Remarkably, CR-DT exhibited excellent recyclability, maintained high yield even after ten cycles, providing a viable candidate for industrial applications. Recently, metal-organic frameworks (MOFs) have emerged as a distinctive class of materials with well-defined structures, large porosity, and customizable functions, which have established MOFs as a versatile platform for directional construction of high-performance photocatalysts through precise spatial organization of active sites. [23][24][25][26] Choosing a suitable secondary building unit serves as an essential strategy for achieving precise functional customization of MOFs. 27,28 The DT module with HAT","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"96 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101499","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}
Tatyana S. Koptseva, Evgeny V. Baranov, Sergey Yu. Ketkov, Igor L. Fedushkin
The reaction of aluminum hydride [(ArBIG-bian)AlH2]−[Li(THF)4]+ (1) (ArBIG-bian = dianion of 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene) with TM(CO)6 yields σ-complexes [(ArBIG-bian)Al(μ2-H)2TM(CO)4]−[Li(Solv)3]+ (TM = Cr, 2; Mo, 3; W, 4), in which two hydride ligands symmetrically bridge the Al and TM centers. Molybdenum hydride [(ArBIG-bian)Al(μ2-H)2Mo(CO)4Li(THF)3] 3b reacts with ammonia through H2 elimination to form an amido-bridged derivative [(ArBIG-bian)Al(μ2-NH2)2Mo(CO)4]−[Li(THF)4]+ (5). In contrast, the reactions of hydride 1 with Cp2Ni and Cp3Er (Cp = C5H5) afford a unique Ni(II)(μ2-H)2Al(III) complex [(ArBIG-bian)(THF)Al(μ2-H)2NiCp] (6) and dihydride [(ArBIG-bian)Al(μ2-H)2Er(Cp)2THF] (7), respectively. The latter represents the first crystallographically characterized Er/Al complex. Products 2–7 have been identified via IR and NMR spectroscopy, and their molecular structures were determined via single-crystal X-ray analysis. The electronic structures of 2, 3 and 6 were examined via DFT calculations, which revealed direct Al–TM bonding.
{"title":"Plural bonding interactions in Al(μ2-H)2TM species","authors":"Tatyana S. Koptseva, Evgeny V. Baranov, Sergey Yu. Ketkov, Igor L. Fedushkin","doi":"10.1039/d5qi02383a","DOIUrl":"https://doi.org/10.1039/d5qi02383a","url":null,"abstract":"The reaction of aluminum hydride [(Ar<small><sup>BIG</sup></small>-bian)AlH<small><sub>2</sub></small>]<small><sup>−</sup></small>[Li(THF)<small><sub>4</sub></small>]<small><sup>+</sup></small> (<strong>1</strong>) (Ar<small><sup>BIG</sup></small>-bian = dianion of 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene) with TM(CO)<small><sub>6</sub></small> yields σ-complexes [(Ar<small><sup>BIG</sup></small>-bian)Al(μ<small><sup>2</sup></small>-H)<small><sub>2</sub></small>TM(CO)<small><sub>4</sub></small>]<small><sup>−</sup></small>[Li(Solv)<small><sub>3</sub></small>]<small><sup>+</sup></small> (TM = Cr, <strong>2</strong>; Mo, <strong>3</strong>; W, <strong>4</strong>), in which two hydride ligands symmetrically bridge the Al and TM centers. Molybdenum hydride [(Ar<small><sup>BIG</sup></small>-bian)Al(μ<small><sup>2</sup></small>-H)<small><sub>2</sub></small>Mo(CO)<small><sub>4</sub></small>Li(THF)<small><sub>3</sub></small>] <strong>3b</strong> reacts with ammonia through H<small><sub>2</sub></small> elimination to form an amido-bridged derivative [(Ar<small><sup>BIG</sup></small>-bian)Al(μ<small><sup>2</sup></small>-NH<small><sub>2</sub></small>)<small><sub>2</sub></small>Mo(CO)<small><sub>4</sub></small>]<small><sup>−</sup></small>[Li(THF)<small><sub>4</sub></small>]<small><sup>+</sup></small> (<strong>5</strong>). In contrast, the reactions of hydride <strong>1</strong> with Cp<small><sub>2</sub></small>Ni and Cp<small><sub>3</sub></small>Er (Cp = C<small><sub>5</sub></small>H<small><sub>5</sub></small>) afford a unique Ni(<small>II</small>)(μ<small><sup>2</sup></small>-H)<small><sub>2</sub></small>Al(<small>III</small>) complex [(Ar<small><sup>BIG</sup></small>-bian)(THF)Al(μ<small><sup>2</sup></small>-H)<small><sub>2</sub></small>NiCp] (<strong>6</strong>) and dihydride [(Ar<small><sup>BIG</sup></small>-bian)Al(μ<small><sup>2</sup></small>-H)<small><sub>2</sub></small>Er(Cp)<small><sub>2</sub></small>THF] (<strong>7</strong>), respectively. The latter represents the first crystallographically characterized Er/Al complex. Products <strong>2–7</strong> have been identified <em>via</em> IR and NMR spectroscopy, and their molecular structures were determined <em>via</em> single-crystal X-ray analysis. The electronic structures of <strong>2</strong>, <strong>3</strong> and <strong>6</strong> were examined <em>via</em> DFT calculations, which revealed direct Al–TM bonding.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"41 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101498","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}
Laura Cuevas, María Mar Quesada-Moreno, Estibaliz Ruiz-Bilbao, Juan Manuel Gutierrez-Zorrilla, Jurek Krzystek, Mykhaylo Ozerov, Juan Ramón Jiménez, Enrique Colacio
This work reports on a mononuclear trigonal prismatic complex [CoIIL](ClO4)2 (1) and a trinuclear linear phenoxido-bridged complex [(CoIIL1)2CoII] (2), where L and H3L1 are N6 and N3O3 tripodal ligands derived from the respective condensation of the cis, cis-1,3,5-tiaminocyclohexane with either 1-methylimidazol-2-carbaldehyde or salicylaldehyde. These compounds have been studied by X-ray single-crystal diffraction, dc and ac magnetism, High-Frequency and -Field Electron Paramagnetic Resonance spectroscopy (HFEPR), Far Infrared Magnetic Spectroscopy (FIRMS) and quantum chemical calculations. The results obtained for 1 show that N₆-tripodal Schiff-base ligands incorporating 1-methylimidazole donors yield trigonal-prismatic mononuclear complexes that typically display C₃ symmetry and exhibit very large, purely easy-axis magnetic anisotropy. In fact, complex 1 exhibits an energy gap between the ground and the first excited state (2D) of 228 cm-1 (directly measured by FIRMS), that can be considered as the maximum limit for the easy magnetic anisotropy in this type of complexes. The symmetry-driven large 2D value, together with the parallel alignment of the anisotropy axes, reduces QTM (Quantum Tunnelling of Magnetization) and yields mononuclear single-molecule magnet (MSMM) behaviour, with the observation of magnetic relaxation through a Raman process and open hysteresis at zero field. In compound 2, the combination of the strong easy-axis anisotropy of the local CoII ions, collinearity of the local anisotropy axes and sizable intramolecular magnetic exchange interactions between the CoII ions in triple phenoxido-bridged linear trinuclear complexes causes the full quenching to the QTM and the observation of SMM behaviour with open hysteresis at zero field. Theoretical calculations point out that the magnetic interaction between the ground Kramers doublets (KDs) of the local CoII ions generates four KDs and the magnetic relaxation occurs through the first excited KD via an Orbach process. Supporting this suggestion, the experimental value for the effective thermal energy barrier extracted from FIRMS of 76.8 cm-1is not too far from the theoretical calculated value of 59.54 cm-1.
{"title":"Symmetry control and magnetic exchange coupling in SMMs based on Co(II) complexes","authors":"Laura Cuevas, María Mar Quesada-Moreno, Estibaliz Ruiz-Bilbao, Juan Manuel Gutierrez-Zorrilla, Jurek Krzystek, Mykhaylo Ozerov, Juan Ramón Jiménez, Enrique Colacio","doi":"10.1039/d5qi02196k","DOIUrl":"https://doi.org/10.1039/d5qi02196k","url":null,"abstract":"This work reports on a mononuclear trigonal prismatic complex [CoIIL](ClO4)2 (1) and a trinuclear linear phenoxido-bridged complex [(CoIIL1)2CoII] (2), where L and H3L1 are N6 and N3O3 tripodal ligands derived from the respective condensation of the cis, cis-1,3,5-tiaminocyclohexane with either 1-methylimidazol-2-carbaldehyde or salicylaldehyde. These compounds have been studied by X-ray single-crystal diffraction, dc and ac magnetism, High-Frequency and -Field Electron Paramagnetic Resonance spectroscopy (HFEPR), Far Infrared Magnetic Spectroscopy (FIRMS) and quantum chemical calculations. The results obtained for 1 show that N₆-tripodal Schiff-base ligands incorporating 1-methylimidazole donors yield trigonal-prismatic mononuclear complexes that typically display C₃ symmetry and exhibit very large, purely easy-axis magnetic anisotropy. In fact, complex 1 exhibits an energy gap between the ground and the first excited state (2D) of 228 cm-1 (directly measured by FIRMS), that can be considered as the maximum limit for the easy magnetic anisotropy in this type of complexes. The symmetry-driven large 2D value, together with the parallel alignment of the anisotropy axes, reduces QTM (Quantum Tunnelling of Magnetization) and yields mononuclear single-molecule magnet (MSMM) behaviour, with the observation of magnetic relaxation through a Raman process and open hysteresis at zero field. In compound 2, the combination of the strong easy-axis anisotropy of the local CoII ions, collinearity of the local anisotropy axes and sizable intramolecular magnetic exchange interactions between the CoII ions in triple phenoxido-bridged linear trinuclear complexes causes the full quenching to the QTM and the observation of SMM behaviour with open hysteresis at zero field. Theoretical calculations point out that the magnetic interaction between the ground Kramers doublets (KDs) of the local CoII ions generates four KDs and the magnetic relaxation occurs through the first excited KD via an Orbach process. Supporting this suggestion, the experimental value for the effective thermal energy barrier extracted from FIRMS of 76.8 cm-1is not too far from the theoretical calculated value of 59.54 cm-1.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"89 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101505","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}
Maria-Gabriela Alexandru, Diana Visinescu, Sergiu Shova, Fernando Nicolás Moliner, Mario Pacheco, Francesc Lloret
An isostructural series of neutral cyano-bridged tetranuclear iron(III)-lanthanide(III) complexes of general formula {[Fe(htpzb)(CN)(μ-CN)2]2[Ln(dmbpy)(NO3)2(H2O)]2}·2CH3CN·2H2O [Ln = Gd (1), Tb (2), Dy (3), Ho (4), and Er (5); htpzb = hydrotris(pyrazolyl)borate and dmbpy = 4,4’-dimethyl-2,2’-bipyridine] was synthesized and structurally and magnetically characterized. Single-crystal X-ray analysis of 1-5 revealed the formation of neutral cyano-bridged {FeIII2LnIII2} complexes (Ln = Gd, Tb, Dy, Ho, and Er) of square-like topology that crystallize in the triclinic P-1 space group. Solid-state direct-current magnetic susceptibility analysis evidenced weak intramolecular antiferromagnetic FeIII-LnIII interactions in 1 (Ln = Gd) together with large local magnetic anisotropies from the LnIII ion in 2-5 (Ln = Tb, Dy, Ho, and Er). Frequency-dependent alternating current magnetic susceptibility signals occurred for 1-5 under an applied dc magnetic field of H = 1.0 (1) or 0.5 T (2-5), indicating field-induced slow magnetic relaxation effects typical of single-molecule magnets. Depending on the non-Kramer (Tb, Ho) or Kramer (Gd, Dy, Er) nature of the LnIII ion, a single magnetic relaxation process via Orbach or Raman mechanism (2 and 4) or a multiple magnetic relaxation process that combines Orbach or Raman plus quantum tunneling of magnetization and/or direct (1, 3, and 5) mechanisms occurred along this series. 1-5 showed large magnetocaloric effects with a high to moderate maximum value of the magnetic entropy change at optimum working temperatures just above He liquefaction [-ΔSmax = 16.51 (1), 5.42 (2), 6.02 (3), 4.56 (4), and 5.86 J kg-1 K-1 (5) for H = 5 T at Topt = Tmax = 2 (1), 4 (2, 3 and 5), and 6 K (4)], as well as a high to moderate magnetocaloric index at rather low optimum working fields [MCI = 6.4 (1), 3.3 (2), 4.7 (3), 0.9 (4), and 3.6 J kg−1 K−1 T−1 (5) for Hopt = Hmax = 1.0 (1), 0.6 (2), 0.4 (3), 0.8 (4), and 0.6 T (5) at T = 2 K].
{"title":"Cyano-bridged {LnIII 2 Fe III 2 } molecular squares (Ln = Gd, Tb, Dy, Ho, and Er): tuning the slow magnetic relaxation and magnetocaloric effects in zero-dimensional lanthanide Prussian blue analogues","authors":"Maria-Gabriela Alexandru, Diana Visinescu, Sergiu Shova, Fernando Nicolás Moliner, Mario Pacheco, Francesc Lloret","doi":"10.1039/d5qi02520f","DOIUrl":"https://doi.org/10.1039/d5qi02520f","url":null,"abstract":"An isostructural series of neutral cyano-bridged tetranuclear iron(III)-lanthanide(III) complexes of general formula {[Fe(htpzb)(CN)(μ-CN)2]2[Ln(dmbpy)(NO3<small><sub></sub></small>)2<small><sub></sub></small>(H2<small><sub></sub></small>O)]2<small><sub></sub></small>}·2CH3<small><sub></sub></small>CN·2H2<small><sub></sub></small>O [Ln = Gd (1), Tb (2), Dy (3), Ho (4), and Er (5); htpzb = hydrotris(pyrazolyl)borate and dmbpy = 4,4’-dimethyl-2,2’-bipyridine] was synthesized and structurally and magnetically characterized. Single-crystal X-ray analysis of 1-5 revealed the formation of neutral cyano-bridged {FeIII<small><sup></sup></small>2<small><sub></sub></small>LnIII<small><sup></sup></small>2<small><sub></sub></small>} complexes (Ln = Gd, Tb, Dy, Ho, and Er) of square-like topology that crystallize in the triclinic P-1 space group. Solid-state direct-current magnetic susceptibility analysis evidenced weak intramolecular antiferromagnetic FeIII<small><sup></sup></small>-LnIII<small><sup></sup></small> interactions in 1 (Ln = Gd) together with large local magnetic anisotropies from the LnIII<small><sup></sup></small> ion in 2-5 (Ln = Tb, Dy, Ho, and Er). Frequency-dependent alternating current magnetic susceptibility signals occurred for 1-5 under an applied dc magnetic field of H = 1.0 (1) or 0.5 T (2-5), indicating field-induced slow magnetic relaxation effects typical of single-molecule magnets. Depending on the non-Kramer (Tb, Ho) or Kramer (Gd, Dy, Er) nature of the LnIII<small><sup></sup></small> ion, a single magnetic relaxation process via Orbach or Raman mechanism (2 and 4) or a multiple magnetic relaxation process that combines Orbach or Raman plus quantum tunneling of magnetization and/or direct (1, 3, and 5) mechanisms occurred along this series. 1-5 showed large magnetocaloric effects with a high to moderate maximum value of the magnetic entropy change at optimum working temperatures just above He liquefaction [-ΔSmax<small><sub></sub></small> = 16.51 (1), 5.42 (2), 6.02 (3), 4.56 (4), and 5.86 J kg-1<small><sup></sup></small> K-1<small><sup></sup></small> (5) for H = 5 T at Topt<small><sub></sub></small> = Tmax<small><sub></sub></small> = 2 (1), 4 (2, 3 and 5), and 6 K (4)], as well as a high to moderate magnetocaloric index at rather low optimum working fields [MCI = 6.4 (1), 3.3 (2), 4.7 (3), 0.9 (4), and 3.6 J kg−1<small><sup></sup></small> K−1<small><sup></sup></small> T−1<small><sup></sup></small> (5) for Hopt <small><sub></sub></small>= Hmax<small><sub></sub></small> = 1.0 (1), 0.6 (2), 0.4 (3), 0.8 (4), and 0.6 T (5) at T = 2 K].","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"105 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116126","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}
![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
O bonds in biomass under mild conditions to generate high-value-added products via catalytic hydrogenation remains a substantial challenge. We developed a Pd–Fe bimetallic catalyst supported on oxygen vacancy (Ov)-enriched TiO2 for the direct cleavage of C
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