Muhammad Zulqarnain,Wei Zheng,Oleg I. Lebedev,John F Berry,Marcell Hollo,Kathleen A. Dunn,Evgeny V. Dikarev
Cation-distribution engineering enabled by a molecular single-source precursor approach provides atomic-level control over stoichiometry and site occupancy, allowing access to a normal-spinel CoFe2O4 phase that has previously been overlooked as a high-performance oxygen evolution reaction (OER) catalyst. Controlled thermal decomposition of the heterometallic precursor produces phase-pure CoFe2O4 nanoparticles (5–10 nm) with tunable cation distribution between tetrahedral and octahedral sites. At lower synthetic temperatures, the catalyst preferentially adopts a normal-spinel configuration, as confirmed by the 57Fe Mössbauer spectroscopy. This cation arrangement promotes favorable electronic coupling, accelerates charge transfer, and results in a large electrochemically active surface area. Consequently, the material exhibits an overpotential of only 72 mV at 10 mA·cm-2 in alkaline media, along with markedly reduced charge-transfer resistance, outperforming all previously reported spinel-based OER catalysts. The catalyst maintains stable operation for 600 h at current densities of up to 50 mA·cm-2 without measurable degradation or metal leaching. Temperature-dependent studies directly correlate the enhanced activity and durability with cation distribution rather than thermal sintering effects. These findings establish normal-spinel CoFe2O4 as a promising benchmark within the family of spinel OER electrocatalysts and highlight low-temperature molecular precursor strategies as an effective approach for designing intrinsically active and durable earth-abundant OER materials.
{"title":"Cation-Distribution Engineering for High-Performance Noble Metal-Free Electrochemical Water Oxidation","authors":"Muhammad Zulqarnain,Wei Zheng,Oleg I. Lebedev,John F Berry,Marcell Hollo,Kathleen A. Dunn,Evgeny V. Dikarev","doi":"10.1039/d6qi01943a","DOIUrl":"https://doi.org/10.1039/d6qi01943a","url":null,"abstract":"Cation-distribution engineering enabled by a molecular single-source precursor approach provides atomic-level control over stoichiometry and site occupancy, allowing access to a normal-spinel CoFe2O4 phase that has previously been overlooked as a high-performance oxygen evolution reaction (OER) catalyst. Controlled thermal decomposition of the heterometallic precursor produces phase-pure CoFe2O4 nanoparticles (5–10 nm) with tunable cation distribution between tetrahedral and octahedral sites. At lower synthetic temperatures, the catalyst preferentially adopts a normal-spinel configuration, as confirmed by the 57Fe Mössbauer spectroscopy. This cation arrangement promotes favorable electronic coupling, accelerates charge transfer, and results in a large electrochemically active surface area. Consequently, the material exhibits an overpotential of only 72 mV at 10 mA·cm-2 in alkaline media, along with markedly reduced charge-transfer resistance, outperforming all previously reported spinel-based OER catalysts. The catalyst maintains stable operation for 600 h at current densities of up to 50 mA·cm-2 without measurable degradation or metal leaching. Temperature-dependent studies directly correlate the enhanced activity and durability with cation distribution rather than thermal sintering effects. These findings establish normal-spinel CoFe2O4 as a promising benchmark within the family of spinel OER electrocatalysts and highlight low-temperature molecular precursor strategies as an effective approach for designing intrinsically active and durable earth-abundant OER materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"150 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148915223","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}
Halide lead-based perovskite photovoltaics have recently demonstrated exceptional progress, achieving certified power conversion efficiencies above 27% that closely approach the Shockley-Queisser (S-Q) theoretical limit for single-junction solar cells. The development of all-perovskite tandem solar cells integrating wide-bandgap (WBG) lead-based perovskite and mixed tin-lead (Sn-Pb) narrow-bandgap (NBG) perovskite subcells offers a promising strategy to overcome this efficiency limitation. Despite considerable progress, Sn-Pb perovskite solar cells (PSCs) still exhibit a lower power conversion efficiency (PCE) compared to lead-based cells, where substantial open-circuit voltage (VOC) losses are recognized as a major factor limiting further advancement. To address this, the review first outlines the fundamental structural constituents, optoelectronic properties and application scenarios of Sn-Pb perovskite, examines their structure-performance-loss relationships, and culminates in an exploration of the underlying origin and mechanisms of the voltage loss. Furthermore, it highlights the recent advances in mitigating voltage loss of Sn-Pb PSCs, including additive engineering, solvent regulation, interface optimization, and hole-selective contacts. Finally, we discuss the prevailing challenges and future perspectives for improving the performance and stability of Sn-Pb PSCs and all-perovskite tandem solar cells, thereby providing insights for overcoming the barriers to their commercialization.
{"title":"Understanding and Mitigating the Voltage Loss in Tin-Lead Perovskite Solar Cells","authors":"Chunli Xiang,Xiangxi Chen,Xing Zhou,Minhang Liu,Jin Zhao,Qiang Zhou,Xiaojun Li,Hongquan Zhao,Xingzhu Wang,Weichuan Zhang","doi":"10.1039/d6qi01356b","DOIUrl":"https://doi.org/10.1039/d6qi01356b","url":null,"abstract":"Halide lead-based perovskite photovoltaics have recently demonstrated exceptional progress, achieving certified power conversion efficiencies above 27% that closely approach the Shockley-Queisser (S-Q) theoretical limit for single-junction solar cells. The development of all-perovskite tandem solar cells integrating wide-bandgap (WBG) lead-based perovskite and mixed tin-lead (Sn-Pb) narrow-bandgap (NBG) perovskite subcells offers a promising strategy to overcome this efficiency limitation. Despite considerable progress, Sn-Pb perovskite solar cells (PSCs) still exhibit a lower power conversion efficiency (PCE) compared to lead-based cells, where substantial open-circuit voltage (VOC) losses are recognized as a major factor limiting further advancement. To address this, the review first outlines the fundamental structural constituents, optoelectronic properties and application scenarios of Sn-Pb perovskite, examines their structure-performance-loss relationships, and culminates in an exploration of the underlying origin and mechanisms of the voltage loss. Furthermore, it highlights the recent advances in mitigating voltage loss of Sn-Pb PSCs, including additive engineering, solvent regulation, interface optimization, and hole-selective contacts. Finally, we discuss the prevailing challenges and future perspectives for improving the performance and stability of Sn-Pb PSCs and all-perovskite tandem solar cells, thereby providing insights for overcoming the barriers to their commercialization.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"51 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148915224","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}
Ge Gao,Yujie Zhou,Yaxin Wang,Zhuoya Ma,XinCheng Wang,Peixiao Jiang,Jian Zhao,Zhuohao Jiao,Jing Wang,Yuheng Liu
C–N bond formation plays a central role in the construction of nitrogen-containing heterocycles, many of which are privileged structural motifs in antibacterial agents. However, the development of efficient, mild, and recyclable catalytic systems for the synthesis of antibacterial benzothiazole derivatives remains an important challenge. To solve these issues, we rationally designed and constructed a novel Cu-based metal-hydrogen-bonded organic framework (Cu-MHOF) as an efficient and recyclable heterogeneous catalyst for the synthesis of 2-aminophenyl benzothiazoles through C–N coupling. Benefiting from the well-dispersed Cu sites and porous framework structure, the Cu-MHOF enables efficient C–N coupling under mild conditions, affording diverse 2-aminophenyl benzothiazoles in good yields with a broad substrate scope, good functional-group tolerance, and excellent recyclability. Mechanistic studies and DFT calculations further reveal the important role of the accessible Cu sites in substrate activation and C–N bond formation. Recycling experiments, PXRD analysis, and structural characterization further confirm the robustness of the catalyst. Importantly, we further evaluated the antibacterial application of the synthesized benzothiazole derivatives, and selected compounds exhibited antibacterial and antibiofilm activities against Staphylococcus aureus with favorable biocompatibility. This work provides a mild, efficient, and recyclable catalytic strategy for the synthesis of antibacterial benzothiazoles and highlights the value of Cu-MHOFs in bioactive heterocycle construction.
{"title":"A [Cu] cluster-based metal-hydrogen-bonded organic framework for efficient C–N coupling toward antibacterial benzothiazoles","authors":"Ge Gao,Yujie Zhou,Yaxin Wang,Zhuoya Ma,XinCheng Wang,Peixiao Jiang,Jian Zhao,Zhuohao Jiao,Jing Wang,Yuheng Liu","doi":"10.1039/d6qi01181k","DOIUrl":"https://doi.org/10.1039/d6qi01181k","url":null,"abstract":"C–N bond formation plays a central role in the construction of nitrogen-containing heterocycles, many of which are privileged structural motifs in antibacterial agents. However, the development of efficient, mild, and recyclable catalytic systems for the synthesis of antibacterial benzothiazole derivatives remains an important challenge. To solve these issues, we rationally designed and constructed a novel Cu-based metal-hydrogen-bonded organic framework (Cu-MHOF) as an efficient and recyclable heterogeneous catalyst for the synthesis of 2-aminophenyl benzothiazoles through C–N coupling. Benefiting from the well-dispersed Cu sites and porous framework structure, the Cu-MHOF enables efficient C–N coupling under mild conditions, affording diverse 2-aminophenyl benzothiazoles in good yields with a broad substrate scope, good functional-group tolerance, and excellent recyclability. Mechanistic studies and DFT calculations further reveal the important role of the accessible Cu sites in substrate activation and C–N bond formation. Recycling experiments, PXRD analysis, and structural characterization further confirm the robustness of the catalyst. Importantly, we further evaluated the antibacterial application of the synthesized benzothiazole derivatives, and selected compounds exhibited antibacterial and antibiofilm activities against Staphylococcus aureus with favorable biocompatibility. This work provides a mild, efficient, and recyclable catalytic strategy for the synthesis of antibacterial benzothiazoles and highlights the value of Cu-MHOFs in bioactive heterocycle construction.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"32 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148915227","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}
Recent progress in computational methods applied to the justification or prediction of zeolite phases under silica and aluminosilicate composition using organic structure directing agents (OSDAs) is reviewed. Using synthesis energy as descriptor of stability, it was found that zeolites become more stable as the aluminum content increases, and that the preferential order of incorporation of anions is [AlO4]− > F− > SiO−/SiOH. The calculated preference of AEI and CHA as aluminosilicate stable phases over a wide range of OSDAs tested is now explained using the new d escriptor called packing energy, which allows to quantify the role of Si/Al ratio and demonstrate its dominant role over van der Waals zeolite-OSDA interactions in order to predict the most stable zeolite phase. Packing energies however, are less accurate than synthesis energies, and in the current implementation can not take into account the roles of defects and fluoride anions and can only be applied for [AlO4]− as compensation of the OSDA charge.
{"title":"Tuning Zeolite Phase Selection Through Framework Aluminum Content: Insights from Computational and Experimental Studies","authors":"German Sastre","doi":"10.1039/d6qi01826b","DOIUrl":"https://doi.org/10.1039/d6qi01826b","url":null,"abstract":"Recent progress in computational methods applied to the justification or prediction of zeolite phases under silica and aluminosilicate composition using organic structure directing agents (OSDAs) is reviewed. Using synthesis energy as descriptor of stability, it was found that zeolites become more stable as the aluminum content increases, and that the preferential order of incorporation of anions is [AlO4]− > F− > SiO−/SiOH. The calculated preference of AEI and CHA as aluminosilicate stable phases over a wide range of OSDAs tested is now explained using the new d escriptor called packing energy, which allows to quantify the role of Si/Al ratio and demonstrate its dominant role over van der Waals zeolite-OSDA interactions in order to predict the most stable zeolite phase. Packing energies however, are less accurate than synthesis energies, and in the current implementation can not take into account the roles of defects and fluoride anions and can only be applied for [AlO4]− as compensation of the OSDA charge.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"164 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148909063","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}
Shuo Liu,Hongshuo Yang,Yang Zhang,Liming Zhang,Jian Lu,Qingrong Kong,Zhi Su
Lithium-ion batteries generally provide a service life of about five to eight years. With the continuous growth of the global battery market, the number of spent batteries produced has increased sharply. The disposal of spent batteries causes not only environmental pollution but also serious resource waste, with cathode materials representing the most valuable component in lithium-ion battery recycling. This study mainly investigates the regeneration and reutilization of spent lithium manganese oxide (LiMn2O4, LMO) cathode materials. During regeneration, oxygen defects are introduced into the LMO structure, enabling the preparation of fluorine-doped regenerated LMO materials. Electrochemical performance evaluation shows that the 0.2F-RLMO cathode delivers a high reversible capacity (with an initial discharge capacity of 146.7 mAh g−1 at 0.5C and 133.9 mAh g−1 after 200 cycles) and an excellent capacity retention of 91.3%. Density functional theory calculations confirm that F substitution suppresses lattice oxygen activation and reduces the Li+ migration barrier, enhancing stability and kinetics, agreeing with experiments. Moreover, after being assembled into a full cell, the material maintains 83.5% of its initial capacity after 100 cycles at a current density of 0.5C, confirming favorable cycling stability. Fluoride ion doping can generate oxygen vacancies, thereby increasing the lithium-ion diffusion coefficient in LMO and improving the structural stability and electrochemical cycling durability of the material.
锂离子电池的使用寿命一般为5到8年。随着全球电池市场的不断增长，生产的废旧电池数量急剧增加。废旧电池的处理不仅会造成环境污染，还会造成严重的资源浪费，而正极材料是锂离子电池回收利用中最有价值的组成部分。本研究主要研究了废锰酸锂正极材料的再生与再利用。在再生过程中，氧缺陷被引入到LMO结构中，使得制备含氟再生LMO材料成为可能。电化学性能评价表明，0.2F-RLMO阴极具有较高的可逆容量（0.5℃时初始放电容量为146.7 mAh g−1,200次循环后放电容量为133.9 mAh g−1）和91.3%的良好容量保持率。密度泛函理论计算证实，F取代抑制了晶格氧活化，降低了Li+迁移势垒，提高了稳定性和动力学，与实验结果一致。此外，在0.5C的电流密度下，该材料组装成一个完整的电池后，在100次循环后仍保持其初始容量的83.5%，证实了良好的循环稳定性。氟离子掺杂可以产生氧空位，从而增加锂离子在LMO中的扩散系数，提高材料的结构稳定性和电化学循环耐久性。
{"title":"Direct regeneration of spent LiMnO cathodes with F-doping towards stable storage properties","authors":"Shuo Liu,Hongshuo Yang,Yang Zhang,Liming Zhang,Jian Lu,Qingrong Kong,Zhi Su","doi":"10.1039/d6qi01419d","DOIUrl":"https://doi.org/10.1039/d6qi01419d","url":null,"abstract":"Lithium-ion batteries generally provide a service life of about five to eight years. With the continuous growth of the global battery market, the number of spent batteries produced has increased sharply. The disposal of spent batteries causes not only environmental pollution but also serious resource waste, with cathode materials representing the most valuable component in lithium-ion battery recycling. This study mainly investigates the regeneration and reutilization of spent lithium manganese oxide (LiMn2O4, LMO) cathode materials. During regeneration, oxygen defects are introduced into the LMO structure, enabling the preparation of fluorine-doped regenerated LMO materials. Electrochemical performance evaluation shows that the 0.2F-RLMO cathode delivers a high reversible capacity (with an initial discharge capacity of 146.7 mAh g−1 at 0.5C and 133.9 mAh g−1 after 200 cycles) and an excellent capacity retention of 91.3%. Density functional theory calculations confirm that F substitution suppresses lattice oxygen activation and reduces the Li+ migration barrier, enhancing stability and kinetics, agreeing with experiments. Moreover, after being assembled into a full cell, the material maintains 83.5% of its initial capacity after 100 cycles at a current density of 0.5C, confirming favorable cycling stability. Fluoride ion doping can generate oxygen vacancies, thereby increasing the lithium-ion diffusion coefficient in LMO and improving the structural stability and electrochemical cycling durability of the material.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"28 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148909064","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 sustainable production of syngas (H2/CO) from formic acid (FA) offers a promising route for solar-to-chemical energy conversion, yet remains limited by inefficient charge utilization and poor control over competing reaction pathways. Herein, we report a molecular Ni-phenanthroline complex as a cocatalyst for visible-light-driven FA decomposition in aqueous media. When coupled with CdS nanorods, the Ni complex functions as an efficient electron-transfer mediator, facilitating interfacial charge separation and promoting selective syngas evolution. Notably, the catalytic system operates in water without any organic additives, highlighting its environmental compatibility. The optimized system achieves H2 and CO production rates of 125 ± 9.8 and 53 ± 4.6 μmol mg-1 h-1, respectively, with apparent quantum yields of 15.4 ± 1.4% and 7.1 ± 1.2% at 420 nm, respectively, along with excellent stability. This work provides a general strategy for integrating molecular catalysts with semiconductors to enable efficient and selective photocatalytic syngas production from formic acid.
{"title":"A Molecular Nickel-Phenanthroline Catalyst for Photocatalytic Syngas Production from Formic Acid in Aqueous Media","authors":"Taotao Wang,Hongyun Cao,Chenyu Huang,Honghe Ma,Jiewu Cui,Jun Lv,Pingwu Du,Muqing Chen","doi":"10.1039/d6qi01520d","DOIUrl":"https://doi.org/10.1039/d6qi01520d","url":null,"abstract":"The sustainable production of syngas (H2/CO) from formic acid (FA) offers a promising route for solar-to-chemical energy conversion, yet remains limited by inefficient charge utilization and poor control over competing reaction pathways. Herein, we report a molecular Ni-phenanthroline complex as a cocatalyst for visible-light-driven FA decomposition in aqueous media. When coupled with CdS nanorods, the Ni complex functions as an efficient electron-transfer mediator, facilitating interfacial charge separation and promoting selective syngas evolution. Notably, the catalytic system operates in water without any organic additives, highlighting its environmental compatibility. The optimized system achieves H2 and CO production rates of 125 ± 9.8 and 53 ± 4.6 μmol mg-1 h-1, respectively, with apparent quantum yields of 15.4 ± 1.4% and 7.1 ± 1.2% at 420 nm, respectively, along with excellent stability. This work provides a general strategy for integrating molecular catalysts with semiconductors to enable efficient and selective photocatalytic syngas production from formic acid.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"144 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148909031","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}
Tarek El Sayed,Akhil Patel,Jennifer A Salaiza,Husna Azhakath Valappil,Liviu M. Mirica,Kerui Xu,Shreyan Majumdar,Brad Sutton
Alzheimer's disease (AD) is a progressive neurodegenerative disorder whose prevalence is rising with the aging of the global population. Among the proposed pathological hallmarks, the amyloid-beta (Aβ) peptide aggregates and soluble Aβ oligomers are established biomarkers and remain valuable diagnostic targets. While positron emission tomography (PET) imaging agents dominate AD diagnostic imaging, there are no FDA-approved MRI agents for AD. Herein, we report five bifunctional chelators built on the 2,11-diaza[3.3](2,6)pyridinophane framework, and which were evaluated as chelators for Mn 2+ -based MRI contrast agents. Based on in vitro studies, including thermodynamic stability and kinetic inertness measurements, T1 relaxivity and 17O transverse relaxivity measurements to extract hydration numbers and water-exchange parameters, we obtained a clear structure-activity correlation for the corresponding bifunctional chelators: anionic picolinate and acetate arms increase thermodynamic stability and kinetic inertness, while the benzothiazolyl-phenol arm accelerates water exchange. Importantly, a high hydration number alone is insufficient, as a rapid water exchange is also needed for an appreciable contrast. Moreover, we show both the bifunctional chelators and their Mn2+ complexes exhibit appreciable affinity for Aβ aggregates, both in vitro and in 5xFAD mouse brain sections. [Mn(TE-8)], the most kinetically inert complex with favorable relaxivity, log D, and Aβ affinity, was advanced to in vivo MRI studies. Unlike MnCl2, which accumulates non-specifically, [Mn(TE-8)] cleared through renal and hepatobiliary routes and produced measurable brain contrast enhancement. Together, these results establish the diazapyridinophane scaffold as a viable first generation platform for blood-brain-barrier-permeable Mn2+ MRI contrast agents.
{"title":"Design of bifunctional pyridinophane ligands as Mn MRI agents for diagnostic imaging of Alzheimer's disease","authors":"Tarek El Sayed,Akhil Patel,Jennifer A Salaiza,Husna Azhakath Valappil,Liviu M. Mirica,Kerui Xu,Shreyan Majumdar,Brad Sutton","doi":"10.1039/d6qi01745b","DOIUrl":"https://doi.org/10.1039/d6qi01745b","url":null,"abstract":"Alzheimer's disease (AD) is a progressive neurodegenerative disorder whose prevalence is rising with the aging of the global population. Among the proposed pathological hallmarks, the amyloid-beta (Aβ) peptide aggregates and soluble Aβ oligomers are established biomarkers and remain valuable diagnostic targets. While positron emission tomography (PET) imaging agents dominate AD diagnostic imaging, there are no FDA-approved MRI agents for AD. Herein, we report five bifunctional chelators built on the 2,11-diaza[3.3](2,6)pyridinophane framework, and which were evaluated as chelators for Mn 2+ -based MRI contrast agents. Based on in vitro studies, including thermodynamic stability and kinetic inertness measurements, T1 relaxivity and 17O transverse relaxivity measurements to extract hydration numbers and water-exchange parameters, we obtained a clear structure-activity correlation for the corresponding bifunctional chelators: anionic picolinate and acetate arms increase thermodynamic stability and kinetic inertness, while the benzothiazolyl-phenol arm accelerates water exchange. Importantly, a high hydration number alone is insufficient, as a rapid water exchange is also needed for an appreciable contrast. Moreover, we show both the bifunctional chelators and their Mn2+ complexes exhibit appreciable affinity for Aβ aggregates, both in vitro and in 5xFAD mouse brain sections. [Mn(TE-8)], the most kinetically inert complex with favorable relaxivity, log D, and Aβ affinity, was advanced to in vivo MRI studies. Unlike MnCl2, which accumulates non-specifically, [Mn(TE-8)] cleared through renal and hepatobiliary routes and produced measurable brain contrast enhancement. Together, these results establish the diazapyridinophane scaffold as a viable first generation platform for blood-brain-barrier-permeable Mn2+ MRI contrast agents.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"10 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148909065","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}
Xueqian Wu,Xiaodong Gu,Jingwen Chen,Minghui Zhang,Kang Zhou,Feng Xu,Xiuze Hei
Chiral copper(I) iodide hybrids are promising candidates for circularly polarized luminescence (CPL) and multifunctional radiation-responsive photonics, yet understanding how subtle ligand variations regulate the chiroptical response of Cu4I4 cluster emitters remains challenging. Herein, three pairs of zero-dimensional chiral Cu4I4L4 cubane-like clusters were constructed using structurally related enantiopure amine ligands. The structurally related series reveals that small changes in ligand structure modulate Cu···Cu distances, chiral core distortion, and excited-state structural relaxation without changing the cluster-centered emissive nature. Among them, S-1 combines pronounced ground-state chiral distortion with reduced excited-state structural reorganization, leading to efficient yellow-green emission, a PLQY of 96.9 ± 1.5%, and clear mirror-image CPL with |glum| up to 2.7 × 10−3. Benefiting from its high emission efficiency, S-1 also exhibits promising X-ray scintillation performance, with a light yield of 70.1 ± 1.8k photons MeV−1, a low detection limit of 127.3 nGy s−1, and a measurable polarization-dependent radioluminescence response. This work highlights the combined influence of ligand-controlled core distortion and excited-state rigidity on the development of multifunctional chiral Cu4I4 cluster materials.
{"title":"Ligand-Modulated CuI Cubane Clusters for Circularly Polarized Luminescence and Polarization-Dependent X-ray Scintillation","authors":"Xueqian Wu,Xiaodong Gu,Jingwen Chen,Minghui Zhang,Kang Zhou,Feng Xu,Xiuze Hei","doi":"10.1039/d6qi01494a","DOIUrl":"https://doi.org/10.1039/d6qi01494a","url":null,"abstract":"Chiral copper(I) iodide hybrids are promising candidates for circularly polarized luminescence (CPL) and multifunctional radiation-responsive photonics, yet understanding how subtle ligand variations regulate the chiroptical response of Cu4I4 cluster emitters remains challenging. Herein, three pairs of zero-dimensional chiral Cu4I4L4 cubane-like clusters were constructed using structurally related enantiopure amine ligands. The structurally related series reveals that small changes in ligand structure modulate Cu···Cu distances, chiral core distortion, and excited-state structural relaxation without changing the cluster-centered emissive nature. Among them, S-1 combines pronounced ground-state chiral distortion with reduced excited-state structural reorganization, leading to efficient yellow-green emission, a PLQY of 96.9 ± 1.5%, and clear mirror-image CPL with |glum| up to 2.7 × 10−3. Benefiting from its high emission efficiency, S-1 also exhibits promising X-ray scintillation performance, with a light yield of 70.1 ± 1.8k photons MeV−1, a low detection limit of 127.3 nGy s−1, and a measurable polarization-dependent radioluminescence response. This work highlights the combined influence of ligand-controlled core distortion and excited-state rigidity on the development of multifunctional chiral Cu4I4 cluster materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"375 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148902521","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}
Huan Wang,Pratima Sharma,Mahbod Morshedi,Eleni Notaras,Mahesh Kodikara,Yovan de Coene,Koen Clays,Chi Zhang,Mark G Humphrey
The syntheses of (5-(4-N,N-diethylanilinoalkynyl donor)-15-(2-dicyanomethylene-3-cyano-4-methyl-2,5-dihydrofuran-containing acceptor)-10,20-diphenylporphyrinato)nickel(II) complexes, comprising metallated porphyrin cores unsymmetrically functionalized with strongly electron-donating dialkylanilino and strongly electron-withdrawing tricyanofuran (TCF) substituents, are reported. These dipolar complexes exhibit strong quadratic optical nonlinearity towards ns pulsed radiation, with hyper-Rayleigh scattering-derived first hyperpolarizabilities up to 3600 x 10^-30 esu (1064 nm) and 3800 x 10^-30 esu (1300 nm). They also demonstrate remarkable nonlinear absorption activity towards femtosecond pulsed radiation over the spectral range 800-2150 nm, with Z-scan-derived maximal values up to 11,000 GM (950 nm, two-photon absorption), 8400 x 10^-80 cm^6 s^2 photon^-2 (1250 nm, three-photon absorption), and 480 x 10^-110 cm^8 s^3 photon^-3 (1650 nm, four-photon absorption). The two-, three-, and four-photon absorption maxima are close to the corresponding multiples of intense linear absorption bands that time-dependent density functional theory assigns as admixtures of porphyrin-localized π* <- π and charge-transfer transitions.
报道了以强给电子二基亚苯胺和强吸电子三氰呋喃（TCF）取代基不对称功能化的金属卟啉核合成（5-（4-N， n-二乙基苯胺炔基供体）-15-（2-二氰亚甲基-3-氰基-4-甲基-2,5-二氢呋喃受体）-10,20-二苯基卟啉）镍（II）配合物。这些偶极配合物对ns脉冲辐射表现出强烈的二次光学非线性，其超瑞利散射衍生的第一超极化率高达3600 x 10^-30 esu （1064 nm）和3800 x 10^-30 esu （1300 nm）。在800-2150 nm的光谱范围内，它们对飞秒脉冲辐射也表现出显著的非线性吸收活性，z扫描衍生的最大值高达11000 GM （950 nm，双光子吸收），8400 x 10^-80 cm^6 s^2光子^-2 （1250 nm，三光子吸收）和480 x 10^-110 cm^8 s^3光子^-3 （1650 nm，四光子吸收）。二光子、三光子和四光子的吸收最大值接近于随时间密度泛函理论给出的卟啉定域π* <- π和电荷转移跃迁的混合物所对应的强线性吸收带的倍数。
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Wenyi Li,Yudai Huang,Wei Wang,Weihua Wang,Siyi Jing,Haozhe Liu,Yingde Huang,Zhouliang Tan
Mechanical-chemical failure of SiO anodes, driven by severe volume expansion (≈200%) and the associated strain propagation during cycling, causes pronounced capacity decay and kinetic hysteresis, thereby limiting practical application.Herein, natural humic acid (HA), rich in polar functional groups such as hydroxymethyl (-CH 2 OH), carboxyl (-COOH) and phenolic hydroxyl (-C 6 H 5 -OH), is proposed as a supramolecular binder to enhance the mechano-chemical stability of micro-sized SiO anodes. Advanced structural characterization and theoretical calculation results show that HA, anchored onto the SiO surface, form an "elastic buffer network" through dense supramolecular interactions (multivalent hydrogen bonds) that can reversibly dissociate to dissipate stress, thereby preventing irreversible network fracture during SiO expansion. Moreover, the conjugated aromatic domains in HA promote interparticle electron transport via π-π stacking and their intrinsic carbon-like conductivity. As a result, the HA/SiO demonstrates remarkable cycling performance (The capacity decay rate is merely 0.05% per cycle over 1000 cycles at 1.9 A g -1 ) and excellent rate capability (907.9 mAh g -1 at 4 A g -1 ). Furthermore, the assembled PVDF/NCM811||HA/SiO full cell achieves a capacity retention of 76.6% after 350 cycles at 0.5 C, demonstrating its excellent practical viability. This work highlights supramolecular-chemistry-enabled binder design as an effective route toward highperformance and sustainable SiO anodes.
严重的体积膨胀（≈200%）和循环过程中相关的应变传播导致SiO阳极的机械化学失效，导致明显的容量衰减和动力学滞后，从而限制了实际应用。因此，天然腐植酸（HA）富含极性官能团，如羟甲基（- ch2 OH）、羧基（-COOH）和酚羟基（- 6 H 5 -OH），被认为是一种超分子粘合剂，可以增强微尺寸SiO阳极的机械化学稳定性。先进的结构表征和理论计算结果表明，锚定在SiO表面的HA通过密集的超分子相互作用（多价氢键）形成“弹性缓冲网络”，可以可逆地解离以消散应力，从而防止SiO膨胀过程中不可逆的网络断裂。此外，羟基磷酰胺中的共轭芳香结构域通过π-π堆叠促进粒子间电子传递及其固有的类碳电导率。因此，HA/SiO表现出卓越的循环性能（在1.9 a g -1下，在1000次循环中，容量衰减率仅为0.05%）和出色的倍率能力（在4 a g -1下，907.9 mAh g -1）。此外，组装的PVDF/NCM811||HA/SiO全电池在0.5 C下循环350次后，容量保持率达到76.6%，证明了其出色的实用可行性。这项工作强调了超分子化学粘合剂设计是实现高性能和可持续发展的SiO阳极的有效途径。
{"title":"Reversible Supramolecular Dynamic Binder Enables Stress-Regulated SiO with Long-Term Stable Lithium Storage","authors":"Wenyi Li,Yudai Huang,Wei Wang,Weihua Wang,Siyi Jing,Haozhe Liu,Yingde Huang,Zhouliang Tan","doi":"10.1039/d6qi01338d","DOIUrl":"https://doi.org/10.1039/d6qi01338d","url":null,"abstract":"Mechanical-chemical failure of SiO anodes, driven by severe volume expansion (≈200%) and the associated strain propagation during cycling, causes pronounced capacity decay and kinetic hysteresis, thereby limiting practical application.Herein, natural humic acid (HA), rich in polar functional groups such as hydroxymethyl (-CH 2 OH), carboxyl (-COOH) and phenolic hydroxyl (-C 6 H 5 -OH), is proposed as a supramolecular binder to enhance the mechano-chemical stability of micro-sized SiO anodes. Advanced structural characterization and theoretical calculation results show that HA, anchored onto the SiO surface, form an \"elastic buffer network\" through dense supramolecular interactions (multivalent hydrogen bonds) that can reversibly dissociate to dissipate stress, thereby preventing irreversible network fracture during SiO expansion. Moreover, the conjugated aromatic domains in HA promote interparticle electron transport via π-π stacking and their intrinsic carbon-like conductivity. As a result, the HA/SiO demonstrates remarkable cycling performance (The capacity decay rate is merely 0.05% per cycle over 1000 cycles at 1.9 A g -1 ) and excellent rate capability (907.9 mAh g -1 at 4 A g -1 ). Furthermore, the assembled PVDF/NCM811||HA/SiO full cell achieves a capacity retention of 76.6% after 350 cycles at 0.5 C, demonstrating its excellent practical viability. This work highlights supramolecular-chemistry-enabled binder design as an effective route toward highperformance and sustainable SiO anodes.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"40 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148893489","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}
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