Alkali-activated slag cement (AAS) is a sustainable and promising matrix for immobilizing radioactive wastes. Strätlingite (siliceous AFm-type phase), a typical hydration product in AAS, plays a crucial role in stabilizing anionic species. However, the immobilization mechanisms of iodine species within strätlingite remain unclear. In this study, strätlingite demonstrated a greater affinity for IO3– than I–, with adsorption capacities of 0.291 and 0.0016 mmol/g, respectively. Approximate site energy distribution revealed a more diverse energy partitioning of adsorption sites for IO3– than I–, and strong interactions between IO3– and Ca sites through O–Ca bonds forming. Conversely, the differential charge density between I– and Ca sites was weak. The surface adsorption energy of IO3– to Ca sites was −5.05 eV, substantially higher than the −1.08 eV for I– adsorption. A stronger overlap between the 2p orbitals of O atoms and the 3d orbitals of Ca was observed upon IO3– adsorption than I– adsorption. Moreover, the anion selectivity of strätlingite followed the order: CO32– > SO42– ≥ IO3– > OH– > Cl– > NO3– ≥ I–. These findings provide valuable insights into the migration behavior of iodine species in repositories and alkaline environments.
{"title":"Mechanistic Insights into the Interaction between Strätlingite and I–/IO3–: Implications on the Iodine Migration in Alkali-Activated Slag Cement","authors":"Binglin Guo,Cheng Wang,Ping Ye,Huyong Qin,Yuting Chu,Kaixuan Wang,Hengjun Mei,Peng Gao,Binggen Zhan,Qijun Yu,Keiko Sasaki,Yogarajah Elakneswaran","doi":"10.1021/acs.inorgchem.5c04919","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c04919","url":null,"abstract":"Alkali-activated slag cement (AAS) is a sustainable and promising matrix for immobilizing radioactive wastes. Strätlingite (siliceous AFm-type phase), a typical hydration product in AAS, plays a crucial role in stabilizing anionic species. However, the immobilization mechanisms of iodine species within strätlingite remain unclear. In this study, strätlingite demonstrated a greater affinity for IO3– than I–, with adsorption capacities of 0.291 and 0.0016 mmol/g, respectively. Approximate site energy distribution revealed a more diverse energy partitioning of adsorption sites for IO3– than I–, and strong interactions between IO3– and Ca sites through O–Ca bonds forming. Conversely, the differential charge density between I– and Ca sites was weak. The surface adsorption energy of IO3– to Ca sites was −5.05 eV, substantially higher than the −1.08 eV for I– adsorption. A stronger overlap between the 2p orbitals of O atoms and the 3d orbitals of Ca was observed upon IO3– adsorption than I– adsorption. Moreover, the anion selectivity of strätlingite followed the order: CO32– > SO42– ≥ IO3– > OH– > Cl– > NO3– ≥ I–. These findings provide valuable insights into the migration behavior of iodine species in repositories and alkaline environments.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"8 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098052","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}
Multilevel memory is a feasible solution for the explosive demand for data storage in the Big Data era. In this work, ligand engineering has been implemented in cubane-type Cu4I4L4 clusters to obtain three complexes: Cu4I4L4 (L = P(Ph-p-Cl)3 (1), PPh3 (2), P(Ph-p-OCH3)3 (3)), in which the substitutes on the p-position of benzyl vary from electron-withdrawing (–Cl) to electron-donating (−OCH3) groups. Interestingly, with enhancement of electron-donating ability, the trend of more distorted Cu4I4 cores, enhanced Cu···Cu interactions, and higher structural dimensions can be achieved. Consequently, in FTO/Cu4I4L4/Ag memristors, the electron-withdrawing group (–Cl) and neutral group (–H) exhibit bistable resistive switching performances, and a strong electron-donating group (−OCH3) can give ternary resistive switching behavior (OFF/ON1/ON2 current ratio: 1:102.74:103.73, VSet1/VSet2: 1.09/1.48 V). The mechanism about the elevation from binary to ternary memory behavior in these cubane-like Cu4I4L4 clusters has been clarified: the external voltage-induced I···Cl halogen bonding and C–H···π interaction contribute to the binary resistive switching performances in FTO/1/Ag and FTO/2/Ag, and the presence of the second conductive state in FTO/3/Ag stems from the injected carrier delocalization on the Cu4I4 core due to strong Cu···Cu interactions. The rules drawn in this work can provide a feasible strategy for the design of novel multilevel memories.
{"title":"Elevation from Binary to Ternary Resistive Switching Behaviors in Cubane-like Copper Iodide Clusters by Ligand Engineering","authors":"Xueru Zhou,Yanfeng Du,Lintao Fan,Yuanzheng Liu,Junwei Liang,Zefeng Ma,Haohong Li,Huidong Zheng","doi":"10.1021/acs.inorgchem.5c04773","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c04773","url":null,"abstract":"Multilevel memory is a feasible solution for the explosive demand for data storage in the Big Data era. In this work, ligand engineering has been implemented in cubane-type Cu4I4L4 clusters to obtain three complexes: Cu4I4L4 (L = P(Ph-p-Cl)3 (1), PPh3 (2), P(Ph-p-OCH3)3 (3)), in which the substitutes on the p-position of benzyl vary from electron-withdrawing (–Cl) to electron-donating (−OCH3) groups. Interestingly, with enhancement of electron-donating ability, the trend of more distorted Cu4I4 cores, enhanced Cu···Cu interactions, and higher structural dimensions can be achieved. Consequently, in FTO/Cu4I4L4/Ag memristors, the electron-withdrawing group (–Cl) and neutral group (–H) exhibit bistable resistive switching performances, and a strong electron-donating group (−OCH3) can give ternary resistive switching behavior (OFF/ON1/ON2 current ratio: 1:102.74:103.73, VSet1/VSet2: 1.09/1.48 V). The mechanism about the elevation from binary to ternary memory behavior in these cubane-like Cu4I4L4 clusters has been clarified: the external voltage-induced I···Cl halogen bonding and C–H···π interaction contribute to the binary resistive switching performances in FTO/1/Ag and FTO/2/Ag, and the presence of the second conductive state in FTO/3/Ag stems from the injected carrier delocalization on the Cu4I4 core due to strong Cu···Cu interactions. The rules drawn in this work can provide a feasible strategy for the design of novel multilevel memories.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"80 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098087","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}
Charge separation efficiency is the determinant factor for reactive oxygen species (ROS) involved in photocatalytic aerobic oxidation reaction. Metal-organic frameworks (MOFs) provided a formidable platform for designing a donor-acceptor (D-A) system with tunable photoexcited carrier dynamics. Herein, we reported a series of UiO-68 type MOFs (termed as UiO-68-A-D1-A, UiO-68-A-D2-A, and UiO-68-A-D3-A) based on linearly bridged bis-benzothiadiazole as A-D-A linkers. Experimental and density functional theory calculations revealed that regulating the donor units from benzene to naphthalene and anthracene with gradually improved electron-donating capacity significantly enhanced the photogenerated charge separation and transfer efficiency and hence facilitated the ROS generation. As expected, anthracene-containing UiO-68-A-D3-A displayed the highest activity for the visible-light driven aerobic oxidation of benzylamines coupling. This work demonstrated that linker engineering of D-A molecular junctions in MOFs by fine-tuning the electronic nature of donor and acceptor units and their connection mode is a promising strategy to develop novel photocatalysts for efficient organic transformation.
电荷分离效率是光催化好氧反应中活性氧（ROS）的决定因素。金属有机骨架（MOFs）为设计具有可调谐光激发载流子动力学的供体-受体（D-A）系统提供了一个强大的平台。在此，我们报道了一系列UiO-68型mof（称为UiO-68- a - d1 - a， UiO-68- a - d2 - a和UiO-68- a - d3 - a）基于线性桥接的双苯并噻唑作为a - d - a连接体。实验和密度泛函理论计算表明，调节从苯到萘和蒽的供体单元，使其给电子能力逐渐提高，可以显著提高光生电荷分离和转移效率，从而促进ROS的生成。正如预期的那样，含蒽的UiO-68-A-D3-A在可见光驱动下对苄胺偶联的有氧氧化表现出最高的活性。这项工作表明，通过微调供体和受体单元的电子性质及其连接模式来实现mof中D-A分子连接的连接工程是开发高效有机转化的新型光催化剂的一种有前途的策略。
{"title":"Electron Donor Regulation in A-D-A Type Metal-Organic Frameworks for Enhancing Visible-Light Driven Photocatalysis.","authors":"Mingxue Shao,Huadong Guo,Chunyu Liu,Rao Bao,Song Wang,Xianmin Guo","doi":"10.1021/acs.inorgchem.5c06064","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c06064","url":null,"abstract":"Charge separation efficiency is the determinant factor for reactive oxygen species (ROS) involved in photocatalytic aerobic oxidation reaction. Metal-organic frameworks (MOFs) provided a formidable platform for designing a donor-acceptor (D-A) system with tunable photoexcited carrier dynamics. Herein, we reported a series of UiO-68 type MOFs (termed as UiO-68-A-D1-A, UiO-68-A-D2-A, and UiO-68-A-D3-A) based on linearly bridged bis-benzothiadiazole as A-D-A linkers. Experimental and density functional theory calculations revealed that regulating the donor units from benzene to naphthalene and anthracene with gradually improved electron-donating capacity significantly enhanced the photogenerated charge separation and transfer efficiency and hence facilitated the ROS generation. As expected, anthracene-containing UiO-68-A-D3-A displayed the highest activity for the visible-light driven aerobic oxidation of benzylamines coupling. This work demonstrated that linker engineering of D-A molecular junctions in MOFs by fine-tuning the electronic nature of donor and acceptor units and their connection mode is a promising strategy to develop novel photocatalysts for efficient organic transformation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"74 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146088934","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 : 2026-01-31DOI: 10.1021/acs.inorgchem.5c04921
Arya Loloee,Manuel Scharrer,Tullio S Geraci,Hui-Fei Zhai,Matt S Flores,Prajna Bhatt,Aysha A Riaz,Pardeep K Thakur,Tien-Lin Lee,Anna Regoutz,Jakoah Brgoch,Jason F Khoury,Alexandra Navrotsky,Christina S Birkel
MAX phases are a class of compounds known for having both metallic and ceramic properties, such as good electrical conductivity, oxidation resistance, and high hardness. The bulk of the research on their properties focuses on those with titanium at the M-site and metals from groups 13 to 15, e.g., aluminum, at the A-site. Here, we expand the properties repertoire with new arsenic-containing A-site solid solutions, V2(As1-xPx)C and V2(As1-xGex)C. The structure and elemental composition of the solid solutions were resolved with powder X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray spectroscopy, and hard X-ray photoelectron spectroscopy. The electrical resistivity measurements show that both full series are metallic with the parent phases being the most conductive. Thermal analyses show V2GeC is the most oxidation resistant and V2AsC is the least, while substitutions decrease thermal stability, as oxidation resistance of the intermediate compositions shifts toward that of V2AsC. The V2(As1-xGex)C series shows little variation in hardness across compositions, while the incorporation of phosphorus noticeably increases hardness.
{"title":"A-Site Solid Solution Effects on Electrical Resistivity, Oxidation Resistance, and Hardness of MAX Phases V2(As1-xPx)C and V2(As1-xGex)C.","authors":"Arya Loloee,Manuel Scharrer,Tullio S Geraci,Hui-Fei Zhai,Matt S Flores,Prajna Bhatt,Aysha A Riaz,Pardeep K Thakur,Tien-Lin Lee,Anna Regoutz,Jakoah Brgoch,Jason F Khoury,Alexandra Navrotsky,Christina S Birkel","doi":"10.1021/acs.inorgchem.5c04921","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c04921","url":null,"abstract":"MAX phases are a class of compounds known for having both metallic and ceramic properties, such as good electrical conductivity, oxidation resistance, and high hardness. The bulk of the research on their properties focuses on those with titanium at the M-site and metals from groups 13 to 15, e.g., aluminum, at the A-site. Here, we expand the properties repertoire with new arsenic-containing A-site solid solutions, V2(As1-xPx)C and V2(As1-xGex)C. The structure and elemental composition of the solid solutions were resolved with powder X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray spectroscopy, and hard X-ray photoelectron spectroscopy. The electrical resistivity measurements show that both full series are metallic with the parent phases being the most conductive. Thermal analyses show V2GeC is the most oxidation resistant and V2AsC is the least, while substitutions decrease thermal stability, as oxidation resistance of the intermediate compositions shifts toward that of V2AsC. The V2(As1-xGex)C series shows little variation in hardness across compositions, while the incorporation of phosphorus noticeably increases hardness.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"8 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146088928","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 : 2026-01-30DOI: 10.1021/acs.inorgchem.5c05473
Yi-Feng Yuan,Yan Lin,Meng-Ting He,Jin-Ju Zhai,Yuan-Qing Xu,Jun-Xia Liu,Zhong-Yan Cao,Peng-Fei Zhang,Meng-Hua Li
Photocontrollable luminescent materials with highly efficient emission properties offer promising application prospects in the field of intelligent switches, information security, etc. Herein, two stimulus-responsive CPs (CPs 1-2) have been successfully synthesized based on the photoactive TPT ligand (2,4,6-tris-4-pyridyl-1,3,5-triazine) via the solvothermal method. Remarkably, CPs 1-2 exhibit distinct photochromism coupled with photocontrollable luminescence behaviors. Furthermore, by employing an in situ doping strategy, lanthanide ions were immobilized within the pores of CP 2 to generate Eu/Tb@CP 2 composites, which display significantly enhanced fluorescence (QY increased from 0.49% to 16.5%) without compromising photochromic properties. Moreover, leveraging their dynamic, efficient, and multicolor luminescence, these compounds enable the realization of multimode smart displays. This work offers valuable insights for designing novel stimulus-responsive materials with efficient and color-tunable luminescence via in situ doping strategies, thereby advancing the development of photochromic materials toward practical applications in multilevel information display and advanced data encryption.
{"title":"A Strategy to Enhance Luminescence in Photochromic Coordination Polymers for Multi-Mode Smart Displays.","authors":"Yi-Feng Yuan,Yan Lin,Meng-Ting He,Jin-Ju Zhai,Yuan-Qing Xu,Jun-Xia Liu,Zhong-Yan Cao,Peng-Fei Zhang,Meng-Hua Li","doi":"10.1021/acs.inorgchem.5c05473","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05473","url":null,"abstract":"Photocontrollable luminescent materials with highly efficient emission properties offer promising application prospects in the field of intelligent switches, information security, etc. Herein, two stimulus-responsive CPs (CPs 1-2) have been successfully synthesized based on the photoactive TPT ligand (2,4,6-tris-4-pyridyl-1,3,5-triazine) via the solvothermal method. Remarkably, CPs 1-2 exhibit distinct photochromism coupled with photocontrollable luminescence behaviors. Furthermore, by employing an in situ doping strategy, lanthanide ions were immobilized within the pores of CP 2 to generate Eu/Tb@CP 2 composites, which display significantly enhanced fluorescence (QY increased from 0.49% to 16.5%) without compromising photochromic properties. Moreover, leveraging their dynamic, efficient, and multicolor luminescence, these compounds enable the realization of multimode smart displays. This work offers valuable insights for designing novel stimulus-responsive materials with efficient and color-tunable luminescence via in situ doping strategies, thereby advancing the development of photochromic materials toward practical applications in multilevel information display and advanced data encryption.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"34 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073346","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}
Two quasi-iron-based metal-organic frameworks, Q-MIL-100 and Q-MIL-101, were prepared via thermal partial deligandation to create large-scale structural defects. This pore engineering enhanced the density of unsaturated iron sites and created hierarchical porosity, serving as active centers for the catalytic hydrogen generation from NaBH4 hydrolysis. While pristine MIL-101 demonstrated higher activity than MIL-100, defect engineering reversed this trend, resulting in Q-MIL-100 achieving a superior hydrogen generation rate of 5360 mL·min-1·g-1 at 298 K, compared to 3360 mL·min-1·g-1 for Q-MIL-101. This enhanced performance is attributed to the synergistic combination of accessible active sites and an optimally restructured hierarchical pore architecture. Thermal activation to 313 K dramatically enhanced the hydrogen generation rates to 12,160 and 10,160 mL·min-1·g-1 for Q-MIL-100 and Q-MIL-101, respectively─a 2.3- to 3.0-fold increase over their performance at 298 K. The calculated activation energies were 41.7 kJ·mol-1 for Q-MIL-100 and 56.2 kJ·mol-1 for Q-MIL-101. A kinetic isotope effect indicated that the O-H bond cleavage in water was the rate-determining step. Q-MIL-100 demonstrated exceptional stability, retaining 92% of its initial activity after 16 reuse cycles. This work highlights the novel long-term stability of the engineered catalyst for practical hydrogen generation.
{"title":"Exceptional Long-Term Stability in Hydrogen Evolution via Defect-Engineered MIL-100 Synthesized by Controlled Thermolysis.","authors":"Minoo Bagheri,Fatemeh Momeni,Mohammad Yaser Masoomi","doi":"10.1021/acs.inorgchem.5c04976","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c04976","url":null,"abstract":"Two quasi-iron-based metal-organic frameworks, Q-MIL-100 and Q-MIL-101, were prepared via thermal partial deligandation to create large-scale structural defects. This pore engineering enhanced the density of unsaturated iron sites and created hierarchical porosity, serving as active centers for the catalytic hydrogen generation from NaBH4 hydrolysis. While pristine MIL-101 demonstrated higher activity than MIL-100, defect engineering reversed this trend, resulting in Q-MIL-100 achieving a superior hydrogen generation rate of 5360 mL·min-1·g-1 at 298 K, compared to 3360 mL·min-1·g-1 for Q-MIL-101. This enhanced performance is attributed to the synergistic combination of accessible active sites and an optimally restructured hierarchical pore architecture. Thermal activation to 313 K dramatically enhanced the hydrogen generation rates to 12,160 and 10,160 mL·min-1·g-1 for Q-MIL-100 and Q-MIL-101, respectively─a 2.3- to 3.0-fold increase over their performance at 298 K. The calculated activation energies were 41.7 kJ·mol-1 for Q-MIL-100 and 56.2 kJ·mol-1 for Q-MIL-101. A kinetic isotope effect indicated that the O-H bond cleavage in water was the rate-determining step. Q-MIL-100 demonstrated exceptional stability, retaining 92% of its initial activity after 16 reuse cycles. This work highlights the novel long-term stability of the engineered catalyst for practical hydrogen generation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"5 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073347","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 : 2026-01-30DOI: 10.1021/acs.inorgchem.5c05608
Ani T Baker,James H Lovett,Haipei Zou,Justin J Wilson,Hugh H Harris
The dinuclear ruthenium (Ru) compounds Ru265 and Ru360 are inhibitors of the mitochondrial calcium uniporter (MCU) and potential therapeutic agents for conditions associated with mitochondrial calcium (mt-Ca2+) dysregulation. The nitrido-bridged Ru265 offers improved cell permeability and redox stability relative to the oxo-bridged analogue, Ru360, while maintaining high selectivity and potency. In this study, extended X-ray absorption fine-structure (EXAFS) spectroscopy interrogated the stability of these compounds in buffer, saline/DMSO solutions, and human blood by probing the sensitive Ru─X─Ru scattering signal. Both dinuclear compounds remained intact in a pH 7.4 buffered solution, even in the presence of glutathione (5 mol equiv). Following addition to whole blood, EXAFS identified the presence of diaqua-capped Ru265', indicating axial ligand substitution but confirming stability of the Ru─N─Ru backbone during incubation (1 h, 37 °C). In contrast, Ru360' rapidly degraded in saline/DMSO at room temperature, as evidenced by the diminished intensity of the Ru···Ru peak at ∼3.65 Å in the EXAFS Fourier transform. Subsequently, the mononuclear Ru360' degradation products displayed negligible uptake into red blood cells. These findings support previous studies highlighting the improved stability of Ru265 and provide validation of the structure and coordination environment of the complex in an ex vivo human blood sample.
{"title":"EXAFS Analysis of Ru265 and Ru360 in Human Blood.","authors":"Ani T Baker,James H Lovett,Haipei Zou,Justin J Wilson,Hugh H Harris","doi":"10.1021/acs.inorgchem.5c05608","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05608","url":null,"abstract":"The dinuclear ruthenium (Ru) compounds Ru265 and Ru360 are inhibitors of the mitochondrial calcium uniporter (MCU) and potential therapeutic agents for conditions associated with mitochondrial calcium (mt-Ca2+) dysregulation. The nitrido-bridged Ru265 offers improved cell permeability and redox stability relative to the oxo-bridged analogue, Ru360, while maintaining high selectivity and potency. In this study, extended X-ray absorption fine-structure (EXAFS) spectroscopy interrogated the stability of these compounds in buffer, saline/DMSO solutions, and human blood by probing the sensitive Ru─X─Ru scattering signal. Both dinuclear compounds remained intact in a pH 7.4 buffered solution, even in the presence of glutathione (5 mol equiv). Following addition to whole blood, EXAFS identified the presence of diaqua-capped Ru265', indicating axial ligand substitution but confirming stability of the Ru─N─Ru backbone during incubation (1 h, 37 °C). In contrast, Ru360' rapidly degraded in saline/DMSO at room temperature, as evidenced by the diminished intensity of the Ru···Ru peak at ∼3.65 Å in the EXAFS Fourier transform. Subsequently, the mononuclear Ru360' degradation products displayed negligible uptake into red blood cells. These findings support previous studies highlighting the improved stability of Ru265 and provide validation of the structure and coordination environment of the complex in an ex vivo human blood sample.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"34 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073348","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 : 2026-01-30DOI: 10.1021/acs.inorgchem.5c04945
Moena Hirao,Lukas Bichlmaier,Tetsuhiko F Teshima,Rebecca Wilhelm,Shigeyoshi Inoue
Polymers have had widespread applications in industry over the past few decades. Recently, polymers incorporating heavier group 14 elements (Ge, Sn, and Pb) have gained interest since their oxides are promising for semiconductor applications due to their high dielectric constants and charge mobility. Poly(p-xylylene) (PPX), an important class of polymer, is widely recognized for its transparency, biocompatibility, and the conformality afforded by its polymerization method, chemical vapor deposition (CVD). In this work, PPXs incorporating germanium or tin are prepared via CVD polymerization and the optimal pyrolysis temperatures of their precursors are determined. The ductility, thermal stability, crystallinity, surface topography, and comprehensive and surface chemical compositions are investigated. Sequential changes in the surface oxidation state are confirmed following exposure to air and subsequent oxygen plasma treatment. Comparison of the obtained PPXs with the widely applied chlorinated version PPX-Cl (trade name Parylene C) revealed preserved ductility while exhibiting distinct trends in softness.
{"title":"Synthesis, Characterization, and Polymerization of Ge- and Sn-Substituted [2.2]Paracyclophanes toward Poly(para-xylylene) Films and Their Mechanical Properties.","authors":"Moena Hirao,Lukas Bichlmaier,Tetsuhiko F Teshima,Rebecca Wilhelm,Shigeyoshi Inoue","doi":"10.1021/acs.inorgchem.5c04945","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c04945","url":null,"abstract":"Polymers have had widespread applications in industry over the past few decades. Recently, polymers incorporating heavier group 14 elements (Ge, Sn, and Pb) have gained interest since their oxides are promising for semiconductor applications due to their high dielectric constants and charge mobility. Poly(p-xylylene) (PPX), an important class of polymer, is widely recognized for its transparency, biocompatibility, and the conformality afforded by its polymerization method, chemical vapor deposition (CVD). In this work, PPXs incorporating germanium or tin are prepared via CVD polymerization and the optimal pyrolysis temperatures of their precursors are determined. The ductility, thermal stability, crystallinity, surface topography, and comprehensive and surface chemical compositions are investigated. Sequential changes in the surface oxidation state are confirmed following exposure to air and subsequent oxygen plasma treatment. Comparison of the obtained PPXs with the widely applied chlorinated version PPX-Cl (trade name Parylene C) revealed preserved ductility while exhibiting distinct trends in softness.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"261 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146088930","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 : 2026-01-30DOI: 10.1021/acs.inorgchem.5c04619
Melissa Janesch,Florian Pielnhofer,Michal Dušek,Ilya G Shenderovich,Stefanie Gärtner
The synthesis and characterization of two new compounds Na3Rb6In10Au and Na3.25Cs5.75In10Au are reported, which contain [Au@In10]9- clusters as anionic entities. Single-crystal X-ray structure analysis shows that the alkali metal composition is the key factor for structure formation, while the anionic entity remains unchanged. The chemical composition was confirmed by SEM/EDS measurements, and the given compositions of both compounds are fixed according to the line compounds. Quantum chemical calculations for the compound Na3Rb6In10Au were performed and show a band gap at the Fermi level, classifying the materials as salt-like, including endohedral [Au@In10]9- Zintl-type clusters. Dissolution experiments in liquid ammonia were carried out, revealing In2Au as the reaction product.
{"title":"Endohedral [Au@In10]9- Cluster: Synthesis and Characterization of Na3+xA6-xIn10Au (x = 0, 0.25; A = Rb, Cs).","authors":"Melissa Janesch,Florian Pielnhofer,Michal Dušek,Ilya G Shenderovich,Stefanie Gärtner","doi":"10.1021/acs.inorgchem.5c04619","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c04619","url":null,"abstract":"The synthesis and characterization of two new compounds Na3Rb6In10Au and Na3.25Cs5.75In10Au are reported, which contain [Au@In10]9- clusters as anionic entities. Single-crystal X-ray structure analysis shows that the alkali metal composition is the key factor for structure formation, while the anionic entity remains unchanged. The chemical composition was confirmed by SEM/EDS measurements, and the given compositions of both compounds are fixed according to the line compounds. Quantum chemical calculations for the compound Na3Rb6In10Au were performed and show a band gap at the Fermi level, classifying the materials as salt-like, including endohedral [Au@In10]9- Zintl-type clusters. Dissolution experiments in liquid ammonia were carried out, revealing In2Au as the reaction product.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"15 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073344","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 : 2026-01-30DOI: 10.1021/acs.inorgchem.5c04087
Leroy E Laverman,Kalju Kahn,Peter C Ford
Described are multiple approaches using density functional theory to probe the acid catalyzed aquation of the hexaammineruthenium(II) cation (Ru(NH3)62+ + H3O+ → Ru(NH3)5(H2O)2+ + NH4+) reported initially by Taube and co-workers. These computations support the proposal that the initial step is protonation of the Ru(II) center and/or the metal-NH3 bond, thereby activating the latter toward dissociation. DFT analysis was also carried out for the hypothetical acid-mediated aquation of the isoelectronic hexaamminerhodium(III) complex, Rh(NH3)63+. The computations suggest a key mechanistic difference for the latter pathway, namely that protonation of the NH3 occurs late in a reaction coordinate involving dissociation of the Rh-NH3 with no direct interaction of H+ with the metal center. Furthermore, while the calculated activation energy is considerably higher in the latter case, the calculations suggest that protonation could play an important role in such ligand substitution reactions.
{"title":"A DFT Re-Examination of the Acid Catalyzed Aquation of Hexaammineruthenium(II), Ru(NH3)62.","authors":"Leroy E Laverman,Kalju Kahn,Peter C Ford","doi":"10.1021/acs.inorgchem.5c04087","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c04087","url":null,"abstract":"Described are multiple approaches using density functional theory to probe the acid catalyzed aquation of the hexaammineruthenium(II) cation (Ru(NH3)62+ + H3O+ → Ru(NH3)5(H2O)2+ + NH4+) reported initially by Taube and co-workers. These computations support the proposal that the initial step is protonation of the Ru(II) center and/or the metal-NH3 bond, thereby activating the latter toward dissociation. DFT analysis was also carried out for the hypothetical acid-mediated aquation of the isoelectronic hexaamminerhodium(III) complex, Rh(NH3)63+. The computations suggest a key mechanistic difference for the latter pathway, namely that protonation of the NH3 occurs late in a reaction coordinate involving dissociation of the Rh-NH3 with no direct interaction of H+ with the metal center. Furthermore, while the calculated activation energy is considerably higher in the latter case, the calculations suggest that protonation could play an important role in such ligand substitution reactions.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"45 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146088931","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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