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}
Pub Date : 2026-01-29DOI: 10.1021/acs.inorgchem.5c05560
Chaofeng Zhang,Yinhui Yi,Yong Zhao,Gangbing Zhu
This study prepared UiO-66-NH2 MOFs embedded with Ru-tris(2,2'-bipyridyl)(II) hybrids as a nanozyme (designated as Ru/UiO-66-NH2) to propose a bioenzyme-free homogeneous electrochemical (HEC) sensing strategy for detecting organophosphorus pesticides (OPs). Experimental investigation coupled with density functional theory calculation demonstrated that the Ru incorporation significantly amplifies the peroxidase-like (POD-like) activity of UiO-66-NH2 MOFs and that the Ru/UiO-66-NH2 nanozyme exhibits selective responsiveness to coordinate with the OP molecules. Upon OP exposure, the specifical coordination between OPs and MOF structure effectively inhibits the nanozyme's activity. Utilizing o-phenylenediamine as the catalytic substrate and glyphosate as a model of OPs, the optimized HEC sensor achieves an extensive linear detection range (0.5-10,000 ng/mL) and a low detection limit of 0.13 ng/mL as well as satisfactory recoveries in the real samples of tomato extract and water. It is expected that this innovative bioenzyme-free HEC sensing strategy represents a promising advancement for practical OP residue analysis with potential applications in various fields.
{"title":"Sensitive Homogeneous Electrochemical Detection of Organophosphorus Pesticides by UiO-66-NH2 Embedded with a Ruthenium-tris(2,2'-bipyridyl)(II) Nanozyme.","authors":"Chaofeng Zhang,Yinhui Yi,Yong Zhao,Gangbing Zhu","doi":"10.1021/acs.inorgchem.5c05560","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05560","url":null,"abstract":"This study prepared UiO-66-NH2 MOFs embedded with Ru-tris(2,2'-bipyridyl)(II) hybrids as a nanozyme (designated as Ru/UiO-66-NH2) to propose a bioenzyme-free homogeneous electrochemical (HEC) sensing strategy for detecting organophosphorus pesticides (OPs). Experimental investigation coupled with density functional theory calculation demonstrated that the Ru incorporation significantly amplifies the peroxidase-like (POD-like) activity of UiO-66-NH2 MOFs and that the Ru/UiO-66-NH2 nanozyme exhibits selective responsiveness to coordinate with the OP molecules. Upon OP exposure, the specifical coordination between OPs and MOF structure effectively inhibits the nanozyme's activity. Utilizing o-phenylenediamine as the catalytic substrate and glyphosate as a model of OPs, the optimized HEC sensor achieves an extensive linear detection range (0.5-10,000 ng/mL) and a low detection limit of 0.13 ng/mL as well as satisfactory recoveries in the real samples of tomato extract and water. It is expected that this innovative bioenzyme-free HEC sensing strategy represents a promising advancement for practical OP residue analysis with potential applications in various fields.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"2 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146072896","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}
Copper(I)-halide cluster materials have attracted considerable research interest for advanced optoelectronic applications, owing to their exceptional photophysical characteristics. Nevertheless, their luminescent performance is significantly undermined by thermal quenching (TQ) effects, which fundamentally limits their viability in cutting-edge applications. Herein, we present a molecular strategy that dramatically enhances the antithermal quenching (anti-TQ) performance of copper(I)-iodide cluster-based luminescent materials. Through isomeric ligand engineering using ortho- and para-substituted bis(imidazole) benzene ligands, two distinct cluster-based coordination polymers (CP1 and CP2) exhibiting cluster-centered phosphorescence were synthesized. Remarkably, CP2 demonstrates zero-thermal-quenching (ZTQ) behavior, maintaining nearly constant emission intensity even up to 500 K, while CP1 shows conventional TQ with 72% intensity loss at 500 K. Structural and photophysical analyses reveal that the exceptional thermal stability of CP2 originates from its rigid crystalline architecture featuring a confined cluster core structure and ordered π-π stacking networks, which effectively suppress nonradiative decay. As a result, the potential applications of these molecular-based materials have been explored in light-emitting diode technology and anticounterfeiting, showing excellent prospects for practical implementation. This work provides fundamental insights into structure-property relationships in cluster-based emitters and establishes a new design paradigm for anti-TQ luminescent materials.
{"title":"Ligand-Isomerization Strategy Achieves Exceptional Wide-Range Zero-Thermal-Quenching Phosphorescence in Copper-Iodide Cluster-Organic Frameworks.","authors":"Hao Sun,Yang Chen,Yuye Sun,Ran Wang,Mingchen Deng,Wei Huang,Dayu Wu","doi":"10.1021/acs.inorgchem.5c05141","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05141","url":null,"abstract":"Copper(I)-halide cluster materials have attracted considerable research interest for advanced optoelectronic applications, owing to their exceptional photophysical characteristics. Nevertheless, their luminescent performance is significantly undermined by thermal quenching (TQ) effects, which fundamentally limits their viability in cutting-edge applications. Herein, we present a molecular strategy that dramatically enhances the antithermal quenching (anti-TQ) performance of copper(I)-iodide cluster-based luminescent materials. Through isomeric ligand engineering using ortho- and para-substituted bis(imidazole) benzene ligands, two distinct cluster-based coordination polymers (CP1 and CP2) exhibiting cluster-centered phosphorescence were synthesized. Remarkably, CP2 demonstrates zero-thermal-quenching (ZTQ) behavior, maintaining nearly constant emission intensity even up to 500 K, while CP1 shows conventional TQ with 72% intensity loss at 500 K. Structural and photophysical analyses reveal that the exceptional thermal stability of CP2 originates from its rigid crystalline architecture featuring a confined cluster core structure and ordered π-π stacking networks, which effectively suppress nonradiative decay. As a result, the potential applications of these molecular-based materials have been explored in light-emitting diode technology and anticounterfeiting, showing excellent prospects for practical implementation. This work provides fundamental insights into structure-property relationships in cluster-based emitters and establishes a new design paradigm for anti-TQ luminescent materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"42 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070086","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}
Novel Ba2-xSrxInO3F Ruddlesden-Popper phases were synthesized by solid-state routes at high temperatures under Ar and dry air. The structural features were determined through XRD analysis of well-crystallized powders and isolated single crystals. Two In sites were identified with various occupancies, dependent on the Sr content and on the atmosphere applied during annealing. This indium site distribution leads to the consideration of an anionic disorder on the apical site in the vicinity of In. A maximum in the O2-In-O2 bond angles is identified for the Ba1.2Sr0.8InO3F composition and corresponds to a stronger hybridization between the In (s,p) and O(p) orbitals in the equatorial plane, which should be the signature of monovalent indium. 19F MAS NMR investigation recorded at various temperatures shows the F- hopping phenomenon in the mixed (Ba/Sr) environment, which is most present in the Ba1.2Sr0.8InO3F oxyfluoride and linked to the presence of anionic vacancies. Considering the electroneutrality of the composition, monovalent indium should be stabilized in octahedron with a vacant vertex. Excitation (UV range) and emission (visible range) broad bands are clearly detected, but neither excitation nor emission wavelength varies with the Sr content. However, the photoluminescence intensity is strongly correlated with the composition and reaches a maximum for the Ba1.2Sr0.8InO3F compound. Density functional theory calculations allow for the identification of defect states related to anionic vacancies in the band gap, with hybridization mainly between In(s) and O(p) orbitals in the basal plane, thus explaining the self-trapped exciton (STE) mechanism.
在氩气和干燥空气的高温条件下，采用固态法合成了新型的Ba2-xSrxInO3F Ruddlesden-Popper相。通过XRD分析了结晶良好的粉末和分离的单晶的结构特征。根据Sr含量和退火时的气氛，确定了两个In位点具有不同的占有率。这种铟位点的分布导致考虑在铟附近的根尖位置的阴离子紊乱。在Ba1.2Sr0.8InO3F组合物中，O2-In-O2键角最大，对应于赤道面上的in （s,p）和O(p)轨道之间有较强的杂化，这应该是一价铟的特征。在不同温度下记录的19F - MAS NMR研究表明，在混合（Ba/Sr）环境中，F跳变现象主要存在于Ba1.2Sr0.8InO3F氟化氧中，并与阴离子空位的存在有关。考虑到组合物的电中性，单价铟应该稳定在一个空顶点的八面体中。激发（紫外）和发射（可见光）宽波段清晰可见，但激发和发射波长不随锶含量的变化而变化。然而，光致发光强度与组成密切相关，Ba1.2Sr0.8InO3F化合物达到最大。密度泛函数理论计算允许识别与带隙中阴离子空位相关的缺陷态，主要是基面上的in (s)和O(p)轨道之间的杂化，从而解释了自困激子（STE）机制。
{"title":"The Key Role of Monovalent Indium and Anionic Vacancies in Oxyfluorides Inducing Fluoride Ion Mobility and Luminescence.","authors":"Alizée Deslandes,Fouad Alassani,Stanislav Péchev,Véronique Jubera,Mathieu Duttine,Jacinthe Gamon,Antoine Villesuzanne,Leïlou Loiseau-Foucher,Etienne Durand,Alexandre Fargues,Alain Demourgues","doi":"10.1021/acs.inorgchem.5c04288","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c04288","url":null,"abstract":"Novel Ba2-xSrxInO3F Ruddlesden-Popper phases were synthesized by solid-state routes at high temperatures under Ar and dry air. The structural features were determined through XRD analysis of well-crystallized powders and isolated single crystals. Two In sites were identified with various occupancies, dependent on the Sr content and on the atmosphere applied during annealing. This indium site distribution leads to the consideration of an anionic disorder on the apical site in the vicinity of In. A maximum in the O2-In-O2 bond angles is identified for the Ba1.2Sr0.8InO3F composition and corresponds to a stronger hybridization between the In (s,p) and O(p) orbitals in the equatorial plane, which should be the signature of monovalent indium. 19F MAS NMR investigation recorded at various temperatures shows the F- hopping phenomenon in the mixed (Ba/Sr) environment, which is most present in the Ba1.2Sr0.8InO3F oxyfluoride and linked to the presence of anionic vacancies. Considering the electroneutrality of the composition, monovalent indium should be stabilized in octahedron with a vacant vertex. Excitation (UV range) and emission (visible range) broad bands are clearly detected, but neither excitation nor emission wavelength varies with the Sr content. However, the photoluminescence intensity is strongly correlated with the composition and reaches a maximum for the Ba1.2Sr0.8InO3F compound. Density functional theory calculations allow for the identification of defect states related to anionic vacancies in the band gap, with hybridization mainly between In(s) and O(p) orbitals in the basal plane, thus explaining the self-trapped exciton (STE) mechanism.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"23 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146072895","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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