Pub Date : 2026-02-04DOI: 10.1021/acs.inorgchem.6c00021
Tra Phuong Trinh,Hyun Seok Lee,Gajendra Gupta,Gi Hyeok Park,Yena Choe,Chul Hoon Kim,Chang Yeon Lee
Porphyrin–based metal–organic frameworks (MOFs) are promising photocatalysts, but their efficiency is often limited by rapid charge recombination. Herein, we enhance photocatalytic performance by incorporating an electron acceptor, phenyl–C61–butyric acid (PCBA), into the porphyrinic framework PCN–222 and its metalated analogues (M = Co, Ni, Cu) via a solvent–assisted ligand incorporation (SALI) method. The free–base composite PCBA@PCN–222(H2) exhibited outstanding photocatalytic activity for aerobic thioanisole oxidation (>99% conversion), far outperforming PCBA@PCN–222(Cu) (23%), PCBA@PCN–222(Ni) (3%), and PCBA@PCN–222(Co) (2%). Electrochemical and picosecond time–resolved photoluminescence (TRPL) studies revealed that this superior activity originates from a remarkably long–lived charge–transfer (CT) state (τCR = 1.72 ns) in the free–base system. In contrast, the metalated MOFs exhibited intrinsic metal–associated quenching of the porphyrin units that competes with exciton migration within the MOF, and the CT states formed from a fraction of Q–state populations underwent ultrafast charge recombination (τCR = 70 ∼ 100 ps), which severely limited their efficiency. These findings provide a clear correlation between the lifetime of the photo–induced CT state and catalytic performance, highlighting the importance of the porphyrin’s core electronic nature in designing efficient donor–acceptor photocatalysts.
{"title":"Tuning Photocatalytic Activity in Porphyrin–Based Metal–Organic Frameworks by Controlling Charge Recombination Pathways","authors":"Tra Phuong Trinh,Hyun Seok Lee,Gajendra Gupta,Gi Hyeok Park,Yena Choe,Chul Hoon Kim,Chang Yeon Lee","doi":"10.1021/acs.inorgchem.6c00021","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00021","url":null,"abstract":"Porphyrin–based metal–organic frameworks (MOFs) are promising photocatalysts, but their efficiency is often limited by rapid charge recombination. Herein, we enhance photocatalytic performance by incorporating an electron acceptor, phenyl–C61–butyric acid (PCBA), into the porphyrinic framework PCN–222 and its metalated analogues (M = Co, Ni, Cu) via a solvent–assisted ligand incorporation (SALI) method. The free–base composite PCBA@PCN–222(H2) exhibited outstanding photocatalytic activity for aerobic thioanisole oxidation (>99% conversion), far outperforming PCBA@PCN–222(Cu) (23%), PCBA@PCN–222(Ni) (3%), and PCBA@PCN–222(Co) (2%). Electrochemical and picosecond time–resolved photoluminescence (TRPL) studies revealed that this superior activity originates from a remarkably long–lived charge–transfer (CT) state (τCR = 1.72 ns) in the free–base system. In contrast, the metalated MOFs exhibited intrinsic metal–associated quenching of the porphyrin units that competes with exciton migration within the MOF, and the CT states formed from a fraction of Q–state populations underwent ultrafast charge recombination (τCR = 70 ∼ 100 ps), which severely limited their efficiency. These findings provide a clear correlation between the lifetime of the photo–induced CT state and catalytic performance, highlighting the importance of the porphyrin’s core electronic nature in designing efficient donor–acceptor photocatalysts.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"100 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111215","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-04DOI: 10.1021/acs.inorgchem.5c05641
Shujian Liu,Wen Xu,Xiao Han,Li Wang,Yingchun Miao,Jian-Jun Liu
Rationally designing adsorbents for the effective and selective removal of 99TcO4– from a water environment is extremely desired but remains a challenge. In this study, we successfully constructed a nonporous cationic metal–organic framework (MOF-1) with a three-dimensional architecture. Remarkably, nonporous MOF-1 exhibits extremely fast adsorption kinetics toward ReO4– (a nonradioactive analog for 99TcO4–), achieving adsorption equilibrium within 1 min. And the maximum adsorption capacity of MOF-1 for ReO4– is 375 mg/g. Furthermore, MOF-1 exhibits exceptional selectivity for ReO4– removal in the presence of large excesses of competing anions such as NO3–, SO42–, and Cl–, as even 6000 times of SO42– in excess does not significantly affect the sorption of ReO4–. Additionally, MOF-1 shows excellent ReO4– removal efficiency over a broad pH range (2.0–11.0), and it can still remove 97% of ReO4– after four recycles. Furthermore, a combination of characterization analyses, molecular dynamics simulations, and density functional theory calculations is utilized to clearly elucidate the adsorption mechanism of MOF-1 toward 99TcO4–/ReO4–. MOF-1 holds superior adsorption performance and significant potential for large-scale preparation and is proven to be a highly promising material for removing 99Tc from contaminated water sources.
{"title":"Ultrafast and Selective Adsorption of 99TcO4–/ReO4– from Water by Nonporous Cationic Metal–Organic Framework","authors":"Shujian Liu,Wen Xu,Xiao Han,Li Wang,Yingchun Miao,Jian-Jun Liu","doi":"10.1021/acs.inorgchem.5c05641","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05641","url":null,"abstract":"Rationally designing adsorbents for the effective and selective removal of 99TcO4– from a water environment is extremely desired but remains a challenge. In this study, we successfully constructed a nonporous cationic metal–organic framework (MOF-1) with a three-dimensional architecture. Remarkably, nonporous MOF-1 exhibits extremely fast adsorption kinetics toward ReO4– (a nonradioactive analog for 99TcO4–), achieving adsorption equilibrium within 1 min. And the maximum adsorption capacity of MOF-1 for ReO4– is 375 mg/g. Furthermore, MOF-1 exhibits exceptional selectivity for ReO4– removal in the presence of large excesses of competing anions such as NO3–, SO42–, and Cl–, as even 6000 times of SO42– in excess does not significantly affect the sorption of ReO4–. Additionally, MOF-1 shows excellent ReO4– removal efficiency over a broad pH range (2.0–11.0), and it can still remove 97% of ReO4– after four recycles. Furthermore, a combination of characterization analyses, molecular dynamics simulations, and density functional theory calculations is utilized to clearly elucidate the adsorption mechanism of MOF-1 toward 99TcO4–/ReO4–. MOF-1 holds superior adsorption performance and significant potential for large-scale preparation and is proven to be a highly promising material for removing 99Tc from contaminated water sources.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"280 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111227","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-04DOI: 10.1021/acs.inorgchem.6c00075
Zhiming Wang,Lei Wang,Shiwei Dong,Chuanliang Yang,Jinyi Chen,Wentao Wang,Guoqiang Yang,Zhong Han
The utility of lanthanide-based circularly polarized luminescence (CPL) probes in biological systems is frequently limited by kinetic lability and excitation-related toxicity. To overcome these barriers, we have engineered rigid chiral Ir(III)–Eu(III) dyads (Ir–Eu–R and Ir–Eu–S) using a stereoselective ″complex-as-ligand″ strategy. This architecture features a kinetically inert DO3A macrocycle (1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid) that effectively preserves the stereochemical environment, yielding intense CPL (|glum| = 0.12) with substantial brightness (BCPL ≈ 8 M–1 cm–1). Simultaneously, the integrated Ir(III) antenna enables benign visible-light sensitization (λex = 425 nm), facilitating low-phototoxicity confocal imaging in HeLa cells. Crucially, the probe’s structural rigidity ensures exceptional stability against biological interferents; spectroscopic titration with ct-DNA confirms the preservation of chiroptical signals without conformational distortion. This work presents a general coordination strategy for constructing robust, bright, and visible-light-excitable rare-earth chiroptical materials, opening new avenues for specific chiroptical bioimaging and enantioselective sensing applications.
{"title":"Rational Design of Rigid Chiral Ir(III)–Eu(III) Dyads: Intense Circularly Polarized Luminescence via Visible-Light Sensitization","authors":"Zhiming Wang,Lei Wang,Shiwei Dong,Chuanliang Yang,Jinyi Chen,Wentao Wang,Guoqiang Yang,Zhong Han","doi":"10.1021/acs.inorgchem.6c00075","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00075","url":null,"abstract":"The utility of lanthanide-based circularly polarized luminescence (CPL) probes in biological systems is frequently limited by kinetic lability and excitation-related toxicity. To overcome these barriers, we have engineered rigid chiral Ir(III)–Eu(III) dyads (Ir–Eu–R and Ir–Eu–S) using a stereoselective ″complex-as-ligand″ strategy. This architecture features a kinetically inert DO3A macrocycle (1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid) that effectively preserves the stereochemical environment, yielding intense CPL (|glum| = 0.12) with substantial brightness (BCPL ≈ 8 M–1 cm–1). Simultaneously, the integrated Ir(III) antenna enables benign visible-light sensitization (λex = 425 nm), facilitating low-phototoxicity confocal imaging in HeLa cells. Crucially, the probe’s structural rigidity ensures exceptional stability against biological interferents; spectroscopic titration with ct-DNA confirms the preservation of chiroptical signals without conformational distortion. This work presents a general coordination strategy for constructing robust, bright, and visible-light-excitable rare-earth chiroptical materials, opening new avenues for specific chiroptical bioimaging and enantioselective sensing applications.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"57 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111238","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The synthesis and characterization of a series of mononuclear nonoxido [VIV(L2,3)2] (1–2) and dinuclear oxido [(VIVO)2(L1–3)2] (3–5) VIV complexes have been achieved using ONS donor halogen-substituted thiosemicarbazone (TSC) ligands (H2L1–3). The synthesized complexes (1–5) were characterized in the solid state and in aqueous media by using various physicochemical techniques. A comparison of the solution-phase stability and biological potential of the complexes indicated that 1–2 keep their identity in aqueous solution, while 3–5 partially transform into [VIVO(L1–3)(H2O)] and [VVO2(L1–3)]−. Analysis of 1–5 using spectroscopic methods as well as density functional theory (DFT) and docking studies demonstrated that they or their transformation products interact with bovine serum albumin (BSA) and calf thymus DNA (CT-DNA) through noncovalent and covalent binding. Cytotoxic assays against A549 (lung cancer) and MCF-7 (breast cancer) cell lines demonstrated that 1–5 exhibit significant activity, with IC50 values from 8.9 to 19.2 μM. Among them, 5 and its transformation fragments are more effective against both cells, indicating their potential efficacy against cancer. Potential V-based drugs 1–2 reveal efficient cellular internalization, with lysosomes being the primary targets, followed by mitochondria and the nucleus, leading to lysosomal disruption, an increase of reactive oxygen species (ROS) levels, and, ultimately, cellular apoptosis.
{"title":"Mononuclear Nonoxido vs Dinuclear Oxido VIV Metallodrugs: Solution Behavior, Biomolecular Binding, Cytotoxicity, and Internalization in Cells","authors":"Pratikshya Das Pattanayak,Sushree Aradhana Patra,Sanchita Das,Deepika Mohapatra,Sudhir Lima,Daniele Sanna,Federico Pisanu,Eugenio Garribba,Rupam Dinda","doi":"10.1021/acs.inorgchem.5c04486","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c04486","url":null,"abstract":"The synthesis and characterization of a series of mononuclear nonoxido [VIV(L2,3)2] (1–2) and dinuclear oxido [(VIVO)2(L1–3)2] (3–5) VIV complexes have been achieved using ONS donor halogen-substituted thiosemicarbazone (TSC) ligands (H2L1–3). The synthesized complexes (1–5) were characterized in the solid state and in aqueous media by using various physicochemical techniques. A comparison of the solution-phase stability and biological potential of the complexes indicated that 1–2 keep their identity in aqueous solution, while 3–5 partially transform into [VIVO(L1–3)(H2O)] and [VVO2(L1–3)]−. Analysis of 1–5 using spectroscopic methods as well as density functional theory (DFT) and docking studies demonstrated that they or their transformation products interact with bovine serum albumin (BSA) and calf thymus DNA (CT-DNA) through noncovalent and covalent binding. Cytotoxic assays against A549 (lung cancer) and MCF-7 (breast cancer) cell lines demonstrated that 1–5 exhibit significant activity, with IC50 values from 8.9 to 19.2 μM. Among them, 5 and its transformation fragments are more effective against both cells, indicating their potential efficacy against cancer. Potential V-based drugs 1–2 reveal efficient cellular internalization, with lysosomes being the primary targets, followed by mitochondria and the nucleus, leading to lysosomal disruption, an increase of reactive oxygen species (ROS) levels, and, ultimately, cellular apoptosis.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111266","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-04DOI: 10.1021/acs.inorgchem.5c05778
Manami Tanaka,Yasuhiro Niwa,Mizuki Watanabe
Ba3Mn2(1–x)V2xO8 (0 ≤ x5 ≤ 0.25) pigments were synthesized by a conventional solid-state reaction method. This study shows that diluting Mn5+ in the Mn-rich host Ba3Mn2O8 with V5+ provides a high-purity green hue. All samples were obtained in a single phase with the rhombohedral Ba3Mn2O8 structure (space group of R3̅m). Optical absorption bands of the samples were observed around 378 and 689 nm due to d–d transitions of Mn5+. Ba3Mn1.6V0.4O8 showed the pure green hue with a greenness value (−a*) of −31.1 and a hue angle (h°) of 179.9. The values are higher than those of the commercially available Cr2O3 pigments (a* = −16.73, h° = 140.6). XANES analysis confirmed the persistence of Mn5+, suggesting that the enhanced color purity was caused by crystal field modulation rather than a valence change. The decrease in the average Mn–O bond length determined from the Rietveld refinement and EXAFS analysis caused a blue shift of the absorption bands, resulting in a color evolution from yellowish-green to a vivid, high-purity green. Furthermore, the optimized pigment showed excellent thermal stability, humidity, and chemical stability, indicating its significant potential for practical use as a next-generation green pigment.
{"title":"V5+-Induced Crystal Field Modulation in Mn5+-Rich Ba3Mn2O8 for High-Purity Green Pigments","authors":"Manami Tanaka,Yasuhiro Niwa,Mizuki Watanabe","doi":"10.1021/acs.inorgchem.5c05778","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05778","url":null,"abstract":"Ba3Mn2(1–x)V2xO8 (0 ≤ x5 ≤ 0.25) pigments were synthesized by a conventional solid-state reaction method. This study shows that diluting Mn5+ in the Mn-rich host Ba3Mn2O8 with V5+ provides a high-purity green hue. All samples were obtained in a single phase with the rhombohedral Ba3Mn2O8 structure (space group of R3̅m). Optical absorption bands of the samples were observed around 378 and 689 nm due to d–d transitions of Mn5+. Ba3Mn1.6V0.4O8 showed the pure green hue with a greenness value (−a*) of −31.1 and a hue angle (h°) of 179.9. The values are higher than those of the commercially available Cr2O3 pigments (a* = −16.73, h° = 140.6). XANES analysis confirmed the persistence of Mn5+, suggesting that the enhanced color purity was caused by crystal field modulation rather than a valence change. The decrease in the average Mn–O bond length determined from the Rietveld refinement and EXAFS analysis caused a blue shift of the absorption bands, resulting in a color evolution from yellowish-green to a vivid, high-purity green. Furthermore, the optimized pigment showed excellent thermal stability, humidity, and chemical stability, indicating its significant potential for practical use as a next-generation green pigment.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"8 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111217","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-04DOI: 10.1021/acs.inorgchem.5c04163
Rafael Caprani,Philippe Martin,Damien Prieur,Julien Martinez,Florent Lebreton,Elena F. Bazarkina,Kristina O. Kvashnina,Denis Menut,Méghan Alibert,Stéphanie Lecoq,Nicolas Clavier
In the context of spent fuel recycling and the valorization of plutonium, (U,Pu)O2 mixed oxides (MOX) have been developed for use in French Pressurized Water Reactors (PWR). They are also leading candidates for some GEN IV reactor concepts, such as sodium-cooled fast reactors (SFR). One of the critical challenges in the nuclear industry is the mastery of the nuclear fuel cycle, specifically plutonium multirecycling. In order to achieve this goal, it is crucial to identify the secondary phases created during irradiation. In this work, (U,Pu)O2 MOX have been doped with 11 stable fission products (FP) (Sr, Y, La, Nd, Ce, Zr, Mo, Pd, Rh, Ru, Ba) to reproduce FP-based precipitates existing in the real spent fuel. The structural and microstructural properties of these secondary phases were characterized by coupling scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), Electron Probe MicroAnalysis (EPMA), and synchrotron techniques such as X-ray Absorption Spectroscopy (XAS) and Synchrotron Powder X-ray Diffraction (SP-XRD). This analysis highlights the relationship between the partial segregation among metallic FP (Mo, Pd, Rh, Ru) and their crystallographic structures, as well as the speciation shift of several FP induced by the addition of Ba. The synthesized SIMMOX samples present a secondary phase representative of irradiated MOX and can be used as an effective model material to study spent nuclear fuel and its reprocessing.
{"title":"Structural and Microstructural Characterization of Fission Product Phases in MOX Nuclear Fuel for Fast Neutron Reactors","authors":"Rafael Caprani,Philippe Martin,Damien Prieur,Julien Martinez,Florent Lebreton,Elena F. Bazarkina,Kristina O. Kvashnina,Denis Menut,Méghan Alibert,Stéphanie Lecoq,Nicolas Clavier","doi":"10.1021/acs.inorgchem.5c04163","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c04163","url":null,"abstract":"In the context of spent fuel recycling and the valorization of plutonium, (U,Pu)O2 mixed oxides (MOX) have been developed for use in French Pressurized Water Reactors (PWR). They are also leading candidates for some GEN IV reactor concepts, such as sodium-cooled fast reactors (SFR). One of the critical challenges in the nuclear industry is the mastery of the nuclear fuel cycle, specifically plutonium multirecycling. In order to achieve this goal, it is crucial to identify the secondary phases created during irradiation. In this work, (U,Pu)O2 MOX have been doped with 11 stable fission products (FP) (Sr, Y, La, Nd, Ce, Zr, Mo, Pd, Rh, Ru, Ba) to reproduce FP-based precipitates existing in the real spent fuel. The structural and microstructural properties of these secondary phases were characterized by coupling scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), Electron Probe MicroAnalysis (EPMA), and synchrotron techniques such as X-ray Absorption Spectroscopy (XAS) and Synchrotron Powder X-ray Diffraction (SP-XRD). This analysis highlights the relationship between the partial segregation among metallic FP (Mo, Pd, Rh, Ru) and their crystallographic structures, as well as the speciation shift of several FP induced by the addition of Ba. The synthesized SIMMOX samples present a secondary phase representative of irradiated MOX and can be used as an effective model material to study spent nuclear fuel and its reprocessing.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"9 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111236","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-03DOI: 10.1021/acs.inorgchem.5c05428
Mingyang Gu,Wenjun Fan,Haiyou Liu,Rui Ma,Junhao Ma,Rongxing He,Lei Zhou,Ming Li
Organic–inorganic hybrid metal halides (OIHMHs) have garnered significant attention for their exceptional photophysical properties and structural diversity. Zero-dimensional (0D) metal halides are particularly promising for anticounterfeiting and solid-state lighting (SSL) due to their outstanding optical properties and stability. However, achieving precise control over the synthesis of low-dimensional OIHMHs (LD-OIHMHs) remains challenging. This study reports the controlled synthesis of Cd2+-based OIHMHs, achieving structural dimensionality reduction from 1D to 0D through the strategic embedding of hydrated protons. The 0D structure exhibits an enhanced quantum confinement effect, leading to highly efficient luminescence. Furthermore, Sb3+ doping was employed to incorporate optically active centers, resulting in broadband yellow photoluminescence with a large Stokes shift originating from triplet self-trapped excitons in Sb-centered octahedra. The different luminescence properties of these Cd2+-based materials were successfully applied in anticounterfeiting. Additionally, a high-performance white light-emitting diode (WLED) was fabricated using the 0D 10% Sb3+-doped Cd2+-based material as a phosphor, achieving a color rendering index of 90.8 and a luminous efficiency of 43 lm/W, confirming its potential for SSL applications. This work demonstrates an effective strategy for the dimensional and optical engineering of LD-OIHMHs.
{"title":"Tailoring the Dimensionality of Metal Halides for Applications in Anticounterfeiting and High-Efficiency White Light-Emitting Diodes","authors":"Mingyang Gu,Wenjun Fan,Haiyou Liu,Rui Ma,Junhao Ma,Rongxing He,Lei Zhou,Ming Li","doi":"10.1021/acs.inorgchem.5c05428","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05428","url":null,"abstract":"Organic–inorganic hybrid metal halides (OIHMHs) have garnered significant attention for their exceptional photophysical properties and structural diversity. Zero-dimensional (0D) metal halides are particularly promising for anticounterfeiting and solid-state lighting (SSL) due to their outstanding optical properties and stability. However, achieving precise control over the synthesis of low-dimensional OIHMHs (LD-OIHMHs) remains challenging. This study reports the controlled synthesis of Cd2+-based OIHMHs, achieving structural dimensionality reduction from 1D to 0D through the strategic embedding of hydrated protons. The 0D structure exhibits an enhanced quantum confinement effect, leading to highly efficient luminescence. Furthermore, Sb3+ doping was employed to incorporate optically active centers, resulting in broadband yellow photoluminescence with a large Stokes shift originating from triplet self-trapped excitons in Sb-centered octahedra. The different luminescence properties of these Cd2+-based materials were successfully applied in anticounterfeiting. Additionally, a high-performance white light-emitting diode (WLED) was fabricated using the 0D 10% Sb3+-doped Cd2+-based material as a phosphor, achieving a color rendering index of 90.8 and a luminous efficiency of 43 lm/W, confirming its potential for SSL applications. This work demonstrates an effective strategy for the dimensional and optical engineering of LD-OIHMHs.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"295 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111240","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-03DOI: 10.1021/acs.inorgchem.5c05116
Iva Habenšus,Qi Sun,Andrei V. Astashkin,Lily J. North,Jean-Luc Brédas,Veaceslav Coropceanu,Elisa Tomat
Emission from doublet excited states in luminescent radicals enables the design of advantageous properties in optoelectronics and functional materials. Although most investigations focus on polychlorinated triarylmethyl radicals, several other classes of radical emitters are emerging. The tripyrrindione ligand forms a delocalized, luminescent radical when bound to closed-shell ions. Here, we investigate the redox chemistry, coordination, and photophysical properties of tripyrrindione in the presence of the Ag(I) ion, which is also a widely used oxidant. Two-electron oxidation of the ligand and metal insertion lead to a neutral, diamagnetic complex with T-shaped geometry at the metal center. Subsequent one-electron reduction yields a Ag(I)-bound tripyrrindione radical as confirmed by crystallographic, electrochemical, spectroscopic, and computational analyses. The air-sensitive, paramagnetic complex exhibits a fluorescence emission band at 653 nm, even though several absorption bands between 750 and 950 nm attest to excited states below the emissive state. Time-dependent DFT calculations attribute this anti-Kasha emission to the radiative decay of the D3 state, a feature rationalized by the slow internal conversion of the D3 state to the D2 state. Given their rich photophysics and ability to stabilize unpaired spins, tripyrrindiones and other oligopyrrolic pigments provide potentially valuable platforms for innovative design of radical emitters.
{"title":"Ligand-Based Redox Chemistry and Anti-Kasha Fluorescence in Silver(I) Tripyrrindione Radical","authors":"Iva Habenšus,Qi Sun,Andrei V. Astashkin,Lily J. North,Jean-Luc Brédas,Veaceslav Coropceanu,Elisa Tomat","doi":"10.1021/acs.inorgchem.5c05116","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05116","url":null,"abstract":"Emission from doublet excited states in luminescent radicals enables the design of advantageous properties in optoelectronics and functional materials. Although most investigations focus on polychlorinated triarylmethyl radicals, several other classes of radical emitters are emerging. The tripyrrindione ligand forms a delocalized, luminescent radical when bound to closed-shell ions. Here, we investigate the redox chemistry, coordination, and photophysical properties of tripyrrindione in the presence of the Ag(I) ion, which is also a widely used oxidant. Two-electron oxidation of the ligand and metal insertion lead to a neutral, diamagnetic complex with T-shaped geometry at the metal center. Subsequent one-electron reduction yields a Ag(I)-bound tripyrrindione radical as confirmed by crystallographic, electrochemical, spectroscopic, and computational analyses. The air-sensitive, paramagnetic complex exhibits a fluorescence emission band at 653 nm, even though several absorption bands between 750 and 950 nm attest to excited states below the emissive state. Time-dependent DFT calculations attribute this anti-Kasha emission to the radiative decay of the D3 state, a feature rationalized by the slow internal conversion of the D3 state to the D2 state. Given their rich photophysics and ability to stabilize unpaired spins, tripyrrindiones and other oligopyrrolic pigments provide potentially valuable platforms for innovative design of radical emitters.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"31 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111242","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-03DOI: 10.1021/acs.inorgchem.5c04404
Luis Craco, Bo Hou, Stefano Leoni
Normal-state Landau–Fermi-liquid (LFL) behavior is widely regarded as a prerequisite for low-temperature superconductivity in 1T-TiX2 (X = Se, Te) van der Waals (vdW) crystals. Clarifying this role requires a microscopic description of how local electron correlations and Ti–chalcogen covalence cooperate to shape the low-energy electronic structure in the noncharge-density-wave (non-CDW) regime. In the present work, we employ density functional theory combined with dynamical mean-field theory (DFT + DMFT) to investigate an extended multiorbital (MO) two-band Hubbard model specifically constructed for these transition-metal dichalcogenides. The calculations reveal an emergent LFL metal stabilized by dynamical intra- and interorbital correlations in the Ti-based manifold, while the chalcogen 4p/5p states remain comparatively rigid against changes in interaction strength. This orbital-selective reconstruction leads to a strongly anisotropic renormalization of the Ti-3d sector, which we identify as a key ingredient for the superconducting phase diagram of 1T-TiX2. Beyond demonstrating the capability of DFT + DMFT to capture such MO correlation effects, our results show that proximity to a correlated LFL state naturally accounts for the distinct low-temperature transport responses of the Se and Te compounds, where modest variations in interaction-to-bandwidth ratio and orbital occupancy drive markedly different sensitivities to external tuning parameters such as pressure, doping, or gating.
在1T-TiX2 （X = Se, Te）范德华（vdW）晶体中，正常状态的朗道-费米-液体（LFL）行为被广泛认为是低温超导的先决条件。澄清这一作用需要微观描述局部电子相关性和钛-硫共价如何在非电荷密度波（non-CDW）状态下合作形成低能电子结构。在本研究中，我们采用密度泛函理论结合动态平均场理论（DFT + DMFT）来研究专门为这些过渡金属二硫化物构建的扩展多轨道（MO）两波段Hubbard模型。计算结果表明，在钛基流形中，出现了一种由动态轨道内和轨道间关联稳定的低通量金属，而在相互作用强度变化的情况下，4p/5p态仍然保持相对刚性。这种轨道选择性重建导致Ti-3d扇区的强各向异性重整化，我们认为这是1T-TiX2超导相图的关键因素。除了证明DFT + DMFT捕获这种MO相关效应的能力之外，我们的研究结果表明，接近相关的LFL状态自然地解释了Se和Te化合物不同的低温输运响应，其中相互作用与带宽比和轨道占用的适度变化驱动了对外部调谐参数（如压力，掺杂或门控）的显着不同的敏感性。
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Pub Date : 2026-02-03DOI: 10.1021/acs.inorgchem.5c05472
Feng Gao, Xianqing Xie, Feng Luo
Efficient uranium extraction from seawater remains a highly challenging task due to the lack of an available approach to access a precise uranium-identified site in the adsorbent. To this end, we demonstrate herein a novel in situ self-assembly approach by directly using two organic molecules, 2,6-pyridinedicarboxaldehyde and terephthalohydrazide, to execute in situ in-plane self-assembly with [UO2(CO3)3]4–composite anions through both covalent Schiff base condensation and coordination with UO22+ ions. Through such a self-assembly approach, we can create a precise UO22+-identified site conveniently, thus allowing for not only a record uranium selectivity over vanadium (SU/V = 600) but also a uranium uptake of 16.91 mg/g from natural seawater in 7 days.
{"title":"Self-Assembly Approach for Uranium Extraction from Seawater","authors":"Feng Gao, Xianqing Xie, Feng Luo","doi":"10.1021/acs.inorgchem.5c05472","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05472","url":null,"abstract":"Efficient uranium extraction from seawater remains a highly challenging task due to the lack of an available approach to access a precise uranium-identified site in the adsorbent. To this end, we demonstrate herein a novel in situ self-assembly approach by directly using two organic molecules, 2,6-pyridinedicarboxaldehyde and terephthalohydrazide, to execute in situ in-plane self-assembly with [UO<sub>2</sub>(CO<sub>3</sub>)<sub>3</sub>]<sup>4–</sup>composite anions through both covalent Schiff base condensation and coordination with UO<sub>2</sub><sup>2+</sup> ions. Through such a self-assembly approach, we can create a precise UO<sub>2</sub><sup>2+</sup>-identified site conveniently, thus allowing for not only a record uranium selectivity over vanadium (<i>S</i><sub>U/V</sub> = 600) but also a uranium uptake of 16.91 mg/g from natural seawater in 7 days.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"44 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101945","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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