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Exploring Bonding Properties and Photophysical Behavior of Naphthoquinone-Based Rhenium(I) Tricarbonyl Complexes: A Combined Experimental and Theoretical Approach
IF 4.6 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-02-11 DOI: 10.1021/acs.inorgchem.4c04987
Tamara Maldonado, Belén Gómez-Arteaga, Lucas Lodeiro, Alberto Aravena, Geraldine Jara, Andrés Vega, Guillermo Ferraudi, Alejandra Gómez, Sebastián Gallardo-Fuentes
In this work, we describe the synthesis, characterization, and spectroscopic properties of four new rhenium(I) tricarbonyl complexes bearing a pyridyl imidazole-naphthoquinone (Py-Im-Nq) ligand. The spectroscopic, X-ray, and electrochemical analyses confirm the formation of neutral complexes in all cases. Although the Py-Im-Nq ligand possesses two distinct chelating fragments, we observed a selective formation of the N,N-isomer rather than the N,O-coordination. EDA calculations revealed that the origin of the N,N-linkage isomerism results from more favorable electrostatic interactions present in the N,N-coordination. Furthermore, EDA-NOCV analysis indicated that the bonding situation in these complexes can be described by the Dewar–Chatt–Duncanson model, providing a quantitative characterization of the donation and back-donation interaction components in these complexes. Finally, we examined the spectroscopic behavior (UV–vis and photoluminescence) of these new rhenium(I) complexes in solution. The characterization of the excited states was performed using TD-DFT and density difference isosurfaces. It was found that, in contrast to typical fac-[Re(NN)(CO)3L]0/+ systems, the low-lying transitions exhibit intraligand (IL) character, with charge transfer predominantly occurring from the imidazole ring to the carbonyl group in the quinone moiety. In contrast, a mixed metal-to-ligand charge transfer (MLCT)/IL transition is assigned to the electronic excitation at shorter wavelengths.
{"title":"Exploring Bonding Properties and Photophysical Behavior of Naphthoquinone-Based Rhenium(I) Tricarbonyl Complexes: A Combined Experimental and Theoretical Approach","authors":"Tamara Maldonado, Belén Gómez-Arteaga, Lucas Lodeiro, Alberto Aravena, Geraldine Jara, Andrés Vega, Guillermo Ferraudi, Alejandra Gómez, Sebastián Gallardo-Fuentes","doi":"10.1021/acs.inorgchem.4c04987","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04987","url":null,"abstract":"In this work, we describe the synthesis, characterization, and spectroscopic properties of four new rhenium(I) tricarbonyl complexes bearing a pyridyl imidazole-naphthoquinone (<b>Py-Im-Nq</b>) ligand. The spectroscopic, X-ray, and electrochemical analyses confirm the formation of neutral complexes in all cases. Although the <b>Py-Im-Nq</b> ligand possesses two distinct chelating fragments, we observed a selective formation of the <i>N</i>,<i>N</i>-isomer rather than the <i>N,O</i>-coordination. EDA calculations revealed that the origin of the <i>N</i>,<i>N</i>-linkage isomerism results from more favorable electrostatic interactions present in the <i>N</i>,<i>N</i>-coordination. Furthermore, EDA-NOCV analysis indicated that the bonding situation in these complexes can be described by the Dewar–Chatt–Duncanson model, providing a quantitative characterization of the donation and back-donation interaction components in these complexes. Finally, we examined the spectroscopic behavior (UV–vis and photoluminescence) of these new rhenium(I) complexes in solution. The characterization of the excited states was performed using TD-DFT and density difference isosurfaces. It was found that, in contrast to typical <i>fac</i>-[Re(NN)(CO)<sub>3</sub>L]<sup>0/+</sup> systems, the low-lying transitions exhibit intraligand (IL) character, with charge transfer predominantly occurring from the imidazole ring to the carbonyl group in the quinone moiety. In contrast, a mixed metal-to-ligand charge transfer (MLCT)/IL transition is assigned to the electronic excitation at shorter wavelengths.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"16 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385007","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}
引用次数: 0
Absence of Long-Range Magnetic Ordering in a Trirutile High-Entropy Oxide (Mn0.2Fe0.2Co0.2Ni0.2Cu0.2)Ta1.92O6−δ
IF 4.6 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-02-11 DOI: 10.1021/acs.inorgchem.4c04165
Gina Angelo, Liana Klivansky, Jeremy G. Philbrick, Tai Kong, Jian Zhang, Xin Gui
Functionalities of solid-state materials are usually considered to be dependent on their crystal structures. The limited structural types observed in the emerging high-entropy oxides put constraints on the exploration of their physical properties and potential applications. Herein, we synthesized the first high-entropy oxide in a trirutile structure, (Mn0.2Fe0.2Co0.2Ni0.2Cu0.2)Ta1.92O6−δ, and investigated its magnetism. The phase purity and high-entropy nature were confirmed by powder X-ray diffraction and energy-dispersive spectroscopy, respectively. X-ray photoelectron spectroscopy indicated divalent Mn, Co, Ni, and Cu along with trivalent Fe. Magnetic property measurements showed antiferromagnetic coupling and potential short-range magnetic ordering below ∼4 K. The temperature-dependent heat capacity data measured under zero and high magnetic fields confirmed the lack of long-range magnetic ordering and a possible low-temperature phonon excitation. The discovery of the first trirutile high-entropy oxide opens a new pathway for studying the relationship between the highly disordered atomic arrangement and magnetic interaction. Furthermore, it provides a new direction for exploring the functionalities of high-entropy oxides.
{"title":"Absence of Long-Range Magnetic Ordering in a Trirutile High-Entropy Oxide (Mn0.2Fe0.2Co0.2Ni0.2Cu0.2)Ta1.92O6−δ","authors":"Gina Angelo, Liana Klivansky, Jeremy G. Philbrick, Tai Kong, Jian Zhang, Xin Gui","doi":"10.1021/acs.inorgchem.4c04165","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04165","url":null,"abstract":"Functionalities of solid-state materials are usually considered to be dependent on their crystal structures. The limited structural types observed in the emerging high-entropy oxides put constraints on the exploration of their physical properties and potential applications. Herein, we synthesized the first high-entropy oxide in a trirutile structure, (Mn<sub>0.2</sub>Fe<sub>0.2</sub>Co<sub>0.2</sub>Ni<sub>0.2</sub>Cu<sub>0.2</sub>)Ta<sub>1.92</sub>O<sub>6−δ</sub>, and investigated its magnetism. The phase purity and high-entropy nature were confirmed by powder X-ray diffraction and energy-dispersive spectroscopy, respectively. X-ray photoelectron spectroscopy indicated divalent Mn, Co, Ni, and Cu along with trivalent Fe. Magnetic property measurements showed antiferromagnetic coupling and potential short-range magnetic ordering below ∼4 K. The temperature-dependent heat capacity data measured under zero and high magnetic fields confirmed the lack of long-range magnetic ordering and a possible low-temperature phonon excitation. The discovery of the first trirutile high-entropy oxide opens a new pathway for studying the relationship between the highly disordered atomic arrangement and magnetic interaction. Furthermore, it provides a new direction for exploring the functionalities of high-entropy oxides.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143384955","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}
引用次数: 0
Structural Reconstruction via Carbon Nanotube Spatially Confined Metal Catalysis: A Morphology-Controlled Approach to Convert Polycyclic Aromatic Hydrocarbon into Carbon Nanofibers for Highly Active Anodes in Li-Ion Batteries
IF 4.6 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-02-11 DOI: 10.1021/acs.inorgchem.4c05514
Ming Chen, Ming-Yang Zhao, Ke Liu, Feng-Ming Liu, Zhong-Yong Yuan, Xing Qian, Rong Wan, Chun-Sheng Li, Ai-Xiang Ding
By a carbon nanotube (CNT) spatially confined metal-catalyzed structural reconstruction, carbon nanofibers (CNFs) with a hollow, hollow-solid, solid graphite core, and CNT shell are prepared using nitrogen heterocycle (NHC) and polycyclic aromatic hydrocarbon (PAH) as carbon sources. The formation mechanism of CNFs with oriented graphene layers and enlarged intergraphene spacing is studied by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and selected area electron diffraction analysis. It revealed that this one-dimensional nanoconfined metal-catalyzed carbon rearrangement is totally different from the reported spatially localized metal-catalyzed graphitization of electrospun polymer and nanocasted carbohydrate nanofibers, as the graphene orientation, cavity volume, and interlayer distance of CNFs can be controlled by the carbon concentration-related competitive metal-catalyzed tip growth of latitudinal and longitudinal graphene layers from NHC and PAH. The unique CNF structure renders good electronic/ionic conductivity, abundant Li+ storage interlayer gaps, and robust mechanical durability, resulting in outstanding electrochemical properties as anodes in lithium-ion batteries. The optimum CNF anode delivers a stable discharge capacity of 475 mA h g–1 at 0.1 C, an extraordinary rate capability of 303 mA h g–1 at 5 C, and a remarkable long-term cycling stability of 378 mA h g-1 after 600 cycles at 1 C. This 1D nanoconfined metal catalysis synthesis could be useful for the development of efficient CNF anodes in many electrochemical reactions with a potential for industrial applications.
{"title":"Structural Reconstruction via Carbon Nanotube Spatially Confined Metal Catalysis: A Morphology-Controlled Approach to Convert Polycyclic Aromatic Hydrocarbon into Carbon Nanofibers for Highly Active Anodes in Li-Ion Batteries","authors":"Ming Chen, Ming-Yang Zhao, Ke Liu, Feng-Ming Liu, Zhong-Yong Yuan, Xing Qian, Rong Wan, Chun-Sheng Li, Ai-Xiang Ding","doi":"10.1021/acs.inorgchem.4c05514","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05514","url":null,"abstract":"By a carbon nanotube (CNT) spatially confined metal-catalyzed structural reconstruction, carbon nanofibers (CNFs) with a hollow, hollow-solid, solid graphite core, and CNT shell are prepared using nitrogen heterocycle (NHC) and polycyclic aromatic hydrocarbon (PAH) as carbon sources. The formation mechanism of CNFs with oriented graphene layers and enlarged intergraphene spacing is studied by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and selected area electron diffraction analysis. It revealed that this one-dimensional nanoconfined metal-catalyzed carbon rearrangement is totally different from the reported spatially localized metal-catalyzed graphitization of electrospun polymer and nanocasted carbohydrate nanofibers, as the graphene orientation, cavity volume, and interlayer distance of CNFs can be controlled by the carbon concentration-related competitive metal-catalyzed tip growth of latitudinal and longitudinal graphene layers from NHC and PAH. The unique CNF structure renders good electronic/ionic conductivity, abundant Li<sup>+</sup> storage interlayer gaps, and robust mechanical durability, resulting in outstanding electrochemical properties as anodes in lithium-ion batteries. The optimum CNF anode delivers a stable discharge capacity of 475 mA h g<sup>–1</sup> at 0.1 C, an extraordinary rate capability of 303 mA h g<sup>–1</sup> at 5 C, and a remarkable long-term cycling stability of 378 mA h g<sup>-1</sup> after 600 cycles at 1 C. This 1D nanoconfined metal catalysis synthesis could be useful for the development of efficient CNF anodes in many electrochemical reactions with a potential for industrial applications.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"79 5 Pt 1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143384958","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}
引用次数: 0
Zn(II)/La(III) Coordination Polymers Based on New Schiff Base Ligands for Highly Selective and Sensitive Detection of 2,4,6-Trinitrophenol
IF 4.6 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-02-10 DOI: 10.1021/acs.inorgchem.4c04679
Ruonan Xuan, Du Ran, Chao Yang, Yuanying Lin, Weisheng Liu
In recent years, nitro explosives have posed a threat to national security and human health due to their hazard and environmental contamination. The rapid and effective detection of nitro explosives remains a challenge. In this work, a new Schiff base ligand H2L was carefully designed and successfully synthesized, H2L = 1,1′-((1E,1′E)-(cyclohexane-1,4-diylbis (azanylidene)) bis (methylidene) bis (naphthalene-2-ol). Two new coordination polymers, [Zn2L2]n and [La(NO3)3 (H2L)2CH3OH]n, were constructed by a solvothermal reaction. The aforementioned coordination polymers were characterized by X-ray, PXRD, TGA, and FT-IR, and the results demonstrated that the Zn-CP and the La-CP exhibited a one-dimensional chain structure and a two-dimensional reticular structure. Given the excellent performance of coordination polymers (CPs) in the field of fluorescence analysis and sensing, fluorescence sensing experiments were conducted on nitro explosives. The experimental results demonstrated that Zn-CP exhibited high selectivity and sensitivity for the detection of 2,4,6-trinitrophenol (TNP) by fluorescence quenching, with a detection limit of 4 × 10–6 M. The detection limit of La-CP for TNP was even as low as 0.78 × 10–6 M, and the quenching effect constants KSV were 7.03 × 103 and 1.59 × 104 M–1. Through experimentation and density functional theory calculations, the observed fluorescence quenching can be attributed to three mechanisms: photoinduced electron transfer, resonance energy transfer, and electrostatic interactions between CPs and NACs. Moreover, sensor-coated portable test strip devices were fabricated for easy and rapid on-site detection of the TNP explosive.
{"title":"Zn(II)/La(III) Coordination Polymers Based on New Schiff Base Ligands for Highly Selective and Sensitive Detection of 2,4,6-Trinitrophenol","authors":"Ruonan Xuan, Du Ran, Chao Yang, Yuanying Lin, Weisheng Liu","doi":"10.1021/acs.inorgchem.4c04679","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04679","url":null,"abstract":"In recent years, nitro explosives have posed a threat to national security and human health due to their hazard and environmental contamination. The rapid and effective detection of nitro explosives remains a challenge. In this work, a new Schiff base ligand H<sub>2</sub>L was carefully designed and successfully synthesized, H<sub>2</sub>L = 1,1′-((1<i>E</i>,1′<i>E</i>)-(cyclohexane-1,4-diylbis (azanylidene)) bis (methylidene) bis (naphthalene-2-ol). Two new coordination polymers, [Zn<sub>2</sub>L<sub>2</sub>]<sub><i>n</i></sub> and [La(NO<sub>3</sub>)<sub>3</sub> (H<sub>2</sub>L)<sub>2</sub>CH<sub>3</sub>OH]<sub><i>n</i></sub>, were constructed by a solvothermal reaction. The aforementioned coordination polymers were characterized by X-ray, PXRD, TGA, and FT-IR, and the results demonstrated that the Zn-CP and the La-CP exhibited a one-dimensional chain structure and a two-dimensional reticular structure. Given the excellent performance of coordination polymers (CPs) in the field of fluorescence analysis and sensing, fluorescence sensing experiments were conducted on nitro explosives. The experimental results demonstrated that Zn-CP exhibited high selectivity and sensitivity for the detection of 2,4,6-trinitrophenol (TNP) by fluorescence quenching, with a detection limit of 4 × 10<sup>–6</sup> M. The detection limit of La-CP for TNP was even as low as 0.78 × 10<sup>–6</sup> M, and the quenching effect constants <i>K</i><sub>SV</sub> were 7.03 × 10<sup>3</sup> and 1.59 × 10<sup>4</sup> M<sup>–1</sup>. Through experimentation and density functional theory calculations, the observed fluorescence quenching can be attributed to three mechanisms: photoinduced electron transfer, resonance energy transfer, and electrostatic interactions between CPs and NACs. Moreover, sensor-coated portable test strip devices were fabricated for easy and rapid on-site detection of the TNP explosive.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"44 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375792","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}
引用次数: 0
Theoretical Investigations on the n-Type and p-Type Conductivity Mechanisms in BiTaO4 Photocatalysts through Intrinsic Point Defects and Group IIA and Group VIB Element Doping.
IF 4.3 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-02-10 Epub Date: 2025-01-31 DOI: 10.1021/acs.inorgchem.4c04888
HongChun Zheng, Song Ling, Bo Kong, Ti-Xian Zeng, Shan Jiang, Wentao Wang

The n-type and p-type conductivity mechanisms from intrinsic defects and Group IIA and Group VIB element doping in the photocatalyst BiTaO4 are systematically investigated by employing hybrid density functional calculations. The results reveal that vacancies VBi, VTa, VO, and antisite TaBi are the predominant defects, depending on growth conditions. Bi-rich, appropriate Ta-rich, and O-poor conditions can promote BiTaO4 to form n-type conductivity due to the presence of the TaBi donor defect and its easier ionization. This explains the experimental n-type conductivity character well. Meanwhile, under O-rich, Bi-poor, and Ta-poor conditions, BiTaO4 exhibits superior p-type conductivity by forming the excellent acceptor defects VBi and VTa. Moreover, the intrinsic p-type conductivity can be further strengthened via the introductions of the substitutional doping of MBi (M = Mg, Ca, Sr, and Ba) under the Bi-poor, Ta-poor, and O-rich conditions, where the O vacancies should be induced and Sr is the best candidate. On the other hand, Group VIB element (Cr, Mo, and W) doping can improve intrinsic n-type conductivity under Bi-rich, appropriate Ta-rich, and O-poor conditions. W is the best candidate. These findings provide a comprehensive understanding of defect physics in BiTaO4 and offer insights into optimizing its photocatalytic performance through targeted defect engineering and impurity doping.

{"title":"Theoretical Investigations on the n-Type and p-Type Conductivity Mechanisms in BiTaO<sub>4</sub> Photocatalysts through Intrinsic Point Defects and Group IIA and Group VIB Element Doping.","authors":"HongChun Zheng, Song Ling, Bo Kong, Ti-Xian Zeng, Shan Jiang, Wentao Wang","doi":"10.1021/acs.inorgchem.4c04888","DOIUrl":"10.1021/acs.inorgchem.4c04888","url":null,"abstract":"<p><p>The n-type and p-type conductivity mechanisms from intrinsic defects and Group IIA and Group VIB element doping in the photocatalyst BiTaO<sub>4</sub> are systematically investigated by employing hybrid density functional calculations. The results reveal that vacancies <i>V</i><sub>Bi</sub>, <i>V</i><sub>Ta</sub>, <i>V</i><sub>O</sub>, and antisite Ta<sub>Bi</sub> are the predominant defects, depending on growth conditions. Bi-rich, appropriate Ta-rich, and O-poor conditions can promote BiTaO<sub>4</sub> to form n-type conductivity due to the presence of the Ta<sub>Bi</sub> donor defect and its easier ionization. This explains the experimental n-type conductivity character well. Meanwhile, under O-rich, Bi-poor, and Ta-poor conditions, BiTaO<sub>4</sub> exhibits superior p-type conductivity by forming the excellent acceptor defects <i>V</i><sub>Bi</sub> and <i>V</i><sub>Ta</sub>. Moreover, the intrinsic p-type conductivity can be further strengthened via the introductions of the substitutional doping of M<sub>Bi</sub> (M = Mg, Ca, Sr, and Ba) under the Bi-poor, Ta-poor, and O-rich conditions, where the O vacancies should be induced and Sr is the best candidate. On the other hand, Group VIB element (Cr, Mo, and W) doping can improve intrinsic n-type conductivity under Bi-rich, appropriate Ta-rich, and O-poor conditions. W is the best candidate. These findings provide a comprehensive understanding of defect physics in BiTaO<sub>4</sub> and offer insights into optimizing its photocatalytic performance through targeted defect engineering and impurity doping.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":"2443-2457"},"PeriodicalIF":4.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143062439","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}
引用次数: 0
Water-Mediated Chiral Resolution of Ag–NHC(Nucleobase) Complexes
IF 4.6 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-02-10 DOI: 10.1021/acs.inorgchem.4c05384
Alvaro Polo, Ricardo Rodríguez, Ramón Macías, Daniel Cobo Paz, Pablo J. Sanz Miguel
This study reveals a novel role of water as a chiral inducer, demonstrating its ability to drive the asymmetric resolution of prochiral silver-nucleobase complexes. During crystallization, helical water columns spontaneously form, selectively recognizing one enantiomer of the silver complex. This enantiospecific interaction drives the separation of the P and M enantiomers, leading to the formation of enantiopure crystals, whose chirality was confirmed through X-ray crystallography.
{"title":"Water-Mediated Chiral Resolution of Ag–NHC(Nucleobase) Complexes","authors":"Alvaro Polo, Ricardo Rodríguez, Ramón Macías, Daniel Cobo Paz, Pablo J. Sanz Miguel","doi":"10.1021/acs.inorgchem.4c05384","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05384","url":null,"abstract":"This study reveals a novel role of water as a chiral inducer, demonstrating its ability to drive the asymmetric resolution of prochiral silver-nucleobase complexes. During crystallization, helical water columns spontaneously form, selectively recognizing one enantiomer of the silver complex. This enantiospecific interaction drives the separation of the <i>P</i> and <i>M</i> enantiomers, leading to the formation of enantiopure crystals, whose chirality was confirmed through X-ray crystallography.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"58 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375793","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}
引用次数: 0
Generalized Synthetic Strategies toward Oxygen Vacancy-Enriched ZnO–ZnS Hollow Porous Spheres with Enhanced Photocatalytic Hydrogen Evolution
IF 4.6 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-02-10 DOI: 10.1021/acs.inorgchem.4c05389
Yong Xie, Tingwei Wang, Huiquan Li, Chaozhong Sun, Jie Hu, Shunsheng Cao
Constructing a hollow porous ZnO–ZnS sphere is still a big challenge due to the difficulty in controlling the morphology and distribution of ZnO shell originating from the fact that ZnO prefers to grow along particular crystal planes. Here, we demonstrate a novel synthetic strategy for the preparation of oxygen-vacancy-enriched ZnO–ZnS hollow porous (Ov-ZOS (HP)) spheres by combining the concepts of adopting a template-directed method, selecting the sulfidation precursor, and tuning the calcination process of the template. Structural characterization and density functional theory (DFT) calculations reveal that hollow porous nanostructures and oxygen vacancies in the ZnO–ZnS heterojunction are beneficial in promoting efficient charge transfer and separation. The optimized Ov-ZOS (HP) exhibits enhanced rates of hydrogen evolution reaction (71.86 mmol h–1 g–1), which is 1.48, 2.08, and 3.0 times higher than those of ZnO–ZnS hollow porous spheres, oxygen vacancy-enriched ZnO–ZnS nanosheets, ZnO–ZnS nanosheets, respectively. Moreover, the Ov-ZOS (HP) presents excellent cyclability for photocatalytic hydrogen evolution. Therefore, this study provides physical insights into controlling the hollow porous nanostructures of various semiconductor heterojunctions that are hard to form through other existing strategies for solar energy utilization.
{"title":"Generalized Synthetic Strategies toward Oxygen Vacancy-Enriched ZnO–ZnS Hollow Porous Spheres with Enhanced Photocatalytic Hydrogen Evolution","authors":"Yong Xie, Tingwei Wang, Huiquan Li, Chaozhong Sun, Jie Hu, Shunsheng Cao","doi":"10.1021/acs.inorgchem.4c05389","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05389","url":null,"abstract":"Constructing a hollow porous ZnO–ZnS sphere is still a big challenge due to the difficulty in controlling the morphology and distribution of ZnO shell originating from the fact that ZnO prefers to grow along particular crystal planes. Here, we demonstrate a novel synthetic strategy for the preparation of oxygen-vacancy-enriched ZnO–ZnS hollow porous (Ov-ZOS (HP)) spheres by combining the concepts of adopting a template-directed method, selecting the sulfidation precursor, and tuning the calcination process of the template. Structural characterization and density functional theory (DFT) calculations reveal that hollow porous nanostructures and oxygen vacancies in the ZnO–ZnS heterojunction are beneficial in promoting efficient charge transfer and separation. The optimized Ov-ZOS (HP) exhibits enhanced rates of hydrogen evolution reaction (71.86 mmol h<sup>–1</sup> g<sup>–1</sup>), which is 1.48, 2.08, and 3.0 times higher than those of ZnO–ZnS hollow porous spheres, oxygen vacancy-enriched ZnO–ZnS nanosheets, ZnO–ZnS nanosheets, respectively. Moreover, the Ov-ZOS (HP) presents excellent cyclability for photocatalytic hydrogen evolution. Therefore, this study provides physical insights into controlling the hollow porous nanostructures of various semiconductor heterojunctions that are hard to form through other existing strategies for solar energy utilization.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"41 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375794","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}
引用次数: 0
A Porphyrin-Based Metal–Organic Framework Nanozyme with Superior Peroxidase-like Activity for Combating Antibacterial Infections and Promoting Wound Healing
IF 4.6 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-02-10 DOI: 10.1021/acs.inorgchem.4c05258
Han-Xiao Feng, Zijie Zhou, Jilin Jiang, Yi-Fei Hui, Bing-Xin Li, Shulin Li, Huiling Guo, Fa-Qiang Tang, Zu-Jin Lin, Lai-Peng Yan
As an antibacterial agent, H2O2 is widely used to combat pathogenic bacterial infections clinically. To mitigate potential side effects associated with a high dosage of H2O2, it is pivotal to improve its antibacterial efficacy. Herein, a nanoscale porphyrin-based mesoporous metal–organic framework (MOF) nanozyme, Nano-PCN-222(Fe), was readily prepared by a one pot. Nano-PCN-222(Fe) shows a striking peroxidase (POD)-like activity comparable to that of natural enzyme horse radish peroxidase. Such a high POD-like activity of Nano-PCN-222(Fe) nanozyme is primarily attributed to both the monodispersion and the accessibility of single-atom catalytic sites Fe within the framework. As a consequence of its ability to effectively catalyze the decomposition of H2O2 into more toxic hydroxyl radicals, Nano-PCN-222(Fe) shows excellent antibacterial activity against both Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria with the assistance of H2O2. Remarkably, only 10 mM H2O2 is sufficient to fully kill E. coli and S. aureus in the presence of Nano-PCN-222(Fe) (10 ppm), which is significantly lower than that used in actual clinical disinfection (166–1000 mM). Moreover, Nano-PCN-222(Fe) could significantly accelerate infected wound healing due to its superior antimicrobial activity. Additionally, no appreciable biotoxicity of Nano-PCN-222(Fe) was observed even though its dosage was up to 30 ppm.
{"title":"A Porphyrin-Based Metal–Organic Framework Nanozyme with Superior Peroxidase-like Activity for Combating Antibacterial Infections and Promoting Wound Healing","authors":"Han-Xiao Feng, Zijie Zhou, Jilin Jiang, Yi-Fei Hui, Bing-Xin Li, Shulin Li, Huiling Guo, Fa-Qiang Tang, Zu-Jin Lin, Lai-Peng Yan","doi":"10.1021/acs.inorgchem.4c05258","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05258","url":null,"abstract":"As an antibacterial agent, H<sub>2</sub>O<sub>2</sub> is widely used to combat pathogenic bacterial infections clinically. To mitigate potential side effects associated with a high dosage of H<sub>2</sub>O<sub>2</sub>, it is pivotal to improve its antibacterial efficacy. Herein, a nanoscale porphyrin-based mesoporous metal–organic framework (MOF) nanozyme, Nano-PCN-222(Fe), was readily prepared by a one pot. Nano-PCN-222(Fe) shows a striking peroxidase (POD)-like activity comparable to that of natural enzyme horse radish peroxidase. Such a high POD-like activity of Nano-PCN-222(Fe) nanozyme is primarily attributed to both the monodispersion and the accessibility of single-atom catalytic sites Fe within the framework. As a consequence of its ability to effectively catalyze the decomposition of H<sub>2</sub>O<sub>2</sub> into more toxic hydroxyl radicals, Nano-PCN-222(Fe) shows excellent antibacterial activity against both Gram-negative (<i>Escherichia coli</i>) and Gram-positive (<i>Staphylococcus aureus</i>) bacteria with the assistance of H<sub>2</sub>O<sub>2</sub>. Remarkably, only 10 mM H<sub>2</sub>O<sub>2</sub> is sufficient to fully kill <i>E. coli</i> and <i>S. aureus</i> in the presence of Nano-PCN-222(Fe) (10 ppm), which is significantly lower than that used in actual clinical disinfection (166–1000 mM). Moreover, Nano-PCN-222(Fe) could significantly accelerate infected wound healing due to its superior antimicrobial activity. Additionally, no appreciable biotoxicity of Nano-PCN-222(Fe) was observed even though its dosage was up to 30 ppm.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"47 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143384959","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}
引用次数: 0
Studies on a Urea-Complexed Iron(III) Dichromate, a Precursor of Chromium-Rich Nanospinel Catalysts Prepared for the Reductive Transformation of Carbon Dioxide
IF 4.6 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-02-10 DOI: 10.1021/acs.inorgchem.4c05009
Kende Attila Béres, Zoltán Homonnay, Laura Bereczki, Vladimir M. Petruševski, Attila Farkas, Zsuzsanna Czégény, Péter Németh, Péter Pekker, Fanni Béres-Szilágyi, Tomáš Stryšovský, Libor Kvitek, Ágnes Gömöry, László Kótai
Energy-saving and cost-efficient reaction routes to prepare highly active catalysts for CO2 hydrogenation or solid oxide fuel cells (SOFCs) are enormously important. In this paper, we report a detailed study of a dichromate salt of [Fe(urea)6]3+, a member of the [M(urea)6]3+ complex family (M = Fe, Al, Mn, Cr, V, or Ti) with oxidizing anions, which is a promising precursor of a Cr-rich mixed chromium iron oxide catalyst prepared at a low temperature in the solid phase. The single-crystal X-ray structure, various (infrared, ultraviolet–visible, and Raman) spectroscopic studies, and thermal analysis (differential scanning calorimetry and thermogravimetric analysis/mass spectrometry) of [hexakis(urea-O)iron(III)] dichromate {[Fe(urea-O)6]2(Cr2O7)3} and its decomposition products confirmed the presence of a quasi-intramolecular redox reaction between the urea ligands and dichromate anions. The redox reactions result in various mixed Cr–Fe oxides with amorphous structure, whereas above 550 °C, the crystal structure and composition of the final products depend on the atmosphere during the thermal decomposition. The iron–chromium mixed oxides are potential catalysts in CO2 hydrogenation that afford CO, CH4, C2H6, and C3H8. Furthermore, our Mössbauer spectroscopy studies show a possible electron hopping between the FeII and FeIII ions at the tetrahedral sites of the spinel structure, which suggests that the formed chromite is also a potential SOFC material. Our study also demonstrates that hexaureairon(III) dichromate is a selective oxidation agent of sulfur-containing organic compounds.
{"title":"Studies on a Urea-Complexed Iron(III) Dichromate, a Precursor of Chromium-Rich Nanospinel Catalysts Prepared for the Reductive Transformation of Carbon Dioxide","authors":"Kende Attila Béres, Zoltán Homonnay, Laura Bereczki, Vladimir M. Petruševski, Attila Farkas, Zsuzsanna Czégény, Péter Németh, Péter Pekker, Fanni Béres-Szilágyi, Tomáš Stryšovský, Libor Kvitek, Ágnes Gömöry, László Kótai","doi":"10.1021/acs.inorgchem.4c05009","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05009","url":null,"abstract":"Energy-saving and cost-efficient reaction routes to prepare highly active catalysts for CO<sub>2</sub> hydrogenation or solid oxide fuel cells (SOFCs) are enormously important. In this paper, we report a detailed study of a dichromate salt of [Fe(urea)<sub>6</sub>]<sup>3+</sup>, a member of the [<i>M</i>(urea)<sub>6</sub>]<sup>3+</sup> complex family (<i>M</i> = Fe, Al, Mn, Cr, V, or Ti) with oxidizing anions, which is a promising precursor of a Cr-rich mixed chromium iron oxide catalyst prepared at a low temperature in the solid phase. The single-crystal X-ray structure, various (infrared, ultraviolet–visible, and Raman) spectroscopic studies, and thermal analysis (differential scanning calorimetry and thermogravimetric analysis/mass spectrometry) of [hexakis(urea-<i>O</i>)iron(III)] dichromate {[Fe(urea-O)<sub>6</sub>]<sub>2</sub>(Cr<sub>2</sub>O<sub>7</sub>)<sub>3</sub>} and its decomposition products confirmed the presence of a quasi-intramolecular redox reaction between the urea ligands and dichromate anions. The redox reactions result in various mixed Cr–Fe oxides with amorphous structure, whereas above 550 °C, the crystal structure and composition of the final products depend on the atmosphere during the thermal decomposition. The iron–chromium mixed oxides are potential catalysts in CO<sub>2</sub> hydrogenation that afford CO, CH<sub>4</sub>, C<sub>2</sub>H<sub>6</sub>, and C<sub>3</sub>H<sub>8</sub>. Furthermore, our Mössbauer spectroscopy studies show a possible electron hopping between the Fe<sup>II</sup> and Fe<sup>III</sup> ions at the tetrahedral sites of the spinel structure, which suggests that the formed chromite is also a potential SOFC material. Our study also demonstrates that hexaureairon(III) dichromate is a selective oxidation agent of sulfur-containing organic compounds.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"62 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143384957","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}
引用次数: 0
Reductive Coupling of Ketones: Contrasting the Reactivity of an Aluminyl and a Gallyl Anion
IF 4.6 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2025-02-10 DOI: 10.1021/acs.inorgchem.4c05519
Andrea O’Reilly, Rebecca A. Robson, Matthew J. Evans, J. Robin Fulton, Martyn P. Coles
The synthesis of a new potassium gallyl system, K[Ga(NON)] ([NON]2– = [O(SiMe2NDipp)2]2–, Dipp = 2,6-iPr2C6H3), has been reported, and its reactivity toward a variety of ketones has been studied. The potassium gallyl is initially isolated as the contacted dimeric pair (CDP) [K{Ga(NON)}]2 but can be converted to the monomeric ion pair (MIP) (NON)Ga–K(TMEDA)2 or the separated ion pair (SIP) [K(222-crypt)][Ga(NON)] upon addition of coordinating polydentate ligands. The reaction of the CDP with two equivalents of benzophenone or 9-fluorenone per gallium center generates homocoupled pinacolate products. However, the reaction with acetophenone initially forms a gallium 1,3-phenylethene-1-olate, which C–C couples to a second equivalent of acetophenone to form an unprecedented gallium 1,3-diphenylbutane-1,3-diolate. This reactivity is contrasted with the analogous potassium aluminyl CDP [K{Al(NON)}]2, where preferential formation of the pinacolate product is observed under the same reaction conditions.
{"title":"Reductive Coupling of Ketones: Contrasting the Reactivity of an Aluminyl and a Gallyl Anion","authors":"Andrea O’Reilly, Rebecca A. Robson, Matthew J. Evans, J. Robin Fulton, Martyn P. Coles","doi":"10.1021/acs.inorgchem.4c05519","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05519","url":null,"abstract":"The synthesis of a new potassium gallyl system, K[Ga(NON)] ([NON]<sup>2–</sup> = [O(SiMe<sub>2</sub>NDipp)<sub>2</sub>]<sup>2–</sup>, Dipp = 2,6-<i>i</i>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>), has been reported, and its reactivity toward a variety of ketones has been studied. The potassium gallyl is initially isolated as the contacted dimeric pair (CDP) [K{Ga(NON)}]<sub>2</sub> but can be converted to the monomeric ion pair (MIP) (NON)Ga–K(TMEDA)<sub>2</sub> or the separated ion pair (SIP) [K(222-crypt)][Ga(NON)] upon addition of coordinating polydentate ligands. The reaction of the CDP with two equivalents of benzophenone or 9-fluorenone per gallium center generates homocoupled pinacolate products. However, the reaction with acetophenone initially forms a gallium 1,3-phenylethene-1-olate, which C–C couples to a second equivalent of acetophenone to form an unprecedented gallium 1,3-diphenylbutane-1,3-diolate. This reactivity is contrasted with the analogous potassium aluminyl CDP [K{Al(NON)}]<sub>2</sub>, where preferential formation of the pinacolate product is observed under the same reaction conditions.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"29 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143384956","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}
引用次数: 0
期刊
Inorganic Chemistry
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