The development of birefringent materials, espcially for infrared (IR) birefringent crystals, has been limited by conflicting microstructural requirements, such as broad transmission range, wide band gap, and large birefringence. In this work, we propose a “low-dimensional motif intercalation” strategy for designing high-perfomance birefringent materials. Utilizing the layered selenophosphorus Ba₃P₂Se₈ as a prototype compound, a novel IR birefringent crystal Ba₄HgP₂Se₁₀ with enhanced birefringence was successfully synthesized by the intercalation of the linear [HgSe₂]2- moieties, while the outstanding optical properties such as wide band gap and long IR cutoff are maintained.Notably, Ba₄HgP₂Se₁₀ crystal exhibits the largest band gap among known selenophosphorus compounds, accompanied with wide IR transmittance range and substantial birefringence. Theoretical calculations reveal that the outstanding optical properties of Ba₄HgP₂Se₁₀ arise from the synergistic interaction between Ba²⁺ cations, [HgSe₂]2- anions, and layered selenophosphorus framework.
{"title":"Design of high-performance infrared birefringent crystal Ba4HgP2Se10 via a low-dimensional motif intercalation strategy","authors":"Zhihui Xiong, Haotian Tian, Zhixi Li, Guowei Deng, Fang Ding, Qian Wu, Mingjun Xia","doi":"10.1039/d5dt00186b","DOIUrl":"https://doi.org/10.1039/d5dt00186b","url":null,"abstract":"The development of birefringent materials, espcially for infrared (IR) birefringent crystals, has been limited by conflicting microstructural requirements, such as broad transmission range, wide band gap, and large birefringence. In this work, we propose a “low-dimensional motif intercalation” strategy for designing high-perfomance birefringent materials. Utilizing the layered selenophosphorus Ba₃P₂Se₈ as a prototype compound, a novel IR birefringent crystal Ba₄HgP₂Se₁₀ with enhanced birefringence was successfully synthesized by the intercalation of the linear [HgSe₂]2- moieties, while the outstanding optical properties such as wide band gap and long IR cutoff are maintained.Notably, Ba₄HgP₂Se₁₀ crystal exhibits the largest band gap among known selenophosphorus compounds, accompanied with wide IR transmittance range and substantial birefringence. Theoretical calculations reveal that the outstanding optical properties of Ba₄HgP₂Se₁₀ arise from the synergistic interaction between Ba²⁺ cations, [HgSe₂]2- anions, and layered selenophosphorus framework.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"21 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806353","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A series of six isomeric rhenium(I) tricarbonyl complexes featuring asymmetric diimine ligands 5,7-di-tert-butyl-2-(pyridin-2-yl)benzo[d]oxazole, 2-(pyridin-2-yl)naphtho[1,2-d]oxazole, 2-(pyridin-2-yl)naphtho[2,3-d]oxazole, 2-(quinolin-2-yl)benzo[d]oxazole, 2-(quinolin-2-yl)naphtho[1,2-d]oxazole, and 2-(isoquinolin-1-yl)benzo[d]oxazole, was synthesized and comprehensively characterized through analytical techniques, spectroscopy, and single-crystal X-ray diffraction. These complexes were assessed as catalysts for visible-light-driven CO2 reduction, both with and without an external photosensitizer (PS), and also exhibited catalytic activity in electrochemical CO2 reduction, effectively functioning in both regimes. In the presence of a proton donor, trifluoroethanol (TFE), the complexes produced methane and carbon monoxide (CO) electrochemically. Under photochemical conditions, high selectivity for CO production was achieved in acetonitrile with triethanolamine (TEOA) as the proton source. This work highlights the tunability of metal complex photocatalysts for solar-to-fuel conversion through ligand design. Among the complexes studied, the rhenium complex featuring the 2-(pyridin-2-yl)naphtho[1,2-d]oxazole ligand demonstrated the highest catalytic efficiency, achieving a turnover number of 660 for CO2 reduction to CO after 5 hours. Mechanistic studies employing NMR, UV-vis spectroscopy, and time-dependent density functional theory (TD-DFT) calculations provided insights into the catalytic process. These rhenium(I) complexes demonstrate promising potential for photocatalytic CO2 reduction to CO, offering valuable insights into the design and development of efficient catalysts for artificial photosynthesis and solar-to-fuel conversion.
{"title":"Highly efficient photocatalytic reduction of CO2 to CO under visible light using rhenium benzo[d]oxazole complexes","authors":"Uday Shee, Biswajit Khutia, Sneha Ray, Sumona Ghosh, Kajal Krishna Rajak","doi":"10.1039/d4dt03400g","DOIUrl":"https://doi.org/10.1039/d4dt03400g","url":null,"abstract":"A series of six isomeric rhenium(<small>I</small>) tricarbonyl complexes featuring asymmetric diimine ligands 5,7-di-<em>tert</em>-butyl-2-(pyridin-2-yl)benzo[<em>d</em>]oxazole, 2-(pyridin-2-yl)naphtho[1,2-<em>d</em>]oxazole, 2-(pyridin-2-yl)naphtho[2,3-<em>d</em>]oxazole, 2-(quinolin-2-yl)benzo[<em>d</em>]oxazole, 2-(quinolin-2-yl)naphtho[1,2-<em>d</em>]oxazole, and 2-(isoquinolin-1-yl)benzo[<em>d</em>]oxazole, was synthesized and comprehensively characterized through analytical techniques, spectroscopy, and single-crystal X-ray diffraction. These complexes were assessed as catalysts for visible-light-driven CO<small><sub>2</sub></small> reduction, both with and without an external photosensitizer (PS), and also exhibited catalytic activity in electrochemical CO<small><sub>2</sub></small> reduction, effectively functioning in both regimes. In the presence of a proton donor, trifluoroethanol (TFE), the complexes produced methane and carbon monoxide (CO) electrochemically. Under photochemical conditions, high selectivity for CO production was achieved in acetonitrile with triethanolamine (TEOA) as the proton source. This work highlights the tunability of metal complex photocatalysts for solar-to-fuel conversion through ligand design. Among the complexes studied, the rhenium complex featuring the 2-(pyridin-2-yl)naphtho[1,2-<em>d</em>]oxazole ligand demonstrated the highest catalytic efficiency, achieving a turnover number of 660 for CO<small><sub>2</sub></small> reduction to CO after 5 hours. Mechanistic studies employing NMR, UV-vis spectroscopy, and time-dependent density functional theory (TD-DFT) calculations provided insights into the catalytic process. These rhenium(<small>I</small>) complexes demonstrate promising potential for photocatalytic CO<small><sub>2</sub></small> reduction to CO, offering valuable insights into the design and development of efficient catalysts for artificial photosynthesis and solar-to-fuel conversion.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"25 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806356","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Feiyang Tian, Ruixue Cheng, Yujing Shang, Le Pan, Xiuyun Cui, Xuekai Jiang, Kai Chen, Hua-Jun Zhao, Kuiyuan Wang
Cucurbit[n]urils, owing to their unique structural features, exhibit versatility in performing tasks such as adsorption, detection, and catalysis. However, the scope of their catalytic applications remains limited, primarily because most Cucurbituril-based catalytic reactions take place in either aqueous or organic phases. In this study, we have successfully synthesized porous honeycomb composites of cucurbit[6]uril with cobalt and nickel (denoted as Q[6]@Co and Q[6]@Ni, respectively) and applied them in a photothermal synergistic heterogeneous gas-solid reaction for the reduction of nitrogen to ammonia under mild conditions. This represents a groundbreaking achievement, as it is the first instance where a cucurbit[n]uril-based material has demonstrated catalytic functionality in its solid-state form, thereby introducing a novel concept for the design and application of cucurbit[n]uril-based photocatalysts. To characterize the structure of these composites, we employed a range of techniques including XAFS (X-ray Absorption Fine Structure), TEM (Transmission Electron Microscopy), SEM (Scanning Electron Microscopy), XPS (X-ray Photoelectron Spectroscopy), and H2-TPR (Hydrogen Temperature-Programmed Reduction). Our findings revealed that Q[6]@Ni exhibits higher photothermal catalytic ammonia synthesis activity compared to Q[6]@Co. This enhanced activity is attributed to the strong metal-support interaction (MSI) between Ni and Q[6], which facilitates electron transfer and nitrogen activation. Furthermore, the thermal source promotes the transition of electrons from the valence band to the conduction band, thereby enhancing the cleavage of the N≡N bond. Notably, the band gaps of Q[6]@Co and Q[6]@Ni are significantly reduced. In particular, Q[6]@Ni demonstrates the highest efficiency in electron-hole pair separation, as evidenced by PL (Photoluminescence) and EIS (Electrochemical Impedance Spectroscopy) measurements. Overall, Q[6]@Co/Ni provides an effective pathway for nitrogen reduction under mild conditions and advances the application of Cucurbituril-based materials in photothermal catalysis. This work also contributes to the development of environmentally sustainable ammonia synthesis technology.
{"title":"Preparation of Ni/Co Composite Materials Based on Cucurbit[6]uril and Their Photothermal Synergistic Catalysis for Nitrogen Reduction to Ammonia under Mild Conditions","authors":"Feiyang Tian, Ruixue Cheng, Yujing Shang, Le Pan, Xiuyun Cui, Xuekai Jiang, Kai Chen, Hua-Jun Zhao, Kuiyuan Wang","doi":"10.1039/d5dt00418g","DOIUrl":"https://doi.org/10.1039/d5dt00418g","url":null,"abstract":"Cucurbit[n]urils, owing to their unique structural features, exhibit versatility in performing tasks such as adsorption, detection, and catalysis. However, the scope of their catalytic applications remains limited, primarily because most Cucurbituril-based catalytic reactions take place in either aqueous or organic phases. In this study, we have successfully synthesized porous honeycomb composites of cucurbit[6]uril with cobalt and nickel (denoted as Q[6]@Co and Q[6]@Ni, respectively) and applied them in a photothermal synergistic heterogeneous gas-solid reaction for the reduction of nitrogen to ammonia under mild conditions. This represents a groundbreaking achievement, as it is the first instance where a cucurbit[n]uril-based material has demonstrated catalytic functionality in its solid-state form, thereby introducing a novel concept for the design and application of cucurbit[n]uril-based photocatalysts. To characterize the structure of these composites, we employed a range of techniques including XAFS (X-ray Absorption Fine Structure), TEM (Transmission Electron Microscopy), SEM (Scanning Electron Microscopy), XPS (X-ray Photoelectron Spectroscopy), and H2-TPR (Hydrogen Temperature-Programmed Reduction). Our findings revealed that Q[6]@Ni exhibits higher photothermal catalytic ammonia synthesis activity compared to Q[6]@Co. This enhanced activity is attributed to the strong metal-support interaction (MSI) between Ni and Q[6], which facilitates electron transfer and nitrogen activation. Furthermore, the thermal source promotes the transition of electrons from the valence band to the conduction band, thereby enhancing the cleavage of the N≡N bond. Notably, the band gaps of Q[6]@Co and Q[6]@Ni are significantly reduced. In particular, Q[6]@Ni demonstrates the highest efficiency in electron-hole pair separation, as evidenced by PL (Photoluminescence) and EIS (Electrochemical Impedance Spectroscopy) measurements. Overall, Q[6]@Co/Ni provides an effective pathway for nitrogen reduction under mild conditions and advances the application of Cucurbituril-based materials in photothermal catalysis. This work also contributes to the development of environmentally sustainable ammonia synthesis technology.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"40 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806364","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Biplab Mondal, Riya Ghosh, Rakesh Mazumdar, Bapan Samanta, Shankhadeep Saha
A high-spin iron(II) nitrosyl, [(TPz)Fe(NO)](ClO4)2, 2 (TPz = Tris(3,5-dimethylpyrazol-1-ylmethyl)amine) was synthesized and characterized structurally. Dioxygen reactivity of complex 2 in acetonitrile solution results in the oxidation of the ligand. Chemical evidence suggests the involvement of a peroxynitrite intermediate in this reaction. Trapping experiment shows the formation of NO2 during the reaction which supports the proposition of the involvement of the peroxynitrite intermediate. This study gives an insight into an alternate possibility from the dioxygen reactivity of metal-nitrosyl leading to NOD activity.
{"title":"Reaction of a non-heme iron-nitrosyl with dioxygen: Decomposition of the ligand through NOD-like activity","authors":"Biplab Mondal, Riya Ghosh, Rakesh Mazumdar, Bapan Samanta, Shankhadeep Saha","doi":"10.1039/d5dt00009b","DOIUrl":"https://doi.org/10.1039/d5dt00009b","url":null,"abstract":"A high-spin iron(II) nitrosyl, [(TPz)Fe(NO)](ClO4)2, 2 (TPz = Tris(3,5-dimethylpyrazol-1-ylmethyl)amine) was synthesized and characterized structurally. Dioxygen reactivity of complex 2 in acetonitrile solution results in the oxidation of the ligand. Chemical evidence suggests the involvement of a peroxynitrite intermediate in this reaction. Trapping experiment shows the formation of NO2 during the reaction which supports the proposition of the involvement of the peroxynitrite intermediate. This study gives an insight into an alternate possibility from the dioxygen reactivity of metal-nitrosyl leading to NOD activity.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"74 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797895","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yaohao Zhang, Chuanmu Tian, Tianshu Jiang, Wei Li, Marcus Einert, Jan Philipp Hofmann, Leopoldo Molina-Luna, Ralf Riedel, Zhaoju Yu
In this study, a novel carbon-rich Ni2Si/SiOC ceramic composite was successfully synthesized by polymer-derived ceramic approach, which is found to be catalytically active in the field of oxygen evolution reaction (OER). The synthesis involves the reaction of a commercially available carbon-rich polysiloxane precursor SPR-684 and nickel acetylacetonate, forming a Ni-containing single-source-precursor (SSP). Besides, to investigate the influence of porosity on OER performance, polystyrene (PS) was used as a sacrificial template for pore formation. Thermal treatment of the obtained mixture of SSP and PS at 1400 °C leads to the Ni2Si particles being encapsulated by structural ordered carbon, potentially enhancing the electrical conductivity of the composite. And the sample prepared at 1400 °C presented weight fractions of the crystalline phases Ni2Si and SiC in the amounts of 39.6 wt% and 29.3 wt%, respectively. Regarding the OER performance, with the support of increased conductive carbon formation, the sample obtained at 1400 °C demonstrated the best overpotential of 336 mV versus the reversible hydrogen electrode (RHE) at a current density of 10 mA cm⁻² in 1 M KOH, indicating enhanced performance in the oxygen evolution reaction region.
{"title":"Single-source-precursor synthesis of porous Ni2Si/SiOC composites as oxygen evolution reaction electrocatalyst","authors":"Yaohao Zhang, Chuanmu Tian, Tianshu Jiang, Wei Li, Marcus Einert, Jan Philipp Hofmann, Leopoldo Molina-Luna, Ralf Riedel, Zhaoju Yu","doi":"10.1039/d5dt00349k","DOIUrl":"https://doi.org/10.1039/d5dt00349k","url":null,"abstract":"In this study, a novel carbon-rich Ni2Si/SiOC ceramic composite was successfully synthesized by polymer-derived ceramic approach, which is found to be catalytically active in the field of oxygen evolution reaction (OER). The synthesis involves the reaction of a commercially available carbon-rich polysiloxane precursor SPR-684 and nickel acetylacetonate, forming a Ni-containing single-source-precursor (SSP). Besides, to investigate the influence of porosity on OER performance, polystyrene (PS) was used as a sacrificial template for pore formation. Thermal treatment of the obtained mixture of SSP and PS at 1400 °C leads to the Ni2Si particles being encapsulated by structural ordered carbon, potentially enhancing the electrical conductivity of the composite. And the sample prepared at 1400 °C presented weight fractions of the crystalline phases Ni2Si and SiC in the amounts of 39.6 wt% and 29.3 wt%, respectively. Regarding the OER performance, with the support of increased conductive carbon formation, the sample obtained at 1400 °C demonstrated the best overpotential of 336 mV versus the reversible hydrogen electrode (RHE) at a current density of 10 mA cm⁻² in 1 M KOH, indicating enhanced performance in the oxygen evolution reaction region.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"87 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797887","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Fency Sunny, Priyakumari Chakkingal Parambil, Nandakumar Kalarikkal, K. B. Subila
Lead free halide perovskites have been explored ardently for optoelectronic applications. Organic-Inorganic hybrid halide perovskites have shown promise with novel optical properties, bandgap tuning and improved carrier dynamics while introducing a quantum well structure. Herein, we have incorporated phenylethyl ammonium (PEA), an organic cation in cesium bismuth bromide (CBB) to enhance the multi-quantum well structure of CBB and form organic-inorganic hybrid nanosheets of PEA doped cesium bismuth bromide (CBB). The optimum addition of dopant led to the formation of stable layered PEA: CBB hybrid nanosheets, evidenced from XRD and HRTEM analysis.The possible stable structure of the hybrid nanosheets was elucidated via DFT calculations. This revealed a minimum energy structure with PEA coordinated in a horizontal configuration in-between inorganic slabs of CBB. PEA incorporation leads to the formation of new electronic states instigating longer tails in luminescence spectrum and variation in carrier lifetime. Third order non-linear optical characterization of the pure and hybrid particles revealed the multi-quantum-well structure and additional trap states brought about by PEA incorporation increases the two-photon absorption coefficient and decreases the optical limiting threshold of CBB. The present study indicates conceivable relevance of lead-free bismuth based halide perovskites and its variants in optical limiting applications.
人们一直在积极探索无铅卤化物包晶在光电领域的应用。有机-无机混合卤化物包晶在引入量子阱结构的同时，还显示出了新颖的光学特性、带隙调整和载流子动力学改进的前景。在此，我们在溴化铯铋（CBB）中加入了有机阳离子苯乙基铵（PEA），以增强 CBB 的多量子阱结构，并形成掺杂 PEA 的溴化铯铋（CBB）有机-无机混合纳米片。XRD 和 HRTEM 分析表明，掺杂剂的最佳添加量导致形成了稳定的层状 PEA：CBB 混合纳米片。通过 DFT 计算阐明了杂化纳米片可能的稳定结构。计算显示，在 CBB 的无机板块之间，PEA 以水平构型配位，形成最低能量结构。PEA 的加入导致形成了新的电子态，从而使发光光谱中的尾巴更长，载流子寿命也发生了变化。纯粒子和混合粒子的三阶非线性光学特性表明，多量子阱结构和 PEA 的加入所带来的额外阱态增加了双光子吸收系数，降低了 CBB 的光学极限阈值。本研究表明，无铅铋基卤化物包晶石及其变体在光学极限应用中的相关性是可以想象的。
{"title":"Probing the Significance of Phenylethyl Ammonium Doping in Cs3Bi2Br9 Halide Perovskite Nanosheets: A Structural and Optical Perspective","authors":"Fency Sunny, Priyakumari Chakkingal Parambil, Nandakumar Kalarikkal, K. B. Subila","doi":"10.1039/d5dt00325c","DOIUrl":"https://doi.org/10.1039/d5dt00325c","url":null,"abstract":"Lead free halide perovskites have been explored ardently for optoelectronic applications. Organic-Inorganic hybrid halide perovskites have shown promise with novel optical properties, bandgap tuning and improved carrier dynamics while introducing a quantum well structure. Herein, we have incorporated phenylethyl ammonium (PEA), an organic cation in cesium bismuth bromide (CBB) to enhance the multi-quantum well structure of CBB and form organic-inorganic hybrid nanosheets of PEA doped cesium bismuth bromide (CBB). The optimum addition of dopant led to the formation of stable layered PEA: CBB hybrid nanosheets, evidenced from XRD and HRTEM analysis.The possible stable structure of the hybrid nanosheets was elucidated via DFT calculations. This revealed a minimum energy structure with PEA coordinated in a horizontal configuration in-between inorganic slabs of CBB. PEA incorporation leads to the formation of new electronic states instigating longer tails in luminescence spectrum and variation in carrier lifetime. Third order non-linear optical characterization of the pure and hybrid particles revealed the multi-quantum-well structure and additional trap states brought about by PEA incorporation increases the two-photon absorption coefficient and decreases the optical limiting threshold of CBB. The present study indicates conceivable relevance of lead-free bismuth based halide perovskites and its variants in optical limiting applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"59 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797888","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mohammad Gholinejad, Mahboobe Eskandari, José Sansano
A novel bimetallic Ag-Au nanoprism incorporating trace levels of gold (ppm range) was synthesized via a wet-chemical method. The material was comprehensively characterized using transmission electron microscopy (TEM), scanning electron microscopy (SEM) mapping, X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). This new nanostructure exhibits a remarkable synergistic interaction between the silver nanoprism and meager amounts of gold, resulting in highly efficient catalytic activity for the A3 coupling reaction involving aldehydes, alkynes, and amines. The reaction proceeds efficiently in water at 60 ℃, accommodating a broad substrate scope and showcasing its versatility. Notably, the catalytic system achieves excellent performance even at ultralow gold loadings (80 ppm), highlighting its cost-effectiveness and sustainability. Furthermore, the catalyst demonstrates robust reusability, retaining its activity over four consecutive cycles in aqueous media.
{"title":"Design and Catalytic Application of Ag-Au Nanoprisms: Enhancing A3 Coupling Efficiency with Minimal Gold Concentration","authors":"Mohammad Gholinejad, Mahboobe Eskandari, José Sansano","doi":"10.1039/d5dt00415b","DOIUrl":"https://doi.org/10.1039/d5dt00415b","url":null,"abstract":"A novel bimetallic Ag-Au nanoprism incorporating trace levels of gold (ppm range) was synthesized via a wet-chemical method. The material was comprehensively characterized using transmission electron microscopy (TEM), scanning electron microscopy (SEM) mapping, X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). This new nanostructure exhibits a remarkable synergistic interaction between the silver nanoprism and meager amounts of gold, resulting in highly efficient catalytic activity for the A3 coupling reaction involving aldehydes, alkynes, and amines. The reaction proceeds efficiently in water at 60 ℃, accommodating a broad substrate scope and showcasing its versatility. Notably, the catalytic system achieves excellent performance even at ultralow gold loadings (80 ppm), highlighting its cost-effectiveness and sustainability. Furthermore, the catalyst demonstrates robust reusability, retaining its activity over four consecutive cycles in aqueous media.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"37 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797857","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hui Li, Hong-Bin Liu, Xiao-Min Tao, Jian Su, Ping-Fan Ning, Xiu-Fang Xu, Yu Zhou, Wen Gu, Xin Liu
Correction for ‘Novel single component tri-rare-earth emitting MOF for warm white light LEDs’ by Hui Li et al., Dalton Trans., 2018, 47, 8427–8433, https://doi.org/10.1039/C8DT01477A.
{"title":"Correction: Novel single component tri-rare-earth emitting MOF for warm white light LEDs","authors":"Hui Li, Hong-Bin Liu, Xiao-Min Tao, Jian Su, Ping-Fan Ning, Xiu-Fang Xu, Yu Zhou, Wen Gu, Xin Liu","doi":"10.1039/d5dt90076j","DOIUrl":"https://doi.org/10.1039/d5dt90076j","url":null,"abstract":"Correction for ‘Novel single component tri-rare-earth emitting MOF for warm white light LEDs’ by Hui Li <em>et al.</em>, <em>Dalton Trans.</em>, 2018, <strong>47</strong>, 8427–8433, https://doi.org/10.1039/C8DT01477A.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"10 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797893","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Two distinct oxyfluorides were synthesized by annealing brownmillerite SrCoO2.5 (BM-SCO) thin film in MgF2 powder through soft-chemistry reduction. Throughout the annealing, BM-SCO undergoes two successive phase transitions which were referred to as perovskite F-doped SrCoOx (P-SCOF) and brownmillerite F-doped SrCoOx (BM-SCOF). P-SCOF retains randomly distributed F-ions; while BM-SCOF forms an F-ordered structure characterized by alternative-stacking of square-planar CoO₂F₂ and octahedral CoO₄F₂. These three phases could change to each other reversibly under moderate conditions, thereby providing a pathway to extract high-purity F2 with perovskite catalysts.
{"title":"Reversible Fluorination in Brownmillerite SrCoO2.5 by MgF2 annealing","authors":"Yongxiang Ma, Yuanmin Zhu, Yihao Yang, Qi Liu, Sixia Hu, Songbai Hu, Lang Chen","doi":"10.1039/d5dt00262a","DOIUrl":"https://doi.org/10.1039/d5dt00262a","url":null,"abstract":"Two distinct oxyfluorides were synthesized by annealing brownmillerite SrCoO2.5 (BM-SCO) thin film in MgF2 powder through soft-chemistry reduction. Throughout the annealing, BM-SCO undergoes two successive phase transitions which were referred to as perovskite F-doped SrCoOx (P-SCOF) and brownmillerite F-doped SrCoOx (BM-SCOF). P-SCOF retains randomly distributed F-ions; while BM-SCOF forms an F-ordered structure characterized by alternative-stacking of square-planar CoO₂F₂ and octahedral CoO₄F₂. These three phases could change to each other reversibly under moderate conditions, thereby providing a pathway to extract high-purity F2 with perovskite catalysts.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"24 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797886","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Imido complexes of late transition metals are of fundamental interest as transient species in bond activation catalysis. In this perspective article, we present late imido metal complexes in uncommon and highly reactive states, concentrating on structurally authenticated imido metal complexes with higher spin states and imidyl or even nitrene character. Further, the few examples of analogous metalla nitridyls and metallanitrenes are discussed. This work serves as an overview of the existing array of these compounds and provides insights into their unequivocal identification or ambiguity, offering an entry point for interested molecular organic/inorganic chemists to contribute to this area.
{"title":"Chasing isolable late d-block metal nitrenes and imidyls","authors":"C. Gunnar Werncke","doi":"10.1039/d5dt00110b","DOIUrl":"https://doi.org/10.1039/d5dt00110b","url":null,"abstract":"Imido complexes of late transition metals are of fundamental interest as transient species in bond activation catalysis. In this perspective article, we present late imido metal complexes in uncommon and highly reactive states, concentrating on structurally authenticated imido metal complexes with higher spin states and imidyl or even nitrene character. Further, the few examples of analogous metalla nitridyls and metallanitrenes are discussed. This work serves as an overview of the existing array of these compounds and provides insights into their unequivocal identification or ambiguity, offering an entry point for interested molecular organic/inorganic chemists to contribute to this area.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"74 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797856","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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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