Here, we present the first instance of a highly efficient red tetramer aggregate with tunable emission based on a cationic platinum(II) complex in conjunction with a silver cluster anion counterpart. This system exhibits multicolor emission response behaviors, which can be conveniently and directly detected through spectroscopic analysis, showcasing intriguing luminescence changes. The self-assembly of Pt⋯, π–π, and hydrogen bonding interactions not only enables an intriguing color adjustment from green to yellow emission, and eventually to red emission, but also demonstrates the co-existence of the monomer, excimer, and aggregation. These phenomena are further accompanied by well-defined nanostructures. The self-assembly process of these structures exhibits an isodesmic growth mechanism, which is dependent on temperature. In this regard, it exhibits potential applicability in multi-mode logic gates that rely on external stimuli such as concentration, solvent, and temperature. The sensitivity of the aggregates towards chemical stimuli combined with their exceptionally bright emission characteristics renders them suitable for diverse applications including solid-state lighting sensing mechanisms and anticounterfeiting measures. The multi-stimuli responsive phosphorescence and self-assembly behaviors of the cationic platinum(II) complex were substantiated by X-ray crystal structure determination, 1H NMR analysis spectroscopic investigations, computational calculations and scanning electron microscopy (SEM) studies.
在这里，我们首次展示了基于阳离子铂(II)配合物与银簇阴离子对应物的、具有可调发射的高效红色四聚体聚合体。该系统呈现出多色发射响应行为，可通过光谱分析方便、直接地检测到这些响应行为，展示出引人入胜的发光变化。Pt⋯、π-π 和氢键相互作用的自组装不仅实现了从绿色发射到黄色发射，最终到红色发射的有趣颜色调整，而且还展示了单体、准分子和聚集的共存。伴随这些现象出现的还有定义明确的纳米结构。这些结构的自组装过程呈现出一种等渗生长机制，这种机制与温度有关。在这方面，它有望应用于依赖浓度、溶剂和温度等外部刺激的多模式逻辑门。聚合体对化学刺激的敏感性加上其异常明亮的发射特性，使其适用于多种应用，包括固态照明传感机制和防伪措施。通过 X 射线晶体结构测定、1H NMR 分析光谱研究、计算和扫描电子显微镜（SEM）研究，证实了阳离子铂（II）复合物的多刺激响应磷光和自组装行为。
{"title":"Visualizing supramolecular assembly behavior, stimulus response, and solid state emission of higher-order Pt2+ aggregates","authors":"Jing Li, Bao-Sen Xu, Shao-Zhe Yi, Xing-Long Zhang, Le-Le Zhao, Yu Meng, Wen-Jin Wang, Bao-Ning Li","doi":"10.1039/d4dt02771j","DOIUrl":"https://doi.org/10.1039/d4dt02771j","url":null,"abstract":"Here, we present the first instance of a highly efficient red tetramer aggregate with tunable emission based on a cationic platinum(<small>II</small>) complex in conjunction with a silver cluster anion counterpart. This system exhibits multicolor emission response behaviors, which can be conveniently and directly detected through spectroscopic analysis, showcasing intriguing luminescence changes. The self-assembly of Pt⋯, π–π, and hydrogen bonding interactions not only enables an intriguing color adjustment from green to yellow emission, and eventually to red emission, but also demonstrates the co-existence of the monomer, excimer, and aggregation. These phenomena are further accompanied by well-defined nanostructures. The self-assembly process of these structures exhibits an isodesmic growth mechanism, which is dependent on temperature. In this regard, it exhibits potential applicability in multi-mode logic gates that rely on external stimuli such as concentration, solvent, and temperature. The sensitivity of the aggregates towards chemical stimuli combined with their exceptionally bright emission characteristics renders them suitable for diverse applications including solid-state lighting sensing mechanisms and anticounterfeiting measures. The multi-stimuli responsive phosphorescence and self-assembly behaviors of the cationic platinum(<small>II</small>) complex were substantiated by X-ray crystal structure determination, <small><sup>1</sup></small>H NMR analysis spectroscopic investigations, computational calculations and scanning electron microscopy (SEM) studies.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"246 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637844","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}
Analysis of emission enhancement in an aggregated state has been developed by focusing on suppression of nonradiative processes by intermolecular interactions. On the other hand, it is difficult to evaluate contribution of radiative processes despite its significant role in improving emission. Herein, the contribution of radiative processes to crystallization-induced emission enhancement (CIEE) is evaluated. By comparing optical properties between isolated and crystalline states at 77 K to minimize structural relaxation, acceleration phenomena of the radiative process originating from the intermolecular interactions in crystal are clarified. Consequently, it is experimentally proved that a large refractive index in an organic crystal mainly promotes the radiative processes in CIEE even without significant intermolecular electronic interactions.
对聚集状态下发射增强的分析是通过重点关注分子间相互作用对非辐射过程的抑制来进行的。另一方面，尽管辐射过程对改善发射有重要作用，但很难评估辐射过程的贡献。本文评估了辐射过程对结晶诱导发射增强（CIEE）的贡献。通过比较孤立态和结晶态在 77 K 时的光学特性，最大限度地减少结构松弛，阐明了源自晶体中分子间相互作用的辐射过程加速现象。因此，实验证明，即使没有明显的分子间电子相互作用，有机晶体中的大折射率也会主要促进 CIEE 的辐射过程。
{"title":"Contribution of Radiative Rate Constants to Crystallization-Induced Emission Enhancement in Boron-Fused Azobenzene Complexes","authors":"Masashi Nakamura, Masayuki Gon, Kazuo Tanaka","doi":"10.1039/d4dt02458c","DOIUrl":"https://doi.org/10.1039/d4dt02458c","url":null,"abstract":"Analysis of emission enhancement in an aggregated state has been developed by focusing on suppression of nonradiative processes by intermolecular interactions. On the other hand, it is difficult to evaluate contribution of radiative processes despite its significant role in improving emission. Herein, the contribution of radiative processes to crystallization-induced emission enhancement (CIEE) is evaluated. By comparing optical properties between isolated and crystalline states at 77 K to minimize structural relaxation, acceleration phenomena of the radiative process originating from the intermolecular interactions in crystal are clarified. Consequently, it is experimentally proved that a large refractive index in an organic crystal mainly promotes the radiative processes in CIEE even without significant intermolecular electronic interactions.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"148 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637486","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}
Yan Xu, Zhaohe Guo, Xuena Xu, Liluo Shi, Xueyao Mo, Lu Li, LiMei Sun, Hongri Wan, Ming Song
Zinc-ion batteries (ZIBs) are promising on account of the inherent safety, minimal toxicity, cost-effectiveness, and high theoretical capacity. However, the thorny issues including the Zn dendrites and side reactions impede their commercial application. Here, we propose a green, non-toxic and biological carrageenan (Carr) serving as an electrolyte additive to address the aforementioned issues. Owing to the multifunctional groups, Carr has the capacity to interact with Zn2+, thereby modulating the solvation configuration of Zn2+ and changing the ion distribution at electrode-electrolyte interface. Moreover, it can adsorb on the Zn electrode and induce the formation of the solid electrolyte interphase (SEI) consisting of ZnO, ZnS and R-SO2 species. It contributes to the uniform Zn2+ ions diffusion and even Zn deposition with preferable (002) plane. Consequently, the Zn||Zn cells exhibit a stable cycle performance for 800 h at 5 mA cm-2 and 5 mAh cm-2. An elevated coulombic efficiency of 99.2% over 1800 cycles is obtained in the Zn||Cu cells using the electrolyte with Carr. Benefitting from the highly stable and reversible Zn anode, the Zn||VO2 full cell also delivers a high performance in comparison with the bare ZnSO4 electrolyte, favoring the practical implementation of ZIBs.
{"title":"Carrageenan-induced Highly Stable Zn Anode by Regulating Interface Chemistry","authors":"Yan Xu, Zhaohe Guo, Xuena Xu, Liluo Shi, Xueyao Mo, Lu Li, LiMei Sun, Hongri Wan, Ming Song","doi":"10.1039/d4dt02671c","DOIUrl":"https://doi.org/10.1039/d4dt02671c","url":null,"abstract":"Zinc-ion batteries (ZIBs) are promising on account of the inherent safety, minimal toxicity, cost-effectiveness, and high theoretical capacity. However, the thorny issues including the Zn dendrites and side reactions impede their commercial application. Here, we propose a green, non-toxic and biological carrageenan (Carr) serving as an electrolyte additive to address the aforementioned issues. Owing to the multifunctional groups, Carr has the capacity to interact with Zn2+, thereby modulating the solvation configuration of Zn2+ and changing the ion distribution at electrode-electrolyte interface. Moreover, it can adsorb on the Zn electrode and induce the formation of the solid electrolyte interphase (SEI) consisting of ZnO, ZnS and R-SO2 species. It contributes to the uniform Zn2+ ions diffusion and even Zn deposition with preferable (002) plane. Consequently, the Zn||Zn cells exhibit a stable cycle performance for 800 h at 5 mA cm-2 and 5 mAh cm-2. An elevated coulombic efficiency of 99.2% over 1800 cycles is obtained in the Zn||Cu cells using the electrolyte with Carr. Benefitting from the highly stable and reversible Zn anode, the Zn||VO2 full cell also delivers a high performance in comparison with the bare ZnSO4 electrolyte, favoring the practical implementation of ZIBs.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"38 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637488","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}
Sulfur-based energetic materials 3 to 7 were synthesized considering the limited availability of structural combinations of polynitrogen and oxygen-based organic scaffolds advancing their limits. All of them were fully characterised using infrared spectroscopy (IR), multinuclear magnetic resonance spectroscopy (NMR), high-resolution mass spectrometry (HRMS), elemental analysis (EA), and differential scanning calorimetry (DSC) studies. Further, the molecular structure of compound 3 was supported using single-crystal X-ray diffraction studies (SC-XRD). All compounds possess good density (1.68- 1.81 g cm-3), moderate detonation performance (VOD= 5747-7075 m s-1; DP= 14.39-19.22 GPa), high thermal stability (159-246 °C) and are insensitive towards impact and friction (IS > 40 J and FS > 360 N) stimuli. This is the first instance of an energetic alliance of pyrazine and thiadiazole frameworks, which can be considered as a developmental step in energetic materials field.
考虑到多氮基和氧基有机支架结构组合的有限性及其局限性，合成了硫基高能材料 3 至 7。利用红外光谱（IR）、多核磁共振光谱（NMR）、高分辨率质谱（HRMS）、元素分析（EA）和差示扫描量热法（DSC）研究对所有化合物进行了全面表征。此外，化合物 3 的分子结构还得到了单晶 X 射线衍射研究（SC-XRD）的支持。所有化合物都具有良好的密度（1.68- 1.81 g cm-3）、适中的引爆性能（VOD= 5747-7075 m s-1；DP= 14.39-19.22 GPa）、较高的热稳定性（159-246 °C），并且对冲击和摩擦（IS > 40 J 和 FS > 360 N）刺激不敏感。这是吡嗪和噻二唑框架高能联盟的首个实例，可视为高能材料领域的一个发展步骤。
{"title":"Advancing Energetic Chemistry: First Synthesis of Sulfur-Based C-C Bonded Thiadiazole-Pyrazine Compounds with Nitrimino Moiety","authors":"Parasar Kumar, Vikas Ghule, Srinivas Dharavath","doi":"10.1039/d4dt02919d","DOIUrl":"https://doi.org/10.1039/d4dt02919d","url":null,"abstract":"Sulfur-based energetic materials 3 to 7 were synthesized considering the limited availability of structural combinations of polynitrogen and oxygen-based organic scaffolds advancing their limits. All of them were fully characterised using infrared spectroscopy (IR), multinuclear magnetic resonance spectroscopy (NMR), high-resolution mass spectrometry (HRMS), elemental analysis (EA), and differential scanning calorimetry (DSC) studies. Further, the molecular structure of compound 3 was supported using single-crystal X-ray diffraction studies (SC-XRD). All compounds possess good density (1.68- 1.81 g cm-3), moderate detonation performance (VOD= 5747-7075 m s-1; DP= 14.39-19.22 GPa), high thermal stability (159-246 °C) and are insensitive towards impact and friction (IS > 40 J and FS > 360 N) stimuli. This is the first instance of an energetic alliance of pyrazine and thiadiazole frameworks, which can be considered as a developmental step in energetic materials field.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"162 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637484","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}
Anindita Chakraborty, Jyoti Sharma, Tapas Kumar Maji
Metal-organic frameworks (MOFs) have become increasingly important as a class of porous crystalline materials because of their diverse applications. At the same time, significant progress has been achieved in the field of MOF-based composite materials toward novel applications based on the synergistic role of two or more different components. Clay materials have been explored recently in MOF chemistry for the synthesis of MOF-clay composites, which are a new class of functional materials synthesized by a cooperative combination of MOF with clay. Such composites have evolved only in the recent past, with important functions and applications, such as enhanced gas storage and separation, CO2 capture and conversion, catalysis, drug delivery, and water-harvesting. Notably, the typical shortcomings of MOFs, like moisture sensitivity, poor water dispersibility, poor thermal and chemical stability, and processability, could be overcome by developing novel MOF-clay composites. This article provides a concise overview of MOF-clay composites and their applications in various fields that would drive the interest of researchers to explore the emerging field of MOF-clay chemistry. In the initial sections, we classified the clays that have been used in MOF chemistry and briefly discussed their structures and chemistry. We also presented the advantages of MOF-clay composites and discussed their synthetic methodologies. In the later sections, we classified the different MOF-clay composites based on the clay and presented some representative examples of such composites showing unique properties and applications. Finally, the development in this field is summarized, and the future scope of such composites is discussed.
{"title":"Integration of Metal-Organic Framework and Clay Toward Functional Composite Materials","authors":"Anindita Chakraborty, Jyoti Sharma, Tapas Kumar Maji","doi":"10.1039/d4dt02789b","DOIUrl":"https://doi.org/10.1039/d4dt02789b","url":null,"abstract":"Metal-organic frameworks (MOFs) have become increasingly important as a class of porous crystalline materials because of their diverse applications. At the same time, significant progress has been achieved in the field of MOF-based composite materials toward novel applications based on the synergistic role of two or more different components. Clay materials have been explored recently in MOF chemistry for the synthesis of MOF-clay composites, which are a new class of functional materials synthesized by a cooperative combination of MOF with clay. Such composites have evolved only in the recent past, with important functions and applications, such as enhanced gas storage and separation, CO2 capture and conversion, catalysis, drug delivery, and water-harvesting. Notably, the typical shortcomings of MOFs, like moisture sensitivity, poor water dispersibility, poor thermal and chemical stability, and processability, could be overcome by developing novel MOF-clay composites. This article provides a concise overview of MOF-clay composites and their applications in various fields that would drive the interest of researchers to explore the emerging field of MOF-clay chemistry. In the initial sections, we classified the clays that have been used in MOF chemistry and briefly discussed their structures and chemistry. We also presented the advantages of MOF-clay composites and discussed their synthetic methodologies. In the later sections, we classified the different MOF-clay composites based on the clay and presented some representative examples of such composites showing unique properties and applications. Finally, the development in this field is summarized, and the future scope of such composites is discussed.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"45 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637485","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}
Tobias Seitz, Marcel Walbeck, Alexander Hoffmann, Sonja Herres-Pawlis
Copper complexes of tripodal ligands have been used as model systems for electron transfer proteins for decades, displaying a broad range of electron self-exchage rates. We herein report a group of six tripodal tetradentate triarylamine ligands which display a varying number of guaninidine and 2-methylquinolinyl moierties. Their corresponding Cu(I) complexes have been (re)synthesized and studied with regard to their electron transfer properties. While their solid state structures are four-coordinate and display an uncommon umbrella distortion, DFT studies of the Cu(II) systems reveal that they gain an additional ligand in form of a solvent molecule and exhibit a range of possible conformers that likely co-exist in thermal equilibrium. The redox-couples’ electron self-exchange rates were analyzed using Marcus theory and vary over four orders of magnitdue which cyclic voltammetry studies suggest to be due to a gated addition-oxidation electron transfer mechanism. This mechanism deviates from previously studied systems, likely due to the structural anomalies of the Cu(I) systems. This demonstrates that the chosen path of tripodal model systems can be influenced by molecular design.
{"title":"Electron Transfer Kinetics of a Series of Copper Complexes with Tripodal Tetradentate Guanidine Quinolinyl Ligands","authors":"Tobias Seitz, Marcel Walbeck, Alexander Hoffmann, Sonja Herres-Pawlis","doi":"10.1039/d4dt02917h","DOIUrl":"https://doi.org/10.1039/d4dt02917h","url":null,"abstract":"Copper complexes of tripodal ligands have been used as model systems for electron transfer proteins for decades, displaying a broad range of electron self-exchage rates. We herein report a group of six tripodal tetradentate triarylamine ligands which display a varying number of guaninidine and 2-methylquinolinyl moierties. Their corresponding Cu(I) complexes have been (re)synthesized and studied with regard to their electron transfer properties. While their solid state structures are four-coordinate and display an uncommon umbrella distortion, DFT studies of the Cu(II) systems reveal that they gain an additional ligand in form of a solvent molecule and exhibit a range of possible conformers that likely co-exist in thermal equilibrium. The redox-couples’ electron self-exchange rates were analyzed using Marcus theory and vary over four orders of magnitdue which cyclic voltammetry studies suggest to be due to a gated addition-oxidation electron transfer mechanism. This mechanism deviates from previously studied systems, likely due to the structural anomalies of the Cu(I) systems. This demonstrates that the chosen path of tripodal model systems can be influenced by molecular design.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"246 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637481","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}
Thi Hien Doan, Linh P.T. Tran, Van Hai Pham, Huy Hoang Luc
This study presents a density functional theory (DFT) investigation into the structural, electronic, and optical properties, thermodynamic stability, phase competition, and reaction pathways of Bi2WO6, a notable compound within the Aurivillius family of oxides. We examine three distinct polymorphs of Bi2WO6: the low-temperature orthorhombic phase (P1), the intermediate-temperature orthorhombic phase (P2), and the high-temperature monoclinic phase (P3).} Electronic structure analysis indicates band gaps of 2.339 eV (P1), 2.312 eV (P2), and 2.128 eV (P3), with the valence band primarily composed of O 2p states and the conduction band of Bi 6p and W 5d states. Optical properties, including the dielectric function and absorption spectra, show distinct behaviors for each phase, particularly P3. Elastic and phonon property analyses confirm the mechanical and dynamical stability of all three phases, with the P1 phase exhibiting the highest bulk modulus and stiffness among the polymorphs. Our effective mass calculations suggest that the P3 phase may have better charge carrier mobility compared to the P1 and P2 phases. Structural optimizations reveal marginal differences in total energy among these phases, suggesting their potential coexistence or easy phase transitions under varying conditions. Detailed Gibbs free energy calculations confirm that the P1 phase is the most stable at low temperatures, in agreement with experimental data in the literature. We also construct a chemical reaction network to explore feasible reaction pathways for the solid--state synthesis of Bi2WO6 from Bi2O3 and WO3 precursors, identifying several low--cost reaction pathways, including both direct and multi--step routes involving intermediates such as Bi14WO24 and Bi2W2O9.
{"title":"Structural Properties, Thermodynamic Stability and Reaction Pathways for Solid--State Synthesis of Bi2WO6 Polymorphs","authors":"Thi Hien Doan, Linh P.T. Tran, Van Hai Pham, Huy Hoang Luc","doi":"10.1039/d4dt02931c","DOIUrl":"https://doi.org/10.1039/d4dt02931c","url":null,"abstract":"This study presents a density functional theory (DFT) investigation into the structural, electronic, and optical properties, thermodynamic stability, phase competition, and reaction pathways of Bi2WO6, a notable compound within the Aurivillius family of oxides. We examine three distinct polymorphs of Bi2WO6: the low-temperature orthorhombic phase (P1), the intermediate-temperature orthorhombic phase (P2), and the high-temperature monoclinic phase (P3).} Electronic structure analysis indicates band gaps of 2.339 eV (P1), 2.312 eV (P2), and 2.128 eV (P3), with the valence band primarily composed of O 2p states and the conduction band of Bi 6p and W 5d states. Optical properties, including the dielectric function and absorption spectra, show distinct behaviors for each phase, particularly P3. Elastic and phonon property analyses confirm the mechanical and dynamical stability of all three phases, with the P1 phase exhibiting the highest bulk modulus and stiffness among the polymorphs. Our effective mass calculations suggest that the P3 phase may have better charge carrier mobility compared to the P1 and P2 phases. Structural optimizations reveal marginal differences in total energy among these phases, suggesting their potential coexistence or easy phase transitions under varying conditions. Detailed Gibbs free energy calculations confirm that the P1 phase is the most stable at low temperatures, in agreement with experimental data in the literature. We also construct a chemical reaction network to explore feasible reaction pathways for the solid--state synthesis of Bi2WO6 from Bi2O3 and WO3 precursors, identifying several low--cost reaction pathways, including both direct and multi--step routes involving intermediates such as Bi14WO24 and Bi2W2O9.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"25 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637490","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}
Over the last two decades, manganese(I) carbonyl complexes have been widely investigated as carbon monoxide releasing molecules (CORMs) to transfer small quantities of CO to biological targets to have beneficial impacts such as preventing ischemia reperfusion injury and reducing organ transplant rejection. Furthermore, these complexes exhibit beneficial anti-coagulative, anti-apoptotic, anti-inflammatory, and anti-proliferative properties. Owing to their highly controlled substitution chemistry and oxidative durability, Mn(I) carbonyl moieties were combined with a wide range of auxiliary ligands, including biomolecules. This review focused on tri- and tetracarbonyl Mn(I) complexes that were exposed to light, changed the redox status, or underwent thermal activation to release carbon monoxide. Kinetic parameters, stability in the dark, number of CO release equivalents, CO detection tools, and the nature of solvents used in the studies are reported and tabulated. An overview of all the previously published Mn(I) CORMs is specifically provided to define the method of action of these promising biologically active compounds and discuss their possible therapeutic applications in relation to their CO-releasing and biocompatibility characteristics.
{"title":"A comprehensive survey of Mn(I) carbonyls as CO-releasing molecules reported over the last two decades.","authors":"Ahmed M Mansour, Rabaa M Khaled, Ola R Shehab","doi":"10.1039/d4dt02091j","DOIUrl":"10.1039/d4dt02091j","url":null,"abstract":"<p><p>Over the last two decades, manganese(I) carbonyl complexes have been widely investigated as carbon monoxide releasing molecules (CORMs) to transfer small quantities of CO to biological targets to have beneficial impacts such as preventing ischemia reperfusion injury and reducing organ transplant rejection. Furthermore, these complexes exhibit beneficial anti-coagulative, anti-apoptotic, anti-inflammatory, and anti-proliferative properties. Owing to their highly controlled substitution chemistry and oxidative durability, Mn(I) carbonyl moieties were combined with a wide range of auxiliary ligands, including biomolecules. This review focused on tri- and tetracarbonyl Mn(I) complexes that were exposed to light, changed the redox status, or underwent thermal activation to release carbon monoxide. Kinetic parameters, stability in the dark, number of CO release equivalents, CO detection tools, and the nature of solvents used in the studies are reported and tabulated. An overview of all the previously published Mn(I) CORMs is specifically provided to define the method of action of these promising biologically active compounds and discuss their possible therapeutic applications in relation to their CO-releasing and biocompatibility characteristics.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":""},"PeriodicalIF":3.5,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142612987","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}
Amie E. Norton, Stephen Taylor, Caroline Williams, Ann Zoller, Watts Dietrich, William Connick, Sayandev Chatterjee
This study explores the vapochromic and vapoluminescent behaviors of [Pt(tpy)Cl]PF6 host molecules (tpy = 2,2':6',2''-terpyridine) under acetonitrile (CH3CN) vapor guest, challenging the conventional view that these phenomena arise solely from direct host-guest interactions. Our findings reveal a cooperative mechanism where mechanochromic surface perturbations prime the Pt(II) host for guest incorporation, leading to initial color and luminescence changes prior to significant structural alterations. While the color transition between the yellow [Pt(tpy)Cl]PF6 form and the red/orange [Pt(tpy)Cl]PF6•CH3CN form is reversible, repeated vapor cycling induces a loss of crystallinity, as indicated by diffraction peak broadening and emission shifts. Scanning electron microscopy analyses show mechanical deformations like bending and surface pitting, emphasizing the role of vapomechanical stress in altering optical properties. These insights highlight the need for integrated design strategies in developing robust vapochromic materials for gas sensing applications.
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Marija Bakija, Saša Opačak, Berislav Peric, Soumyadeep Chakrabortty, Andrea Dell'Acqua, Eszter Barath, Johannes G. de Vries, Sergey Tin, Srećko I. Kirin
This publication describes monodentate phosphine and oxazoline ligands attached to an amino acid ester and the application of their supramolecularly assembled rhodium(I) or iridium(I) complexes in asymmetric catalysis. The major feature of these complexes is the transmission of chirality from distant hydrogen bonded amino acids to the prochiral catalytic metal center ("backdoor induction"). The in situ generated homoleptic and heteroleptic rhodium(I) or iridium(I) precatalysts were studied by NMR, UV-VIS and CD spectroscopy as well as X-ray single crystal diffraction. In asymmetric hydrogenation of methyl α-acetamidocinnamate, rhodium(I) and iridium(I) complexes afforded complete conversions with enantioselectivities up to 85 %, while iridium complexes proved to be more sensitive to the variation of reaction conditions, including catalyst loading, metal to ligand ratio and temperature. The hydrogenation of four other dehydroamino acid substrates resulted in similar conversion and selectivity as obtained with methyl α-acetamidocinnamate. The influence of the phosphine/oxazoline heteroleptic mixtures in catalysis was studied using both rhodium(I) and iridium(I) complexes. Finally, a homoleptic phosphine rhodium(I) complex was successfully applied in asymmetric hydroformylation of styrene and 1-octene with complete conversions and selectivity up to 40% e.e. for the branched styrene product.
本出版物介绍了与氨基酸酯相连的单齿膦和噁唑啉配体，以及其超分子组装的铑(I)或铱(I)配合物在不对称催化中的应用。这些配合物的主要特点是手性从远处氢键氨基酸传递到原手性催化金属中心（"后门诱导"）。研究人员通过核磁共振、紫外可见光谱、CD 光谱以及 X 射线单晶衍射对原位生成的同性和异性铑（I）或铱（I）前催化剂进行了研究。在α-乙酰氨基肉桂酸甲酯的不对称氢化反应中，铑（I）和铱（I）配合物能实现完全转化，对映体选择性高达 85%，而铱配合物对反应条件的变化（包括催化剂负载、金属与配体的比例和温度）更为敏感。对其他四种脱氢氨基酸底物进行氢化时，获得了与α-乙酰胺肉桂酸甲酯类似的转化率和选择性。使用铑（I）和铱（I）络合物研究了膦/噁唑啉杂环混合物在催化过程中的影响。最后，在苯乙烯和 1-辛烯的不对称加氢甲酰化反应中成功地应用了同性膦铑（I）络合物，其转化率完全，支链苯乙烯产物的选择性高达 40%。
{"title":"Supramolecular bidentate rhodium(I) or iridium(I) phosphine and oxazoline amino acid bioconjugates as selective catalysts for enantioselective reactions","authors":"Marija Bakija, Saša Opačak, Berislav Peric, Soumyadeep Chakrabortty, Andrea Dell'Acqua, Eszter Barath, Johannes G. de Vries, Sergey Tin, Srećko I. Kirin","doi":"10.1039/d4dt02519a","DOIUrl":"https://doi.org/10.1039/d4dt02519a","url":null,"abstract":"This publication describes monodentate phosphine and oxazoline ligands attached to an amino acid ester and the application of their supramolecularly assembled rhodium(I) or iridium(I) complexes in asymmetric catalysis. The major feature of these complexes is the transmission of chirality from distant hydrogen bonded amino acids to the prochiral catalytic metal center (\"backdoor induction\"). The in situ generated homoleptic and heteroleptic rhodium(I) or iridium(I) precatalysts were studied by NMR, UV-VIS and CD spectroscopy as well as X-ray single crystal diffraction. In asymmetric hydrogenation of methyl α-acetamidocinnamate, rhodium(I) and iridium(I) complexes afforded complete conversions with enantioselectivities up to 85 %, while iridium complexes proved to be more sensitive to the variation of reaction conditions, including catalyst loading, metal to ligand ratio and temperature. The hydrogenation of four other dehydroamino acid substrates resulted in similar conversion and selectivity as obtained with methyl α-acetamidocinnamate. The influence of the phosphine/oxazoline heteroleptic mixtures in catalysis was studied using both rhodium(I) and iridium(I) complexes. Finally, a homoleptic phosphine rhodium(I) complex was successfully applied in asymmetric hydroformylation of styrene and 1-octene with complete conversions and selectivity up to 40% e.e. for the branched styrene product.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"197 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637483","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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