Pub Date : 2023-12-30DOI: 10.3390/inorganics12010016
R. Parra
The formation of a halogen-bonded network using four NHX-(CH2)3-NX-(CH2)3-NHX molecules (X = Cl, Br, or I) is investigated using DFT. The self-assembly of the four basic motifs results in a tube-like structure with C4h symmetry, with one halogen-bonded network located at each end of the structure and one at its center. Each halogen-bonded network has four quasi-planar N-X···N interactions with binding energies that increase with the size of X. The structure is found to bind Li+ at each of the halogen-bonded networks, albeit more strongly at its center. The binding of Li+ is driven by halogen atom lone pairs that produce a rich electron density orthogonal to the halogen bond. The presence and strength of the interactions are further examined using AIM and NBO calculations. Lastly, IRC calculations are performed to examine the transitions between the Li+ complex minima and, thus, the potential for transporting the metal ion from one end of the tube to the other. Based on the tetrameric structure, a model intramolecular structure is built and considered as a potential host for Li+. In this case, the central intermolecular N-X···N network is replaced by an intramolecular Si-C≡C-Si network. Interestingly, both intermolecular and intramolecular structures exhibit similar Li+ binding abilities.
{"title":"A Model Halogen-Bonded Network as a Potential Tube-like Host for Li+: A DFT Study","authors":"R. Parra","doi":"10.3390/inorganics12010016","DOIUrl":"https://doi.org/10.3390/inorganics12010016","url":null,"abstract":"The formation of a halogen-bonded network using four NHX-(CH2)3-NX-(CH2)3-NHX molecules (X = Cl, Br, or I) is investigated using DFT. The self-assembly of the four basic motifs results in a tube-like structure with C4h symmetry, with one halogen-bonded network located at each end of the structure and one at its center. Each halogen-bonded network has four quasi-planar N-X···N interactions with binding energies that increase with the size of X. The structure is found to bind Li+ at each of the halogen-bonded networks, albeit more strongly at its center. The binding of Li+ is driven by halogen atom lone pairs that produce a rich electron density orthogonal to the halogen bond. The presence and strength of the interactions are further examined using AIM and NBO calculations. Lastly, IRC calculations are performed to examine the transitions between the Li+ complex minima and, thus, the potential for transporting the metal ion from one end of the tube to the other. Based on the tetrameric structure, a model intramolecular structure is built and considered as a potential host for Li+. In this case, the central intermolecular N-X···N network is replaced by an intramolecular Si-C≡C-Si network. Interestingly, both intermolecular and intramolecular structures exhibit similar Li+ binding abilities.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2023-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139137686","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The preparation of environmentally friendly inorganic encapsulated pigments with a bright color and sufficient stability provides an effective strategy for expanding their applications in plastic, paint, glass, and ceramic decoration. The challenges facing the use of such pigments include the formation of a dense protective coating with the required endurance, the relatively weak color of the encapsulated pigments, and the preferable inclusion particle size. Environmentally friendly BiVO4 is regarded as a very promising pigment for multiple coloring applications due to its brilliant yellow color with high saturation. However, its poor thermal and chemical stability greatly limit the application of BiVO4. Herein, we report a sol–gel method to synthesize inorganic BiVO4@SiO2 yellow pigment with a core–shell structure. By controlling the synthesis conditions, including the particle size and dispersion of BiVO4 and the calcination temperature, a BiVO4@SiO2 encapsulated pigment with excellent chromatic properties was achieved. The obtained environmentally friendly BiVO4@SiO2 pigment with encapsulation modification has a comparable color-rendering performance to BiVO4, and it has a high thermal stability at 700 °C, excellent acid resistance, and good compatibility in plastics. The present research is expected to expand the application of yellow BiVO4 pigment in harsh environments.
{"title":"Preparation of Environmentally Friendly BiVO4@SiO2 Encapsulated Yellow Pigment with Remarkable Thermal and Chemical Stability","authors":"Renhua Chen, Xiaozhen Zhang, Rui Tao, Yuhua Jiang, Huafeng Liu, Lanlan Cheng","doi":"10.3390/inorganics12010017","DOIUrl":"https://doi.org/10.3390/inorganics12010017","url":null,"abstract":"The preparation of environmentally friendly inorganic encapsulated pigments with a bright color and sufficient stability provides an effective strategy for expanding their applications in plastic, paint, glass, and ceramic decoration. The challenges facing the use of such pigments include the formation of a dense protective coating with the required endurance, the relatively weak color of the encapsulated pigments, and the preferable inclusion particle size. Environmentally friendly BiVO4 is regarded as a very promising pigment for multiple coloring applications due to its brilliant yellow color with high saturation. However, its poor thermal and chemical stability greatly limit the application of BiVO4. Herein, we report a sol–gel method to synthesize inorganic BiVO4@SiO2 yellow pigment with a core–shell structure. By controlling the synthesis conditions, including the particle size and dispersion of BiVO4 and the calcination temperature, a BiVO4@SiO2 encapsulated pigment with excellent chromatic properties was achieved. The obtained environmentally friendly BiVO4@SiO2 pigment with encapsulation modification has a comparable color-rendering performance to BiVO4, and it has a high thermal stability at 700 °C, excellent acid resistance, and good compatibility in plastics. The present research is expected to expand the application of yellow BiVO4 pigment in harsh environments.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2023-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139141148","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-12-29DOI: 10.3390/inorganics12010015
Leonardo Querci, Letizia Fiorucci, E. Ravera, Mario Piccioli
Nuclear Magnetic Resonance (NMR) spectroscopy is the ideal tool to address the structure, reactivity and dynamics of both inorganic and biological substances. The knowledge of nuclear spin interaction and spin dynamics is increasingly consolidated, and this allows for tailoring pulse sequences. When dealing with paramagnetic systems, several decades of research have led to the development of rule-of-the-thumb criteria for optimizing the experiments, allowing for the detection of nuclei that are in very close proximity to the metal center. In turn, the observation of these systems, coupled with the development of robust and accessible quantum chemical methods, is promising to provide a link between the spectra and the structural features through the interpretation of the electronic structure. In this review, we list the challenges encountered and propose solutions for dealing with paramagnetic systems with the greatest satisfaction. In our intentions, this is a practical toolkit for optimizing acquisition and processing parameters for routine experiments aimed at detecting signals influenced by the hyperfine interaction. The implications of paramagnetic shift and line broadening are examined. With this endeavor, we wish to encourage non-expert users to consider the application of paramagnetic NMR to their systems.
{"title":"Paramagnetic Nuclear Magnetic Resonance: The Toolkit","authors":"Leonardo Querci, Letizia Fiorucci, E. Ravera, Mario Piccioli","doi":"10.3390/inorganics12010015","DOIUrl":"https://doi.org/10.3390/inorganics12010015","url":null,"abstract":"Nuclear Magnetic Resonance (NMR) spectroscopy is the ideal tool to address the structure, reactivity and dynamics of both inorganic and biological substances. The knowledge of nuclear spin interaction and spin dynamics is increasingly consolidated, and this allows for tailoring pulse sequences. When dealing with paramagnetic systems, several decades of research have led to the development of rule-of-the-thumb criteria for optimizing the experiments, allowing for the detection of nuclei that are in very close proximity to the metal center. In turn, the observation of these systems, coupled with the development of robust and accessible quantum chemical methods, is promising to provide a link between the spectra and the structural features through the interpretation of the electronic structure. In this review, we list the challenges encountered and propose solutions for dealing with paramagnetic systems with the greatest satisfaction. In our intentions, this is a practical toolkit for optimizing acquisition and processing parameters for routine experiments aimed at detecting signals influenced by the hyperfine interaction. The implications of paramagnetic shift and line broadening are examined. With this endeavor, we wish to encourage non-expert users to consider the application of paramagnetic NMR to their systems.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2023-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139142318","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-12-25DOI: 10.3390/inorganics12010009
Xuan Bie, Yawei Dong, M. Xiong, Ben Wang, Zhongxue Chen, Qunchao Zhang, Yi Liu, Ronghua Huang
This study prepared silicon oxide anode materials with nitrogen-doped carbon matrices (SiOx/C–N) through silicon-containing polyester thermal carbonization. Melamine was introduced as a nitrogen source during the experiment. This nitrogen doping process resulted in a porous structure in the carbon matrices, a fact confirmed by scanning electron microscopy (SEM). Pyridinic and quaternary nitrogen, but mainly tertiary nitrogen, were generated, as shown via X-ray photoelectron spectroscopy (XPS). Electrochemical tests confirmed that, as anode materials for a lithium-ion battery, SiOx/C–N provided better cycle stability, improved rate capability, and lower Li+ diffusion resistance. The best performance showed an activated capacity at 493.5 mAh/g, preserved at 432.8 mAh/g after the 100th cycle, with 87.7% total Columbic efficiency. Those without nitrogen doping gave 1126.7 mAh/g, 249.0 mAh/g, and 22.1%, respectively. The most noteworthy point was that, after 100 cycles, anodes without nitrogen doping were pulverized into fine powders (SEM); meanwhile, in the case of anodes with nitrogen doping, powders of a larger size (0.5–1.0 µm) formed, with the accumulation of surrounding cavities. We suggest that the formation of more prominent powders may have resulted from the more substantial nitrogen-doped carbon matrices, which prevented the anode from further breaking down to a smaller size. The volume expansion stress decreased when the powders decreased to nanosize, which is why the nanosized silicon anode materials showed better cycling stability. When the anodes were cracked into powders with a determined diameter, the stress from volume expansion decreased to a level at which the powders could preserve their shape, and the breakage of the powders was stopped. Hence, the diameters of the final reserved powders are contingent on the strength of the matrix. As reported, nitrogen-doped carbon matrices are more robust than those not doped with nitrogen. Thus, in our research, anodes with nitrogen-doped carbon matrices presented more large-diameter powders, as SEM confirmed. Anodes with nitrogen doping will not be further broken at a larger diameter. At this point, the SEI film will not show continuous breakage and formation compared to the anode without doping. This was validated by the lower deposition content of the SEI-film-related elements (phosphorous and fluorine) in the cycled anodes with nitrogen doping. The anode without nitrogen doping presented higher content, meaning that the SEI films were broken many times during lithiation/delithiation (EDS mapping).
{"title":"Nitrogen-Doped Carbon Matrix to Optimize Cycling Stability of Lithium Ion Battery Anode from SiOx Materials","authors":"Xuan Bie, Yawei Dong, M. Xiong, Ben Wang, Zhongxue Chen, Qunchao Zhang, Yi Liu, Ronghua Huang","doi":"10.3390/inorganics12010009","DOIUrl":"https://doi.org/10.3390/inorganics12010009","url":null,"abstract":"This study prepared silicon oxide anode materials with nitrogen-doped carbon matrices (SiOx/C–N) through silicon-containing polyester thermal carbonization. Melamine was introduced as a nitrogen source during the experiment. This nitrogen doping process resulted in a porous structure in the carbon matrices, a fact confirmed by scanning electron microscopy (SEM). Pyridinic and quaternary nitrogen, but mainly tertiary nitrogen, were generated, as shown via X-ray photoelectron spectroscopy (XPS). Electrochemical tests confirmed that, as anode materials for a lithium-ion battery, SiOx/C–N provided better cycle stability, improved rate capability, and lower Li+ diffusion resistance. The best performance showed an activated capacity at 493.5 mAh/g, preserved at 432.8 mAh/g after the 100th cycle, with 87.7% total Columbic efficiency. Those without nitrogen doping gave 1126.7 mAh/g, 249.0 mAh/g, and 22.1%, respectively. The most noteworthy point was that, after 100 cycles, anodes without nitrogen doping were pulverized into fine powders (SEM); meanwhile, in the case of anodes with nitrogen doping, powders of a larger size (0.5–1.0 µm) formed, with the accumulation of surrounding cavities. We suggest that the formation of more prominent powders may have resulted from the more substantial nitrogen-doped carbon matrices, which prevented the anode from further breaking down to a smaller size. The volume expansion stress decreased when the powders decreased to nanosize, which is why the nanosized silicon anode materials showed better cycling stability. When the anodes were cracked into powders with a determined diameter, the stress from volume expansion decreased to a level at which the powders could preserve their shape, and the breakage of the powders was stopped. Hence, the diameters of the final reserved powders are contingent on the strength of the matrix. As reported, nitrogen-doped carbon matrices are more robust than those not doped with nitrogen. Thus, in our research, anodes with nitrogen-doped carbon matrices presented more large-diameter powders, as SEM confirmed. Anodes with nitrogen doping will not be further broken at a larger diameter. At this point, the SEI film will not show continuous breakage and formation compared to the anode without doping. This was validated by the lower deposition content of the SEI-film-related elements (phosphorous and fluorine) in the cycled anodes with nitrogen doping. The anode without nitrogen doping presented higher content, meaning that the SEI films were broken many times during lithiation/delithiation (EDS mapping).","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2023-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139157651","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-12-25DOI: 10.3390/inorganics12010011
I. Karadashka, Vladislava Ivanova, Valeri Jordanov, Veronika Karadjova
Chalcogenide alloys of As2Se3-Ag2Te-GeTe were synthesized using the melt-quenching technique. By the visual and XRD analyses, the state of obtaining alloys was proven (glass, crystalline, glass + crystalline), and the glass formation region in the system was established. The thermal characteristics of some samples were determined—temperatures of glass transition (Tg); crystallization (Tcr); and melting (Tm). The basic physicochemical parameters, such as density (d) and Vickers microhardness (HV), were measured. Compactness (C), as well as some thermomechanical characteristics, such as module of elasticity (E), volume (Vh), and formation energy (Eh) of micro-voids, were calculated, and the influence of the composition on these characteristics was investigated. The addition of silver telluride resulted in a decrease in Tg and HV values and an increase in d and Vh values. No thermochemical effects of crystallization or melting were detected in some of the alloys. The obtained results were in agreement with the available literature data for similar systems.
{"title":"Glass Formation and Properties of Multicomponent Glasses of the As2Se3-Ag2Te-GeTe System","authors":"I. Karadashka, Vladislava Ivanova, Valeri Jordanov, Veronika Karadjova","doi":"10.3390/inorganics12010011","DOIUrl":"https://doi.org/10.3390/inorganics12010011","url":null,"abstract":"Chalcogenide alloys of As2Se3-Ag2Te-GeTe were synthesized using the melt-quenching technique. By the visual and XRD analyses, the state of obtaining alloys was proven (glass, crystalline, glass + crystalline), and the glass formation region in the system was established. The thermal characteristics of some samples were determined—temperatures of glass transition (Tg); crystallization (Tcr); and melting (Tm). The basic physicochemical parameters, such as density (d) and Vickers microhardness (HV), were measured. Compactness (C), as well as some thermomechanical characteristics, such as module of elasticity (E), volume (Vh), and formation energy (Eh) of micro-voids, were calculated, and the influence of the composition on these characteristics was investigated. The addition of silver telluride resulted in a decrease in Tg and HV values and an increase in d and Vh values. No thermochemical effects of crystallization or melting were detected in some of the alloys. The obtained results were in agreement with the available literature data for similar systems.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2023-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139158719","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-12-25DOI: 10.3390/inorganics12010010
M. Stogniy
The fifth element of the Periodic Table is boron [...]
元素周期表中的第五种元素是硼 [...]
{"title":"Fifth Element: The Current State of Boron Chemistry","authors":"M. Stogniy","doi":"10.3390/inorganics12010010","DOIUrl":"https://doi.org/10.3390/inorganics12010010","url":null,"abstract":"The fifth element of the Periodic Table is boron [...]","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2023-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139158940","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The development of cathode materials with high specific capacity is the key to obtaining high-performance lithium-ion batteries, which are crucial for the efficient utilization of clean energy and the realization of carbon neutralization goals. Li-rich Mn-based cathode materials (LRM) exhibit high specific capacity because of both cationic and anionic redox activity and are expected to be developed and applied as cathode materials for a new generation of high-energy density lithium-ion batteries. Nevertheless, the difficulty of regulating anionic redox reactions poses significant challenges to LRM, such as low initial Coulombic efficiency, poor rate capability, and fast cycling capacity and voltage decay. To address the existing challenges of LRM, this review introduces their basic physicochemical characteristics in detail, analyzes the original causes of these challenges, focuses on the recent progress of the modification strategies, and then especially discusses the development prospects of LRM from different aspects.
{"title":"Li-Rich Mn-Based Cathode Materials for Li-Ion Batteries: Progress and Perspective","authors":"Weibin Guo, Zhangzhao Weng, Chongyang Zhou, Min Han, Naien Shi, Qingshui Xie, Dong Peng","doi":"10.3390/inorganics12010008","DOIUrl":"https://doi.org/10.3390/inorganics12010008","url":null,"abstract":"The development of cathode materials with high specific capacity is the key to obtaining high-performance lithium-ion batteries, which are crucial for the efficient utilization of clean energy and the realization of carbon neutralization goals. Li-rich Mn-based cathode materials (LRM) exhibit high specific capacity because of both cationic and anionic redox activity and are expected to be developed and applied as cathode materials for a new generation of high-energy density lithium-ion batteries. Nevertheless, the difficulty of regulating anionic redox reactions poses significant challenges to LRM, such as low initial Coulombic efficiency, poor rate capability, and fast cycling capacity and voltage decay. To address the existing challenges of LRM, this review introduces their basic physicochemical characteristics in detail, analyzes the original causes of these challenges, focuses on the recent progress of the modification strategies, and then especially discusses the development prospects of LRM from different aspects.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2023-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139160400","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-12-23DOI: 10.3390/inorganics12010007
A. Pradhan, Shippy Jaiswal, Marie Cordier, J. Halet, Sundargopal Ghosh
The synthesis and structural characterization of a series of heterotrimetallic ruthenaborane clusters are reported. The photolytic reaction of nido-[(Cp*Ru)2(µ-H)2B3H7] (nido-1) (Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl) with [M(CO)5·THF] (THF = tetrahydrofuran, M = Mo and W) yielded the heterotrimetallic clusters pileo-[(Cp*Ru)2{M(CO)3}(µ-CO)(µ-H)(µ3-BH)B2H5], M = Mo (2), W (3) and the known arachno ruthenaboranes [1,2-(Cp*Ru)(Cp*RuCO)(µ-H)B3H8] (I) and [{Cp*Ru(CO)}2B2H6] (II). In an attempt to synthesize the Mn-analog of 2 and 3, we performed a similar reaction of nido-1 with [Mn2(CO)10], which afforded the heterotrimetallic pileo-[(Cp*Ru){Mn(CO)3}(µ-H)2(µ3-BH)B2H5] (4) cluster along with the reported trimetallic hydrido(hydroborylene) species [(Cp*Ru)2{Mn(CO)3}(µ-H)(µ-CO)3(µ-BH)] (III). Ruthenaboranes 2, 3 and 4 are isoelectronic and isostructural. The geometry of 2–4 can be viewed as a triangle face-fused square pyramidal and tetrahedral geometry, in which the apical vertex of the tetrahedron is occupied by a µ3–BH moiety. All of these pileo ruthenaborane clusters obey Mingos’ fusion formalism. Clusters 2–4 were characterized using multinuclear NMR, IR spectroscopies and electrospray ionization mass spectrometry. The single-crystal X-ray diffraction studies of clusters 2 and 4 confirmed their structures. Further, density functional theory (DFT) studies of these pileo ruthenaboranes have been carried out to investigate the nature of bonding, fusion and electronic structures.
{"title":"Metal Rich Metallaboranes: Synthesis, Structure and Bonding of pileo-[(Cp*Ru)2M(CO)3(µ-H)(µ-E)(µ3-BH)B2H5] (M = Mo, W, E = CO, and M = Mn, E = H) Clusters","authors":"A. Pradhan, Shippy Jaiswal, Marie Cordier, J. Halet, Sundargopal Ghosh","doi":"10.3390/inorganics12010007","DOIUrl":"https://doi.org/10.3390/inorganics12010007","url":null,"abstract":"The synthesis and structural characterization of a series of heterotrimetallic ruthenaborane clusters are reported. The photolytic reaction of nido-[(Cp*Ru)2(µ-H)2B3H7] (nido-1) (Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl) with [M(CO)5·THF] (THF = tetrahydrofuran, M = Mo and W) yielded the heterotrimetallic clusters pileo-[(Cp*Ru)2{M(CO)3}(µ-CO)(µ-H)(µ3-BH)B2H5], M = Mo (2), W (3) and the known arachno ruthenaboranes [1,2-(Cp*Ru)(Cp*RuCO)(µ-H)B3H8] (I) and [{Cp*Ru(CO)}2B2H6] (II). In an attempt to synthesize the Mn-analog of 2 and 3, we performed a similar reaction of nido-1 with [Mn2(CO)10], which afforded the heterotrimetallic pileo-[(Cp*Ru){Mn(CO)3}(µ-H)2(µ3-BH)B2H5] (4) cluster along with the reported trimetallic hydrido(hydroborylene) species [(Cp*Ru)2{Mn(CO)3}(µ-H)(µ-CO)3(µ-BH)] (III). Ruthenaboranes 2, 3 and 4 are isoelectronic and isostructural. The geometry of 2–4 can be viewed as a triangle face-fused square pyramidal and tetrahedral geometry, in which the apical vertex of the tetrahedron is occupied by a µ3–BH moiety. All of these pileo ruthenaborane clusters obey Mingos’ fusion formalism. Clusters 2–4 were characterized using multinuclear NMR, IR spectroscopies and electrospray ionization mass spectrometry. The single-crystal X-ray diffraction studies of clusters 2 and 4 confirmed their structures. Further, density functional theory (DFT) studies of these pileo ruthenaboranes have been carried out to investigate the nature of bonding, fusion and electronic structures.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2023-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139162867","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-12-22DOI: 10.3390/inorganics12010005
K. Bilińska, Maciej J. Winiarski
Machine learning models (Support Vector Regression) were applied for predictions of several targets for 18-electron half-Heusler phases: a lattice parameter, a bulk modulus, a band gap, and a lattice thermal conductivity. The training subset, which consisted of 47 stable phases, was studied with the use of Density Functional Theory calculations with two Exchange-Correlation Functionals employed (GGA, MBJGGA). The predictors for machine learning models were defined among the basic properties of the elements. The most optimal combinations of predictors for each target were proposed and discussed. Root Mean Squared Errors obtained for the best combinations of predictors for the particular targets are as follows: 0.1 Å (lattice parameters), 11–12 GPa (bulk modulus), 0.22 eV (band gaps, GGA and MBJGGA), and 9–9.5 W/mK (lattice thermal conductivity). The final results of the predictions for a large set of 74 semiconducting half-Heusler compounds were disclosed and compared to the available literature and experimental data. The findings presented in this work encourage further studies with the use of combined machine learning and ab initio calculations.
应用机器学习模型（支持向量回归）预测了 18 电子半休斯勒相的几个目标：晶格参数、体模量、带隙和晶格热导率。训练子集由 47 个稳定相组成，使用密度泛函理论计算进行研究，并采用了两种交换相关函数（GGA、MBJGGA）。机器学习模型的预测因子是根据元素的基本特性确定的。针对每个目标提出并讨论了预测因子的最佳组合。针对特定目标的预测因子最佳组合的均方根误差如下：0.1 Å（晶格参数）、11-12 GPa（体积模量）、0.22 eV（带隙，GGA 和 MBJGGA）和 9-9.5 W/mK（晶格热导率）。对一大批 74 种半导体半休斯勒化合物的最终预测结果进行了披露，并与现有文献和实验数据进行了比较。这项工作中的发现鼓励了使用机器学习和 ab initio 计算相结合的方法开展进一步研究。
{"title":"Machine Learning-Based Predictions for Half-Heusler Phases","authors":"K. Bilińska, Maciej J. Winiarski","doi":"10.3390/inorganics12010005","DOIUrl":"https://doi.org/10.3390/inorganics12010005","url":null,"abstract":"Machine learning models (Support Vector Regression) were applied for predictions of several targets for 18-electron half-Heusler phases: a lattice parameter, a bulk modulus, a band gap, and a lattice thermal conductivity. The training subset, which consisted of 47 stable phases, was studied with the use of Density Functional Theory calculations with two Exchange-Correlation Functionals employed (GGA, MBJGGA). The predictors for machine learning models were defined among the basic properties of the elements. The most optimal combinations of predictors for each target were proposed and discussed. Root Mean Squared Errors obtained for the best combinations of predictors for the particular targets are as follows: 0.1 Å (lattice parameters), 11–12 GPa (bulk modulus), 0.22 eV (band gaps, GGA and MBJGGA), and 9–9.5 W/mK (lattice thermal conductivity). The final results of the predictions for a large set of 74 semiconducting half-Heusler compounds were disclosed and compared to the available literature and experimental data. The findings presented in this work encourage further studies with the use of combined machine learning and ab initio calculations.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2023-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139164103","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-12-21DOI: 10.3390/inorganics12010004
Nikola D. Radnović, Nađa Štetin, M. Radanović, Ivana Đ. Borišev, M. Rodić, Ž. Jaćimović, Berta Barta Holló
The synthesis of the first Ag(I) complexes with ethyl-5-amino-1-methyl-1H-pyrazole-4-carboxylate (L) is presented. The reaction of AgClO4 with the ligand in a molar ratio of 1:1 gives a bis(ligand) complex [AgL2]ClO4 (1) in the presence of 4-formylbenzonitrile, monoperiodic polymer {[AgL2]ClO4}n (2). Characterization involved IR spectroscopy, conductometric measurements, thermogravimetric analysis, antioxidant tests, powder, and single crystal X-ray diffraction. Structural analysis revealed ligand coordination in a monodentate manner through the nitrogen atom of the pyrazole ring in both complexes. Complex 1 displayed a linear coordination environment for Ag(I), whereas, in complex 2, square-planar coordination was achieved with the additional involvement of two oxygen atoms from bridging perchlorate anions. Notably, the thermal properties of both isomers are found to be nearly identical. The significant antioxidant activity of the isomer with a reverse-oriented pyrazole-type ligand suggests its potential relevance in biological studies.
{"title":"Two Isomers of a Novel Ag(I) Complex with Pyrazole-Type Ligand—Synthesis, Structural, Thermal, and Antioxidative Characterization","authors":"Nikola D. Radnović, Nađa Štetin, M. Radanović, Ivana Đ. Borišev, M. Rodić, Ž. Jaćimović, Berta Barta Holló","doi":"10.3390/inorganics12010004","DOIUrl":"https://doi.org/10.3390/inorganics12010004","url":null,"abstract":"The synthesis of the first Ag(I) complexes with ethyl-5-amino-1-methyl-1H-pyrazole-4-carboxylate (L) is presented. The reaction of AgClO4 with the ligand in a molar ratio of 1:1 gives a bis(ligand) complex [AgL2]ClO4 (1) in the presence of 4-formylbenzonitrile, monoperiodic polymer {[AgL2]ClO4}n (2). Characterization involved IR spectroscopy, conductometric measurements, thermogravimetric analysis, antioxidant tests, powder, and single crystal X-ray diffraction. Structural analysis revealed ligand coordination in a monodentate manner through the nitrogen atom of the pyrazole ring in both complexes. Complex 1 displayed a linear coordination environment for Ag(I), whereas, in complex 2, square-planar coordination was achieved with the additional involvement of two oxygen atoms from bridging perchlorate anions. Notably, the thermal properties of both isomers are found to be nearly identical. The significant antioxidant activity of the isomer with a reverse-oriented pyrazole-type ligand suggests its potential relevance in biological studies.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":2.9,"publicationDate":"2023-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138949555","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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