Pub Date : 2023-12-14DOI: 10.3390/inorganics11120478
S. Mangelsen, Patrick Zimmer, Christian Näther, W. Bensch
Transition metal inserted NbS2 (TxNbS2) compounds receive great attention due to their intriguing and diverse magnetic and electric transport properties. Typically, these compounds are prepared by high-temperature synthesis from the elements, which is time and energy-consuming and yields highly crystalline products. So far, no route for preparing these compounds from precursors by thermal decomposition has been reported. Herein, we report the synthesis of a dithiocarbamate of niobium Nb2S4(CS2NH2)4 as a precursor for the synthesis of NbS2 by this preparative strategy. Furthermore, we demonstrate that a co-decomposition with dithiocarbamates of transition metals (here, Co and Pd) is a viable route for the synthesis of TxNbS2-type compounds. This is a promising route for the exploration of these compounds’ properties in the form of, e.g., nanocrystalline or thin film samples.
过渡金属插入 NbS2（TxNbS2）化合物因其引人入胜的多样化磁性和电传输特性而备受关注。通常情况下，这些化合物是通过元素高温合成法制备的，这种方法耗时耗能，而且生成的产品结晶度很高。迄今为止，还没有报道过通过热分解从前驱体制备这些化合物的路线。在此，我们报告了铌的二硫代氨基甲酸盐 Nb2S4(CS2NH2)4 的合成，以此为前驱体，通过这种制备策略合成 NbS2。此外，我们还证明了与过渡金属（此处为 Co 和 Pd）的二硫代氨基甲酸酯共分解是合成 TxNbS2 型化合物的可行路线。这对于探索这些化合物的特性（如纳米晶体或薄膜样品）是一条很有前景的途径。
{"title":"Nb2S4(CS2NH2)4—A New Precursor for NbS2 and Its Transition Metal Inserted Derivatives","authors":"S. Mangelsen, Patrick Zimmer, Christian Näther, W. Bensch","doi":"10.3390/inorganics11120478","DOIUrl":"https://doi.org/10.3390/inorganics11120478","url":null,"abstract":"Transition metal inserted NbS2 (TxNbS2) compounds receive great attention due to their intriguing and diverse magnetic and electric transport properties. Typically, these compounds are prepared by high-temperature synthesis from the elements, which is time and energy-consuming and yields highly crystalline products. So far, no route for preparing these compounds from precursors by thermal decomposition has been reported. Herein, we report the synthesis of a dithiocarbamate of niobium Nb2S4(CS2NH2)4 as a precursor for the synthesis of NbS2 by this preparative strategy. Furthermore, we demonstrate that a co-decomposition with dithiocarbamates of transition metals (here, Co and Pd) is a viable route for the synthesis of TxNbS2-type compounds. This is a promising route for the exploration of these compounds’ properties in the form of, e.g., nanocrystalline or thin film samples.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"26 1","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138973318","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 : 2023-12-14DOI: 10.3390/inorganics11120479
Chourouk Kefi, J. Huot
In this paper, we report the effect of the Cr/Mn ratio on the thermodynamic properties of Ti30V60Mn(10−x)Crx (x = 0, 3.3, 6.6 and 10) + 4 wt.% Zr alloys. It was found that the enthalpy and entropy change with the Cr/MN ratio and that the entropy and entropy variation is coupled in an enthalpy-entropy compensation fashion. Using a compensation quality factor, it was established that the enthalpy-entropy compensation is not due to a statistical origin, with a confidence of more than 95%.
{"title":"Entropy-Enthalpy Compensation in Ti-V-Mn-Cr BCC Alloys Used as Hydrogen Storage Materials","authors":"Chourouk Kefi, J. Huot","doi":"10.3390/inorganics11120479","DOIUrl":"https://doi.org/10.3390/inorganics11120479","url":null,"abstract":"In this paper, we report the effect of the Cr/Mn ratio on the thermodynamic properties of Ti30V60Mn(10−x)Crx (x = 0, 3.3, 6.6 and 10) + 4 wt.% Zr alloys. It was found that the enthalpy and entropy change with the Cr/MN ratio and that the entropy and entropy variation is coupled in an enthalpy-entropy compensation fashion. Using a compensation quality factor, it was established that the enthalpy-entropy compensation is not due to a statistical origin, with a confidence of more than 95%.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"34 2","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139003209","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 : 2023-12-11DOI: 10.3390/inorganics11120476
T. Humphries, C. Buckley, M. Paskevicius, Torben R. Jensen
Hydrogen is heralded as a future global energy carrier [...]
氢被誉为未来的全球能源载体 [...]
{"title":"State-of-the-Art and Progress in Metal-Hydrogen Systems","authors":"T. Humphries, C. Buckley, M. Paskevicius, Torben R. Jensen","doi":"10.3390/inorganics11120476","DOIUrl":"https://doi.org/10.3390/inorganics11120476","url":null,"abstract":"Hydrogen is heralded as a future global energy carrier [...]","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"14 7","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138980065","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 prediction of stack output power in solid oxide fuel cell (SOFC) systems is a key technology that urgently needs improvement, which will promote SOFC systems towards high-power multi-stack applications. The accuracy of power prediction directly determines the control effect and working condition recognition accuracy of the SOFC system controller. In order to achieve this goal, a genetic algorithm back propagation (GA-BP) neural network is constructed to predict output power in the SOFC system. By testing 40 sets of sample data collected from the experimental platform, it is found that the GA-BP method overcomes the limitation of the traditional back propagation (BP) method—falling into local optima. Further analysis shows that the average relative error of GA-BP has decreased to 1%. The reduction of the relative error improves the accuracy of the prediction results and the average prediction accuracy. Compared with the long short-term memory (LSTM) and BP algorithm, the GA-BP prediction model significantly reduces the relative error of power output prediction, which provides a solid foundation for multi-stack SOFC systems.
{"title":"A Single-Stack Output Power Prediction Method for High-Power, Multi-Stack SOFC System Requirements","authors":"Daihui Zhang, Jiangong Hu, Wei Zhao, Meilin Lai, Zilin Gao, Xiaolong Wu","doi":"10.3390/inorganics11120474","DOIUrl":"https://doi.org/10.3390/inorganics11120474","url":null,"abstract":"The prediction of stack output power in solid oxide fuel cell (SOFC) systems is a key technology that urgently needs improvement, which will promote SOFC systems towards high-power multi-stack applications. The accuracy of power prediction directly determines the control effect and working condition recognition accuracy of the SOFC system controller. In order to achieve this goal, a genetic algorithm back propagation (GA-BP) neural network is constructed to predict output power in the SOFC system. By testing 40 sets of sample data collected from the experimental platform, it is found that the GA-BP method overcomes the limitation of the traditional back propagation (BP) method—falling into local optima. Further analysis shows that the average relative error of GA-BP has decreased to 1%. The reduction of the relative error improves the accuracy of the prediction results and the average prediction accuracy. Compared with the long short-term memory (LSTM) and BP algorithm, the GA-BP prediction model significantly reduces the relative error of power output prediction, which provides a solid foundation for multi-stack SOFC systems.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"2 3","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138595729","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 : 2023-12-06DOI: 10.3390/inorganics11120475
Trent Quist, Jiahua Chen, Alex MacNeil, M. Pandelia
Fe-S clusters are ubiquitous inorganic cofactors found in proteins across all domains of life, including viruses. Their prevalence stems from their unique redox and structural plasticity that supports functions ranging from electron transfer and catalysis to stabilization of protein structure. Although the ability of Fe-S clusters to exchange electrons is often functionally crucial, it can also act as an Achilles heel when these cofactors are exposed to oxidizing conditions, often leading to their degradation. This O2 sensitivity has rendered certain Fe-S clusters untraceable, particularly when the nascent proteins are isolated under ambient conditions. As a consequence of this O2 sensitivity, a growing number of proteins with roles in viral infection have been found to harbor Fe-S clusters rather than the annotated Zn2+ cofactor. The enigmatic protein X (HBx) of the Hepatitis B Virus is a multifunctional protein essential for viral replication and development of liver disease. Although HBx has defied biochemical characterization for over forty years, it has been shown to coordinate a redox-active Fe-S cluster that represents a significant feature for establishing its molecular function. The present review narrates the approaches to validate the HBx metallocofactor that can be broadly applied as a guide for uncovering the presence of Fe-S clusters in proteins with non-canonical sequence motifs.
{"title":"The Cryptic Nature of Fe-S Clusters: A Case Study of the Hepatitis B HBx Oncoprotein","authors":"Trent Quist, Jiahua Chen, Alex MacNeil, M. Pandelia","doi":"10.3390/inorganics11120475","DOIUrl":"https://doi.org/10.3390/inorganics11120475","url":null,"abstract":"Fe-S clusters are ubiquitous inorganic cofactors found in proteins across all domains of life, including viruses. Their prevalence stems from their unique redox and structural plasticity that supports functions ranging from electron transfer and catalysis to stabilization of protein structure. Although the ability of Fe-S clusters to exchange electrons is often functionally crucial, it can also act as an Achilles heel when these cofactors are exposed to oxidizing conditions, often leading to their degradation. This O2 sensitivity has rendered certain Fe-S clusters untraceable, particularly when the nascent proteins are isolated under ambient conditions. As a consequence of this O2 sensitivity, a growing number of proteins with roles in viral infection have been found to harbor Fe-S clusters rather than the annotated Zn2+ cofactor. The enigmatic protein X (HBx) of the Hepatitis B Virus is a multifunctional protein essential for viral replication and development of liver disease. Although HBx has defied biochemical characterization for over forty years, it has been shown to coordinate a redox-active Fe-S cluster that represents a significant feature for establishing its molecular function. The present review narrates the approaches to validate the HBx metallocofactor that can be broadly applied as a guide for uncovering the presence of Fe-S clusters in proteins with non-canonical sequence motifs.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"97 1","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138596095","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 : 2023-12-05DOI: 10.3390/inorganics11120473
Sophie Riedel, Maik Gerwig, D. Gerlach, Erica Brendler, R. Gericke, E. Kroke, J. Wagler
4-Azidopyridine (1) and SiCl4 react with the formation of the hexacoordinate silicon complex SiCl4(4-azidopyridine)2 (2). Upon dissolving in warm chloroform, the complex dissociates into the constituents 1 and SiCl4 and forms back upon cooling. Depending on the cooling, two different crystalline modifications of 2 were obtained, which feature two different trans-conformers. Slow cooling to room temperature afforded conformer 2′, which features coplanar pyridine rings. Rapid cooling to −39 °C afforded crystals of conformer 2″, in which the planes of the pyridine ligands are nearly orthogonal to one another. Whereas 2′ resembles the molecular arrangement of various other known SiX4(pyridine)2 (X = halide) complexes, 2″ represents the first crystallographically confirmed example of a SiX4(pyridine)2 complex in this conformation. Conformers 2′ and 2″ were studied with 13C and 29Si solid state NMR spectroscopy. Their differences in 29Si chemical shift anisotropy, as well as energetic differences, were further investigated with computational analyses. In spite of the similar stabilities of the two conformers as isolated molecules, the crystal packing of 2″ is less stable, and its crystallization is interpreted as a kinetically controlled effect of seed formation. (3+2)-cycloaddition of 1 and phenylacetylene in toluene at 110 °C yields a mixture of 1-(4-pyridyl)-4-phenyl-1,2,3-triazole (1,4-3) and 1-(4-pyridyl)-5-phenyl-1,2,3-triazole (1,5-3) in approximate 1:2 molar ratio. The crystal structures of the two isomers were determined via X-ray diffraction. In chloroform (at 60 °C), this reaction is slow (less than 2% conversion within 4 h), but the presence of SiCl4 enhanced the rate of the reaction slightly, and it shifted the triazole isomer ratio to ca. 1:6 in favor of 1,5-3.
{"title":"The Hexacoordinate Si Complex SiCl4(4-Azidopyridine)2—Crystallographic Characterization of Two Conformers and Probing the Influence of SiCl4-Complexation on a Click Reaction with Phenylacetylene","authors":"Sophie Riedel, Maik Gerwig, D. Gerlach, Erica Brendler, R. Gericke, E. Kroke, J. Wagler","doi":"10.3390/inorganics11120473","DOIUrl":"https://doi.org/10.3390/inorganics11120473","url":null,"abstract":"4-Azidopyridine (1) and SiCl4 react with the formation of the hexacoordinate silicon complex SiCl4(4-azidopyridine)2 (2). Upon dissolving in warm chloroform, the complex dissociates into the constituents 1 and SiCl4 and forms back upon cooling. Depending on the cooling, two different crystalline modifications of 2 were obtained, which feature two different trans-conformers. Slow cooling to room temperature afforded conformer 2′, which features coplanar pyridine rings. Rapid cooling to −39 °C afforded crystals of conformer 2″, in which the planes of the pyridine ligands are nearly orthogonal to one another. Whereas 2′ resembles the molecular arrangement of various other known SiX4(pyridine)2 (X = halide) complexes, 2″ represents the first crystallographically confirmed example of a SiX4(pyridine)2 complex in this conformation. Conformers 2′ and 2″ were studied with 13C and 29Si solid state NMR spectroscopy. Their differences in 29Si chemical shift anisotropy, as well as energetic differences, were further investigated with computational analyses. In spite of the similar stabilities of the two conformers as isolated molecules, the crystal packing of 2″ is less stable, and its crystallization is interpreted as a kinetically controlled effect of seed formation. (3+2)-cycloaddition of 1 and phenylacetylene in toluene at 110 °C yields a mixture of 1-(4-pyridyl)-4-phenyl-1,2,3-triazole (1,4-3) and 1-(4-pyridyl)-5-phenyl-1,2,3-triazole (1,5-3) in approximate 1:2 molar ratio. The crystal structures of the two isomers were determined via X-ray diffraction. In chloroform (at 60 °C), this reaction is slow (less than 2% conversion within 4 h), but the presence of SiCl4 enhanced the rate of the reaction slightly, and it shifted the triazole isomer ratio to ca. 1:6 in favor of 1,5-3.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"129 5","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138599289","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 : 2023-12-04DOI: 10.3390/inorganics11120471
Ludwig Zapf, Maik Finze
Novel hexafluoroisopropylboranes (CF3)(CF2H)CFBH2·L and -borate anions [(CF3)(CF2H)CFBH2X]− with Lewis basic heterocyclic ligands L and the anionic substituents X = F− and CN− were obtained. The syntheses were accomplished by substitution reactions of the dimethyl sulfide adduct (CF3)(CF2H)CFBH2·SMe2, which was synthesized on a large scale. The hexafluoroisopropylboranes and -borates were characterized by NMR and vibrational spectroscopy, elemental analysis, and single-crystal X-ray diffraction. In addition, the thermal and electrochemical stabilities were investigated by DSC measurements and cyclic voltammetry and selected experimental data and trends are compared with theoretical ones.
{"title":"Hexafluoroisopropylboranes and -Borates","authors":"Ludwig Zapf, Maik Finze","doi":"10.3390/inorganics11120471","DOIUrl":"https://doi.org/10.3390/inorganics11120471","url":null,"abstract":"Novel hexafluoroisopropylboranes (CF3)(CF2H)CFBH2·L and -borate anions [(CF3)(CF2H)CFBH2X]− with Lewis basic heterocyclic ligands L and the anionic substituents X = F− and CN− were obtained. The syntheses were accomplished by substitution reactions of the dimethyl sulfide adduct (CF3)(CF2H)CFBH2·SMe2, which was synthesized on a large scale. The hexafluoroisopropylboranes and -borates were characterized by NMR and vibrational spectroscopy, elemental analysis, and single-crystal X-ray diffraction. In addition, the thermal and electrochemical stabilities were investigated by DSC measurements and cyclic voltammetry and selected experimental data and trends are compared with theoretical ones.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"35 24","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138602642","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 : 2023-12-02DOI: 10.3390/inorganics11120470
Panagiota Tryfon, N. Kamou, S. Mourdikoudis, George Vourlias, U. Menkissoglu-Spiroudi, C. Dendrinou-Samara
Nanotechnology presents promising opportunities for enhancing pest management strategies, particularly in protecting active ingredients to prolong their shelf life and effectiveness. Among different approaches, the combination of inorganic nanoparticles with active ingredients such as the main constituents of natural essential oils in one nanoarchitecture is challenging. In this study, hydrophobic calcium hydroxide nanoparticles coated with oleylamime [Ca(OH)2@OAm NPs] were synthesized using microwave-assisted synthesis. These primary NPs were physicochemically characterized and subsequently utilized to prepare nanocapsules (NCs) either alone (Ca NCs) and/or in combination with geraniol at different ratios of Ca(OH)2@OAm NPs and geraniol, i.e. 1:1 (CaGer1 NCs), 1:2 (CaGer2 NCs), and 1:3 (CaGer3 NCs), respectively. Among the formulations, the CaGer2 NCs demonstrated higher encapsulation efficiency (EE) and loading capacity (LC) of 95% and 20%, correspondingly. They exhibited a hydrodynamic size of 306 nm, a ζ-potential of −35 mV, and a monodisperse distribution. Release kinetics of geraniol from CaGer2 NCs indicated a pH-dependent slow release over 96 h at both 25 °C and 35 °C. In vitro antifungal assay against B. cinerea revealed a concentration-dependent activity, and the EC50 values for Ca(OH)2@OAm NPs, Ca NCs, and CaGer2 NCs were estimated to be 654 µg/mL, 395 µg/mL, and 507 µg/mL, respectively. These results underscore the potential of Ca-based nanoformulations to control plant pathogens, suggesting that while Ca NCs showcase potent antifungal attributes, the different architectures/structures play a critical role in the antifungal effectiveness of the nanoformulations that have to be explored further.
{"title":"Microwave-Mediated Synthesis and Characterization of Ca(OH)2 Nanoparticles Destined for Geraniol Encapsulation","authors":"Panagiota Tryfon, N. Kamou, S. Mourdikoudis, George Vourlias, U. Menkissoglu-Spiroudi, C. Dendrinou-Samara","doi":"10.3390/inorganics11120470","DOIUrl":"https://doi.org/10.3390/inorganics11120470","url":null,"abstract":"Nanotechnology presents promising opportunities for enhancing pest management strategies, particularly in protecting active ingredients to prolong their shelf life and effectiveness. Among different approaches, the combination of inorganic nanoparticles with active ingredients such as the main constituents of natural essential oils in one nanoarchitecture is challenging. In this study, hydrophobic calcium hydroxide nanoparticles coated with oleylamime [Ca(OH)2@OAm NPs] were synthesized using microwave-assisted synthesis. These primary NPs were physicochemically characterized and subsequently utilized to prepare nanocapsules (NCs) either alone (Ca NCs) and/or in combination with geraniol at different ratios of Ca(OH)2@OAm NPs and geraniol, i.e. 1:1 (CaGer1 NCs), 1:2 (CaGer2 NCs), and 1:3 (CaGer3 NCs), respectively. Among the formulations, the CaGer2 NCs demonstrated higher encapsulation efficiency (EE) and loading capacity (LC) of 95% and 20%, correspondingly. They exhibited a hydrodynamic size of 306 nm, a ζ-potential of −35 mV, and a monodisperse distribution. Release kinetics of geraniol from CaGer2 NCs indicated a pH-dependent slow release over 96 h at both 25 °C and 35 °C. In vitro antifungal assay against B. cinerea revealed a concentration-dependent activity, and the EC50 values for Ca(OH)2@OAm NPs, Ca NCs, and CaGer2 NCs were estimated to be 654 µg/mL, 395 µg/mL, and 507 µg/mL, respectively. These results underscore the potential of Ca-based nanoformulations to control plant pathogens, suggesting that while Ca NCs showcase potent antifungal attributes, the different architectures/structures play a critical role in the antifungal effectiveness of the nanoformulations that have to be explored further.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"116 16","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138607530","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 : 2023-12-01DOI: 10.3390/inorganics11120468
R. Gomila, E. R. Tiekink, A. Frontera
Three homoleptic Hg(S2CNR2)2, for R = ethyl (1), isobutyl (2), and cyclohexyl (3), compounds apparently exhibit a steric-dependent supramolecular association in their crystals. The small group in 1 allows for dimer formation via covalent Hg–S interactions through an eight-membered {–HgSCS}2 ring as the dithiocarbamato ligands bridge centrosymmetrically related Hg atoms; intradimer Hg···S interactions are noted. By contrast, centrosymmetrically related molecules in 2 are aligned to enable intermolecular Hg···S interactions, but the separations greatly exceed the van der Waals radii. The large group in 3 precludes both dimerization and intermolecular Hg···S interactions. Computational chemistry indicates that the potential region at the Hg atom is highly dependent on the coordination geometry about the Hg atom. Intramolecular (1) and intermolecular (2) spodium bonding (SpB) is demonstrated. Even at separations approaching 0.4 Å beyond the sum of the assumed van der Waals radii, the energy of the stabilization afforded by the structure directs SpB in 2 amounts to approximately 2.5 kcal/mol. A natural bond orbital (NBO) analysis points to the importance of the LP(S) → σ*(Hg–S) charge transfer and to the dominance of the dispersion forces and electron correlation to the SpB in 2.
{"title":"A Computational Chemistry Investigation of the Influence of Steric Bulk of Dithiocarbamato-Bound Organic Substituents upon Spodium Bonding in Three Homoleptic Mercury(II) Bis(N,N-dialkyldithiocarbamato) Compounds for Alkyl = Ethyl, Isobutyl, and Cyclohexyl","authors":"R. Gomila, E. R. Tiekink, A. Frontera","doi":"10.3390/inorganics11120468","DOIUrl":"https://doi.org/10.3390/inorganics11120468","url":null,"abstract":"Three homoleptic Hg(S2CNR2)2, for R = ethyl (1), isobutyl (2), and cyclohexyl (3), compounds apparently exhibit a steric-dependent supramolecular association in their crystals. The small group in 1 allows for dimer formation via covalent Hg–S interactions through an eight-membered {–HgSCS}2 ring as the dithiocarbamato ligands bridge centrosymmetrically related Hg atoms; intradimer Hg···S interactions are noted. By contrast, centrosymmetrically related molecules in 2 are aligned to enable intermolecular Hg···S interactions, but the separations greatly exceed the van der Waals radii. The large group in 3 precludes both dimerization and intermolecular Hg···S interactions. Computational chemistry indicates that the potential region at the Hg atom is highly dependent on the coordination geometry about the Hg atom. Intramolecular (1) and intermolecular (2) spodium bonding (SpB) is demonstrated. Even at separations approaching 0.4 Å beyond the sum of the assumed van der Waals radii, the energy of the stabilization afforded by the structure directs SpB in 2 amounts to approximately 2.5 kcal/mol. A natural bond orbital (NBO) analysis points to the importance of the LP(S) → σ*(Hg–S) charge transfer and to the dominance of the dispersion forces and electron correlation to the SpB in 2.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"4 4","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138627474","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 : 2023-12-01DOI: 10.3390/inorganics11120465
Katja Engel, Thomas Schleid
The new rubidium-containing erbium sulfide thioarsenate(III) with the structured formula RbEr2S(S2)[AsS2(S2)] was obtained from the syntheses of elemental erbium (Er), arsenic sesquisulfide (As2S3) and rubidium sesquisulfide (Rb2S3) with elemental sulfur (S) at 773 K as transparent, orange, needle-shaped crystals. RbEr2AsS7 crystallizes monoclinically in the space group C2/c with a = 2339.86(12) pm, b = 541.78(3) pm, c = 1686.71(9) pm and β = 93.109(3) ° for Z = 8. The crystal structure features complex [AsS2(S2)]3− anions with two S2− anions and a (S2)2− disulfide dumbbell coordinating end-on as ligands for each As3+ cation. Even outside the ligand sphere of As3+, S2− and (S2)2− can be found as sulfide anions. Two distinct Er3+ cations are surrounded by either nine or seven sulfur atoms. The [ErS9] polyhedra are corner- and face-connected, while the [ErS7] units share common edges, both building chains along [010]. These different chains undergo edge connectivity with each other, resulting in the formation of corrugated layers, which are held together by Rb+ in chains of condensed [RbS9] polyhedra. So, a three-dimensional network is generated, offering empty channels along [010] apt to take up the As3+ lone-pair cations. Wavelength-dispersive X-ray spectroscopy verified a molar Rb:Er:As:S ratio of approximately 1:2:1:7 and diffuse reflectance spectroscopy showed the typical f–f transitions of Er3+, while the optical band gap was found to be 2.42 eV.
{"title":"RbEr2AsS7: A Rubidium-Containing Erbium Sulfide Thioarsenate(III) with (S2)2− Ligands According to RbEr2S(S2)[AsS2(S2)]","authors":"Katja Engel, Thomas Schleid","doi":"10.3390/inorganics11120465","DOIUrl":"https://doi.org/10.3390/inorganics11120465","url":null,"abstract":"The new rubidium-containing erbium sulfide thioarsenate(III) with the structured formula RbEr2S(S2)[AsS2(S2)] was obtained from the syntheses of elemental erbium (Er), arsenic sesquisulfide (As2S3) and rubidium sesquisulfide (Rb2S3) with elemental sulfur (S) at 773 K as transparent, orange, needle-shaped crystals. RbEr2AsS7 crystallizes monoclinically in the space group C2/c with a = 2339.86(12) pm, b = 541.78(3) pm, c = 1686.71(9) pm and β = 93.109(3) ° for Z = 8. The crystal structure features complex [AsS2(S2)]3− anions with two S2− anions and a (S2)2− disulfide dumbbell coordinating end-on as ligands for each As3+ cation. Even outside the ligand sphere of As3+, S2− and (S2)2− can be found as sulfide anions. Two distinct Er3+ cations are surrounded by either nine or seven sulfur atoms. The [ErS9] polyhedra are corner- and face-connected, while the [ErS7] units share common edges, both building chains along [010]. These different chains undergo edge connectivity with each other, resulting in the formation of corrugated layers, which are held together by Rb+ in chains of condensed [RbS9] polyhedra. So, a three-dimensional network is generated, offering empty channels along [010] apt to take up the As3+ lone-pair cations. Wavelength-dispersive X-ray spectroscopy verified a molar Rb:Er:As:S ratio of approximately 1:2:1:7 and diffuse reflectance spectroscopy showed the typical f–f transitions of Er3+, while the optical band gap was found to be 2.42 eV.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":"21 10","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138627254","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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