Aiming at the problem of poor stability of traditional hydrogels in flexible sensing applications, in this paper, a ternary eutectic solvent is successfully constructed by using choline chloride, acrylic acid, and ethylene glycol. By introducing α‐methacrylic acid (MAA) monomer and N , N ′‐methylene diacrylamide crosslinking agent, a new type of eutectic solvent gel is prepared by ultraviolet light‐initiated polymerization. The influence of MAA content on the mechanical properties of the gel is systematically studied. When the MAA content is 25 wt%, the comprehensive performance of the gel is the best, the fracture strain reaches 404%, the compressive strength is 1.38 MPa, and the elastic modulus (122 kPa) matched that of human skin. Differential scanning calorimetry confirmes that it still have no crystallization peak from room temperature to −80 °C and have excellent frost resistance. The maximum shear adhesion strength to nine substrates such as metals and plastics reached 343.4 kPa. The sensing test showes that the gel have a significant sensitivity (gauge factor = 1.64–4.06) within the strain range of 0%–320%, and could stably monitor human joint movements. This work provides a new strategy for developing high‐performance flexible wearable sensors suitable for extreme environments.
{"title":"Eutectic Solvent Gel for Flexible Wearable Sensors","authors":"Dengke Song, Zhiqing Li, Shihui Qiu, Songmei Ma, Gang Liu, Shaohua Zhang","doi":"10.1002/zaac.202500118","DOIUrl":"https://doi.org/10.1002/zaac.202500118","url":null,"abstract":"Aiming at the problem of poor stability of traditional hydrogels in flexible sensing applications, in this paper, a ternary eutectic solvent is successfully constructed by using choline chloride, acrylic acid, and ethylene glycol. By introducing α‐methacrylic acid (MAA) monomer and N , N ′‐methylene diacrylamide crosslinking agent, a new type of eutectic solvent gel is prepared by ultraviolet light‐initiated polymerization. The influence of MAA content on the mechanical properties of the gel is systematically studied. When the MAA content is 25 wt%, the comprehensive performance of the gel is the best, the fracture strain reaches 404%, the compressive strength is 1.38 MPa, and the elastic modulus (122 kPa) matched that of human skin. Differential scanning calorimetry confirmes that it still have no crystallization peak from room temperature to −80 °C and have excellent frost resistance. The maximum shear adhesion strength to nine substrates such as metals and plastics reached 343.4 kPa. The sensing test showes that the gel have a significant sensitivity (gauge factor = 1.64–4.06) within the strain range of 0%–320%, and could stably monitor human joint movements. This work provides a new strategy for developing high‐performance flexible wearable sensors suitable for extreme environments.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"651 17","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147332871","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jun Zhao, Feng-Qi Jiang, Rui Zhang, Dan Ba, Wen‐Wen Dong, Dong‐Sheng Li
Metal‐organic frameworks (MOFs) exhibit exceptional potential for proton conduction owing to their unique structural characteristics, including tunable porosity and functional surfaces. In this study, a novel proton exchange membrane is developed by incorporating a protic ionic liquid (IL) into NH 2 ‐MIL‐53(Al) materials of institute Lavoisier (MIL)and embedding the resulting composite within a sulfonated poly(ether ether ketone) (SPEEK) matrix. The porous architecture of the MOF facilitates the formation of an extensive hydrogen‐bonding network between the IL cations and water molecules, which is critical for efficient proton transport. Furthermore, the synergistic interaction between the NH 2 groups of NH 2 ‐MIL‐53(Al) and the SO 3 H groups of SPEEK enables dual‐proton‐conduction pathways, resulting in a remarkable proton conductivity of 0.42 S cm −1 for the IL@NH 2 ‐MIL‐53(Al)/SPEEK‐7 composite. Additionally, the IL@NH 2 ‐MIL‐53(Al)/SPEEK‐7 membrane demonstrates exceptional stability in proton conduction under tested conditions. This work provides a strategic approach for designing high‐performance and durable‐proton exchange membranes with significantly enhanced conductivity, offering valuable insights for future research in this field.
金属有机框架（mof）由于其独特的结构特征，包括可调节的孔隙率和功能表面，表现出非凡的质子传导潜力。在本研究中，将质子离子液体（IL）掺入拉瓦锡研究所（MIL）的nh2‐MIL‐53（Al）材料中，并将所得到的复合材料嵌入磺化聚醚醚酮（SPEEK）基质中，开发了一种新型质子交换膜。MOF的多孔结构有助于在IL离子和水分子之间形成广泛的氢键网络，这对于有效的质子传输至关重要。此外，nh2‐MIL‐53（Al）的nh2基团和SPEEK的so3 H基团之间的协同相互作用实现了双质子传导途径，导致IL@NH 2‐MIL‐53(Al)/SPEEK‐7复合材料的质子电导率达到0.42 S cm−1。此外，IL@NH 2‐MIL‐53(Al)/SPEEK‐7膜在测试条件下表现出优异的质子传导稳定性。这项工作为设计具有显著增强导电性的高性能和耐用的质子交换膜提供了一种战略方法，为该领域的未来研究提供了有价值的见解。
{"title":"Enhanced Proton Conductivity in Proton Exchange Membranes via Integration of Protic Ionic Liquid–Encapsulated NH<sub>2</sub>‐MIL‐53(Al) with Sulfonated Poly(Ether Ether Ketone)","authors":"Jun Zhao, Feng-Qi Jiang, Rui Zhang, Dan Ba, Wen‐Wen Dong, Dong‐Sheng Li","doi":"10.1002/zaac.202500038","DOIUrl":"https://doi.org/10.1002/zaac.202500038","url":null,"abstract":"Metal‐organic frameworks (MOFs) exhibit exceptional potential for proton conduction owing to their unique structural characteristics, including tunable porosity and functional surfaces. In this study, a novel proton exchange membrane is developed by incorporating a protic ionic liquid (IL) into NH 2 ‐MIL‐53(Al) materials of institute Lavoisier (MIL)and embedding the resulting composite within a sulfonated poly(ether ether ketone) (SPEEK) matrix. The porous architecture of the MOF facilitates the formation of an extensive hydrogen‐bonding network between the IL cations and water molecules, which is critical for efficient proton transport. Furthermore, the synergistic interaction between the NH 2 groups of NH 2 ‐MIL‐53(Al) and the SO 3 H groups of SPEEK enables dual‐proton‐conduction pathways, resulting in a remarkable proton conductivity of 0.42 S cm −1 for the IL@NH 2 ‐MIL‐53(Al)/SPEEK‐7 composite. Additionally, the IL@NH 2 ‐MIL‐53(Al)/SPEEK‐7 membrane demonstrates exceptional stability in proton conduction under tested conditions. This work provides a strategic approach for designing high‐performance and durable‐proton exchange membranes with significantly enhanced conductivity, offering valuable insights for future research in this field.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"651 9","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147332555","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ziyue Zhang, Zhuoer Cai, Yinan Zhang, Jian Chen, Xiu‐Ni Hua, Bai Wang Sun, Baiwang Sun
The focus of this study is on the development of novel host–guest inclusion compounds, which is a crucial molecule model for the synthesis of dielectric phase transition materials. In this research, a new host–guest inclusion compound is successfully synthesized by selecting 18‐crown‐6 as the host and 3‐aminocyclobutanone as the guest molecule. The thermal behavior and crystal structure of the compound are analyzed in this article. It is found that the compound exhibits a reversible phase transition near 147 K, accompanied by a dielectric anomaly, exhibiting dielectric switching characteristics. The 18‐crown‐6 molecule and the 3‐aminocyclobutanone molecule are connected via hydrogen bonding. Furthermore, the enthalpy changes of the heating process and cooling process are also calculated. This finding is expected to yield valuable new insights into the design of host–guest inclusions.
{"title":"Synthesis and Characterization of 18‐Crown‐6 with 3‐Aminocyclobutanone Guest: A Novel Host–Guest Inclusion Compound with Phase Transition","authors":"Ziyue Zhang, Zhuoer Cai, Yinan Zhang, Jian Chen, Xiu‐Ni Hua, Bai Wang Sun, Baiwang Sun","doi":"10.1002/zaac.202400210","DOIUrl":"https://doi.org/10.1002/zaac.202400210","url":null,"abstract":"The focus of this study is on the development of novel host–guest inclusion compounds, which is a crucial molecule model for the synthesis of dielectric phase transition materials. In this research, a new host–guest inclusion compound is successfully synthesized by selecting 18‐crown‐6 as the host and 3‐aminocyclobutanone as the guest molecule. The thermal behavior and crystal structure of the compound are analyzed in this article. It is found that the compound exhibits a reversible phase transition near 147 K, accompanied by a dielectric anomaly, exhibiting dielectric switching characteristics. The 18‐crown‐6 molecule and the 3‐aminocyclobutanone molecule are connected via hydrogen bonding. Furthermore, the enthalpy changes of the heating process and cooling process are also calculated. This finding is expected to yield valuable new insights into the design of host–guest inclusions.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"651 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147334161","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Anthony West, Yangyang Roy Zhao, Laurence Roy Middlemiss, Xuan Roy Zhi, Peter Roy Gross
It is widely recognised that oxygen redox makes a significant contribution to the high capacity of some cathode materials in addition to transition metal redox. We attribute this to the presence of underbonded oxide ions, either in bulk structures or at surfaces, which are the initial source of oxygen redox during charging. Underbonded oxide ions experience departures from local electroneutrality; examples include Li4Mn5O12 spinel and Li‐rich layered rock salt structures but not stoichiometric LiCoO2 or Li2MnO3. Underbonded oxide ions ionise more readily than fully‐stabilised lattice oxide ions since, using an ionic bonding description, they are associated with a deficiency of positive charge in the coordination sphere of surrounding cations. Pauling’s electrostatic bond strength criterion gives a simple guide to structures or compositions that show departures from local electroneutrality and provides the starting point for a new way to consider oxygen redox. Li4Mn5O12 behaves as an anode due to Mn redox below 3V and as a cathode due to reversible oxygen redox above ~3.8 V. Underbonded oxygens are also identified in other structures, including high capacity Li‐rich layered rock salt structures.
{"title":"Oxygen redox activity in battery cathodes and the role of underbonded oxygen","authors":"Anthony West, Yangyang Roy Zhao, Laurence Roy Middlemiss, Xuan Roy Zhi, Peter Roy Gross","doi":"10.1002/zaac.202400067","DOIUrl":"https://doi.org/10.1002/zaac.202400067","url":null,"abstract":"It is widely recognised that oxygen redox makes a significant contribution to the high capacity of some cathode materials in addition to transition metal redox. We attribute this to the presence of underbonded oxide ions, either in bulk structures or at surfaces, which are the initial source of oxygen redox during charging. Underbonded oxide ions experience departures from local electroneutrality; examples include Li4Mn5O12 spinel and Li‐rich layered rock salt structures but not stoichiometric LiCoO2 or Li2MnO3. Underbonded oxide ions ionise more readily than fully‐stabilised lattice oxide ions since, using an ionic bonding description, they are associated with a deficiency of positive charge in the coordination sphere of surrounding cations. Pauling’s electrostatic bond strength criterion gives a simple guide to structures or compositions that show departures from local electroneutrality and provides the starting point for a new way to consider oxygen redox. Li4Mn5O12 behaves as an anode due to Mn redox below 3V and as a cathode due to reversible oxygen redox above ~3.8 V. Underbonded oxygens are also identified in other structures, including high capacity Li‐rich layered rock salt structures.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"18 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142249060","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The novel inoborate Ni[B2O2(OH)4] was synthesized under high‐pressure/high‐temperature conditions of 9 GPa and 800 °C. Its structure was determined via single‐crystal X‐ray diffraction analysis. The single‐grain IR‐spectrum of Ni[B2O2(OH)4] supports the existence of O–H bonds. The structural similarities and differences with the mineral vimsite possessing the sum formula Ca[B2O2(OH)4], as well as with the phylloborate HP‐Ni(B2O4) is discussed. The title compound can be described as the structural hydrolysis product of the latter.
新型铌酸镍[B2O2(OH)4]是在 9 GPa 和 800 °C 的高压/高温条件下合成的。通过单晶 X 射线衍射分析确定了其结构。镍[B2O2(OH)4]的单晶红外光谱证明了 O-H 键的存在。本文讨论了该化合物与总式为 Ca[B2O2(OH)4] 的矿物 vimsite 以及栅硼酸盐 HP-Ni(B2O4) 在结构上的异同。标题化合物可以说是后者的结构水解产物。
{"title":"High‐Pressure Synthesis and Crystal Structure of the Inoborate Ni[B2O2(OH)4]","authors":"Leonard Conrad Pasqualini, Hubert Huppertz","doi":"10.1002/zaac.202400137","DOIUrl":"https://doi.org/10.1002/zaac.202400137","url":null,"abstract":"The novel inoborate Ni[B2O2(OH)4] was synthesized under high‐pressure/high‐temperature conditions of 9 GPa and 800 °C. Its structure was determined via single‐crystal X‐ray diffraction analysis. The single‐grain IR‐spectrum of Ni[B2O2(OH)4] supports the existence of O–H bonds. The structural similarities and differences with the mineral vimsite possessing the sum formula Ca[B2O2(OH)4], as well as with the phylloborate HP‐Ni(B2O4) is discussed. The title compound can be described as the structural hydrolysis product of the latter.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"43 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142190629","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The extraction of the solid state materials “MSnBix“ (M/x=Cs/1, Na/3) in liquid ammonia in the presence of different chelating agents yielded the novel Zintl anion [Sn5Bi3]3−. The anion could be crystallized and characterized via single crystal X‐ray diffraction in [Cs@[18]crown‐6]3[Sn5Bi3] ⋅ 7NH3, [K@[18]crown‐6]1.5[Cs@[18]crown‐6][Cs@([18]crown‐6)2]0.5[Sn5Bi3] ⋅ 3.98NH3, [Na@DB[18]crown‐6]2[Na(NH3)6][Sn5Bi3] ⋅ 14NH3 and [Cs@[2.2.2]crypt]6[Sn5Bi3]2 ⋅ 9.53NH3. The [Sn5Bi3]3− anion is further investigated by mass spectrometry and DFT calculations to confirm its composition and elucidate its electronic structure.
固态材料 "MSnBix"（M/x=Cs/1，Na/3）在不同螯合剂存在下于液氨中萃取，得到了新型 Zintl 阴离子[Sn5Bi3]3-。该阴离子可以结晶，并通过单晶 X 射线衍射在[Cs@[18]crown-6]3[Sn5Bi3]⋅7NH3、[K@[18]crown-6]1.5[Cs@[18]crown-6][Cs@([18]crown-6)2]0.5[Sn5Bi3]⋅3.98NH3，[Na@DB[18]crown-6]2[Na(NH3)6][Sn5Bi3]⋅14NH3 和 [Cs@[2.2.2]crypt]6[Sn5Bi3]2⋅9.53NH3。质谱法和 DFT 计算进一步研究了[Sn5Bi3]3-阴离子，以确认其组成并阐明其电子结构。
{"title":"Synthesis and Single Crystal X‐ray Characterization of [Sn5Bi3]3−","authors":"Ute Friedrich, Franz Schmidt, Nikolaus Korber","doi":"10.1002/zaac.202400086","DOIUrl":"https://doi.org/10.1002/zaac.202400086","url":null,"abstract":"The extraction of the solid state materials <jats:italic>“M</jats:italic>SnBi<jats:sub><jats:italic>x</jats:italic></jats:sub><jats:italic>“</jats:italic> (<jats:italic>M</jats:italic>/<jats:italic>x</jats:italic>=Cs/1, Na/3) in liquid ammonia in the presence of different chelating agents yielded the novel Zintl anion [Sn<jats:sub>5</jats:sub>Bi<jats:sub>3</jats:sub>]<jats:sup>3−</jats:sup>. The anion could be crystallized and characterized via single crystal X‐ray diffraction in [Cs@[18]crown‐6]<jats:sub>3</jats:sub>[Sn<jats:sub>5</jats:sub>Bi<jats:sub>3</jats:sub>] ⋅ 7NH<jats:sub>3</jats:sub>, [K@[18]crown‐6]<jats:sub>1.5</jats:sub>[Cs@[18]crown‐6][Cs@([18]crown‐6)<jats:sub>2</jats:sub>]<jats:sub>0.5</jats:sub>[Sn<jats:sub>5</jats:sub>Bi<jats:sub>3</jats:sub>] ⋅ 3.98NH<jats:sub>3</jats:sub>, [Na@DB[18]crown‐6]<jats:sub>2</jats:sub>[Na(NH<jats:sub>3</jats:sub>)<jats:sub>6</jats:sub>][Sn<jats:sub>5</jats:sub>Bi<jats:sub>3</jats:sub>] ⋅ 14NH<jats:sub>3</jats:sub> and [Cs@[2.2.2]crypt]<jats:sub>6</jats:sub>[Sn<jats:sub>5</jats:sub>Bi<jats:sub>3</jats:sub>]<jats:sub>2</jats:sub> ⋅ 9.53NH<jats:sub>3</jats:sub>. The [Sn<jats:sub>5</jats:sub>Bi<jats:sub>3</jats:sub>]<jats:sup>3−</jats:sup> anion is further investigated by mass spectrometry and DFT calculations to confirm its composition and elucidate its electronic structure.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142190637","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A pair of enantiomerically chiral dysprosium homodinuclear complexes: [(acac)4Dy2(R,R,R,R‐L)] (R‐Dy) and [(acac)4Dy2(S,S,S,S‐L)] (S‐Dy) (Hacac = acetylacetone) have been synthesized based on macrocyclic chiral ligands (R,R,R,R‐H2L/S,S,S,S‐H2L), derived from the [2+2] template condensation of 4‐tert‐butyl‐2,6‐diformylphenol, dysprosium acetylacetonate and (1R,2R)‐/(1S,2S)‐1,2‐cyclohexanediamine, respectively. Circular dichroism spectra confirms their enantiomeric chirality. Single‐crystal structures show two crystallographic independent dysprosium(III) ions have square antiprismatic coordination with different D4d local symmetry. Furthermore, the selected R‐Dy complex owns the slow magnetic relaxation behaviour with the ferromagnetic Dy3+···Dy3+ coupling.
{"title":"Chiral Homodinuclear Dysprosium Macrocyclic Complexes with Single‐molecule Magnetic Behaviours","authors":"Zi-Hang Cheng, Ru-Chan Liu, Feng Gao","doi":"10.1002/zaac.202400139","DOIUrl":"https://doi.org/10.1002/zaac.202400139","url":null,"abstract":"A pair of enantiomerically chiral dysprosium homodinuclear complexes: [(acac)4Dy2(R,R,R,R‐L)] (R‐Dy) and [(acac)4Dy2(S,S,S,S‐L)] (S‐Dy) (Hacac = acetylacetone) have been synthesized based on macrocyclic chiral ligands (R,R,R,R‐H2L/S,S,S,S‐H2L), derived from the [2+2] template condensation of 4‐tert‐butyl‐2,6‐diformylphenol, dysprosium acetylacetonate and (1R,2R)‐/(1S,2S)‐1,2‐cyclohexanediamine, respectively. Circular dichroism spectra confirms their enantiomeric chirality. Single‐crystal structures show two crystallographic independent dysprosium(III) ions have square antiprismatic coordination with different D4d local symmetry. Furthermore, the selected R‐Dy complex owns the slow magnetic relaxation behaviour with the ferromagnetic Dy3+···Dy3+ coupling.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"24 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142190630","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A highly selective approach with high yields of two diastereomeric silicon‐stereogenic menthoxysilanes, (RSi)‐3 and (SSi)‐3, introduced by Sommer et al., could be established as well as investigated in detail using different analytical tools. Single‐crystal X‐ray diffraction analysis was used to examine the different crystallization rates while Hirshfeld surface analysis was applied to extend supramolecular interactions in the solid state which showed stronger hydrogen bridges for the faster crystallizing diastereomer (SSi)‐3. In addition, similar ground‐state energies have been found for both diastereomers by DFT calculations. Subsequent NMR studies showed stable Si‐configurations wherein epimerization only started after more than 4 hours at 110 °C. Access to both diastereomers with opposite configuration at the stereogenic silicon center is achievable in high yields and high stereochemical purity using only naturally occurring (–)‐menthol as a reagent.
通过使用不同的分析工具对 Sommer 等人提出的两种非对映生硅薄荷硅烷--(RSi)-3 和 (SSi)-3 进行详细研究，建立了一种高产率的高选择性方法。单晶 X 射线衍射分析用于研究不同的结晶速度，而 Hirshfeld 表面分析则用于扩展固态超分子相互作用，结果表明结晶速度更快的非对映异构体 (SSi)-3 具有更强的氢桥。此外，通过 DFT 计算还发现两种非对映异构体的基态能量相似。随后的核磁共振研究显示，Si-构型稳定，在 110 °C 下超过 4 小时后才开始发生外延。只需使用天然存在的 (-)- 薄荷醇作为试剂，就能以高产率和高立体化学纯度获得立体硅中心构型相反的两种非对映异构体。
{"title":"Supramolecular Interactions as Key in Racemic Resolution: New Insights into the (SSi)‐ and (RSi)‐Diastereomers of (1R,2S,5R)‐Methyl(1‐naphthyl)‐phenylmenthoxysilane of Sommer","authors":"Jan-Lukas Kirchhoff, Carsten Strohmann","doi":"10.1002/zaac.202400135","DOIUrl":"https://doi.org/10.1002/zaac.202400135","url":null,"abstract":"A highly selective approach with high yields of two diastereomeric silicon‐stereogenic menthoxysilanes, (RSi)‐3 and (SSi)‐3, introduced by Sommer et al., could be established as well as investigated in detail using different analytical tools. Single‐crystal X‐ray diffraction analysis was used to examine the different crystallization rates while Hirshfeld surface analysis was applied to extend supramolecular interactions in the solid state which showed stronger hydrogen bridges for the faster crystallizing diastereomer (SSi)‐3. In addition, similar ground‐state energies have been found for both diastereomers by DFT calculations. Subsequent NMR studies showed stable Si‐configurations wherein epimerization only started after more than 4 hours at 110 °C. Access to both diastereomers with opposite configuration at the stereogenic silicon center is achievable in high yields and high stereochemical purity using only naturally occurring (–)‐menthol as a reagent.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"8 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142190632","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hans Reuter, Simona Schröder, Natalie Röwekamp-Krugley, Markus Imwalle
In order to study the formation of complexes independently from stoichiometry we developed a microscale experiment that allows us to monitor the reaction progress by light microscopy In the present study, the complex formation between SnF2 and 1,10‐phenanthroline (phen) with N,N‐dimethylformamide as solvent was investigated over a period of some weeks. By use of this setup, the formation of three different crystals has been observed, whose compositions and structures were determined by single crystal X‐ray diffraction: 3SnF2 · phen, 1, 2SnF2 · SnF4 · phen, 2, SnF4 · phen, 3. While the octahedral fluorine environment of the tin(IV) atoms of 2 and 3 is very regular, the coordinations of the tin(II) atoms in 1 and 2 is irregular. Assuming a non‐bonding 5s electron pair, classical 2c‐2e‐ and symmetrical and asymmetrical, hypervalent 3c‐4e‐bonds ‐ all based on the orthogonal p atomic orbitals of Sn – an approach to analyse and describe these coordinations in a simple comprehensive way is presented.
为了研究络合物的形成而不受化学计量学的影响，我们开发了一种微尺度实验，使我们能够通过光学显微镜监测反应的进展。通过使用这种装置，观察到了三种不同晶体的形成，并通过单晶 X 射线衍射确定了它们的成分和结构：2 和 3 中锡（IV）原子的八面体氟环境非常规则，而 1 和 2 中锡（II）原子的配位则不规则。假定存在非成键的 5s 电子对、经典的 2c-2e-、对称和不对称的高价 3c-4e-键--所有这些都基于锡的正交 p 原子轨道--本文提出了一种以简单全面的方式分析和描述这些配位的方法。
{"title":"From tin(II) to tin(IV): Following solid‐liquid reactions by microscopy","authors":"Hans Reuter, Simona Schröder, Natalie Röwekamp-Krugley, Markus Imwalle","doi":"10.1002/zaac.202400091","DOIUrl":"https://doi.org/10.1002/zaac.202400091","url":null,"abstract":"In order to study the formation of complexes independently from stoichiometry we developed a microscale experiment that allows us to monitor the reaction progress by light microscopy In the present study, the complex formation between SnF2 and 1,10‐phenanthroline (phen) with N,N‐dimethylformamide as solvent was investigated over a period of some weeks. By use of this setup, the formation of three different crystals has been observed, whose compositions and structures were determined by single crystal X‐ray diffraction: 3SnF2 · phen, 1, 2SnF2 · SnF4 · phen, 2, SnF4 · phen, 3. While the octahedral fluorine environment of the tin(IV) atoms of 2 and 3 is very regular, the coordinations of the tin(II) atoms in 1 and 2 is irregular. Assuming a non‐bonding 5s electron pair, classical 2c‐2e‐ and symmetrical and asymmetrical, hypervalent 3c‐4e‐bonds ‐ all based on the orthogonal p atomic orbitals of Sn – an approach to analyse and describe these coordinations in a simple comprehensive way is presented.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"2 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142190631","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Bin Liu, Liang He, Zi-chen Shi, Wen-hui Huang, Qi Xue, Jian-hui Yang
Sodium salt of 1,3‐bis(5‐tetrazolyl)triazene (NaH2BTT‧4H2O) was obtained through diazo‐couple reaction with 5‐aminotetrazole as starting reactants, and a family of energetic ionic crystals of the 1,3‐bis(5‐tetrazolyl)triazene anions HnBTT(3‐n)‐ with different cations were investigated, including protonated amines (ethanediamine, hydrazinium, aminoguanidine, methylhydrazinium) and Y(H2O)83+. The structures and physicochemical properties of these compounds were characterized by IR, Raman, X‐ray diffraction (XRPD) and TG‐DSC. Ethanediamine salt is the best thermal stable, while hydrazinium salt possess a highest nitrogen rich value of 79.76%. Both of them show a rapid collapse of the BTT main frame, and almost all of the dissociation products are released in the form of gas.
{"title":"Syntheses, structures, properties, and calculation of a family of ionic crystals based on 1,3‐bis(5‐tetrazolyl)triazene","authors":"Bin Liu, Liang He, Zi-chen Shi, Wen-hui Huang, Qi Xue, Jian-hui Yang","doi":"10.1002/zaac.202400049","DOIUrl":"https://doi.org/10.1002/zaac.202400049","url":null,"abstract":"Sodium salt of 1,3‐bis(5‐tetrazolyl)triazene (NaH2BTT‧4H2O) was obtained through diazo‐couple reaction with 5‐aminotetrazole as starting reactants, and a family of energetic ionic crystals of the 1,3‐bis(5‐tetrazolyl)triazene anions HnBTT(3‐n)‐ with different cations were investigated, including protonated amines (ethanediamine, hydrazinium, aminoguanidine, methylhydrazinium) and Y(H2O)83+. The structures and physicochemical properties of these compounds were characterized by IR, Raman, X‐ray diffraction (XRPD) and TG‐DSC. Ethanediamine salt is the best thermal stable, while hydrazinium salt possess a highest nitrogen rich value of 79.76%. Both of them show a rapid collapse of the BTT main frame, and almost all of the dissociation products are released in the form of gas.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"114 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142190633","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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