Abstract Cesium-containing thioarsenates(V) of lanthanoids with the composition Cs3Ln[AsS4]2 can be prepared for Ln = La–Nd and Sm by the oxidation of the lanthanoid metals in the presence of orpiment (As2S3), cesium sesquisulfide (Cs2S3) and elemental sulfur (S). The reaction mixtures were handled under argon atmosphere and heated in fused silica ampoules to a moderate reaction temperature of 500 °C. Single crystals of this Cs3Ln[AsS4]2 series appear as yellowish, transparent rods that are not stable to moist air and water. Their monoclinic crystal structure was determined from single-crystal X-ray diffraction data. The cesium-containing thioarsenates(V) Cs3Ln[AsS4]2 with Ln = La–Nd and Sm crystallize isotypically with Rb3Sm[PS4]2 in the non-centrosymmetric monoclinic space group P21 with Z = 2. The lattice parameters range between a = 997–1015 pm, b = 699–703 pm, c = 1192–1195 pm and β = 90.2–90.4°. There are two crystallographically different As5+ cations and one unique Ln3+ cation present, all coordinated by sulfur anions. Tetrahedral [AsS4]3− anions form two functionally different units working either as bridging units between three Ln3+ cations or as terminal ligands for Ln3+. [LnS8]13− polyhedra form ∞ 1 { [ Ln S 2 / 2 v S 6 / 1 t ] 11 − } ${}_{infty }^{1}left{{[mathit{Ln}{mathrm{S}}_{2/2}^{mathrm{v}}{mathrm{S}}_{6/1}^{mathrm{t}}]}^{11-}right}$ chains propagating along [010], which are separated by Cs+ cations with coordination numbers as high as C.N. = 9, 10 and 11. Surprisingly, the eighth interatomic distance d(Ln–S3) does not follow the lanthanoid contraction, but increases with decreasing ionic radius, changing the coordination polyhedron of Ln3+ from a bicapped to a monocapped trigonal prism upon the transition from Nd to Sm, and causing a structural break in the crystal structure of this series. The results of Raman spectroscopic measurements on single crystals of Cs3La[AsS4]2 have confirmed the presence of [AsS4]3− tetrahedra as structural building blocks.
摘要 在雌黄（As2S3）、硫化铯（Cs2S3）和元素硫（S）的存在下，通过氧化镧系金属，可以制备出成分为 Cs3Ln[AsS4]2 的镧系硫代砷酸盐（V），其中镧系元素为 La-Nd 和 Sm。反应混合物在氩气环境下处理，并在熔融石英安瓿瓶中加热至 500 °C 的中等反应温度。Cs3Ln[AsS4]2 系列单晶体呈淡黄色透明棒状，对潮湿空气和水不稳定。根据单晶 X 射线衍射数据确定了它们的单斜晶体结构。含铯硫代砷酸盐（V）Cs3Ln[AsS4]2（Ln = La-Nd 和 Sm）与 Rb3Sm[PS4]2 在 Z = 2 的非中心对称单斜空间群 P21 中形成同型晶体。晶格参数范围在 a = 997-1015 pm、b = 699-703 pm、c = 1192-1195 pm 和 β = 90.2-90.4° 之间。存在两个晶体学上不同的 As5+ 阳离子和一个独特的 Ln3+ 阳离子，它们都由硫阴离子配位。四面体[AsS4]3-阴离子形成了两个功能不同的单元，它们既可以作为三个 Ln3+ 阳离子之间的桥接单元，也可以作为 Ln3+ 的终端配体。[LnS8]13- 多面体形成 ∞ 1 { [ Ln S 2 / 2 v S 6 / 1 t ] 11 - }。${}_{infty}^{1}left/{[mathit{Ln}{mathrm{S}}_{2/2}^{mathrm{v}}{mathrm{S}}_{6/1}^{mathrm{t}}]}^{11-}right/}$链沿着[010]传播，它们被配位数高达 C.N. = 9、10 和 11 的 Cs+ 阳离子隔开。令人惊奇的是，第八原子间距离 d(Ln-S3) 并没有随着镧系收缩而收缩，而是随着离子半径的减小而增大，在从 Nd 到 Sm 的转变过程中，Ln3+ 的配位多面体从双帽三棱柱变成了单帽三棱柱，导致该系列晶体结构的断裂。对 Cs3La[AsS4]2 单晶体的拉曼光谱测量结果证实，[AsS4]3- 四面体作为结构构件的存在。
{"title":"Die Serie caesiumhaltiger Thioarsenate(V) der Lanthanoide vom Formeltyp Cs3Ln[AsS4]2 mit Ln = La–Nd und Sm","authors":"K. Engel, T. Schleid","doi":"10.1515/znb-2023-0066","DOIUrl":"https://doi.org/10.1515/znb-2023-0066","url":null,"abstract":"Abstract Cesium-containing thioarsenates(V) of lanthanoids with the composition Cs3Ln[AsS4]2 can be prepared for Ln = La–Nd and Sm by the oxidation of the lanthanoid metals in the presence of orpiment (As2S3), cesium sesquisulfide (Cs2S3) and elemental sulfur (S). The reaction mixtures were handled under argon atmosphere and heated in fused silica ampoules to a moderate reaction temperature of 500 °C. Single crystals of this Cs3Ln[AsS4]2 series appear as yellowish, transparent rods that are not stable to moist air and water. Their monoclinic crystal structure was determined from single-crystal X-ray diffraction data. The cesium-containing thioarsenates(V) Cs3Ln[AsS4]2 with Ln = La–Nd and Sm crystallize isotypically with Rb3Sm[PS4]2 in the non-centrosymmetric monoclinic space group P21 with Z = 2. The lattice parameters range between a = 997–1015 pm, b = 699–703 pm, c = 1192–1195 pm and β = 90.2–90.4°. There are two crystallographically different As5+ cations and one unique Ln3+ cation present, all coordinated by sulfur anions. Tetrahedral [AsS4]3− anions form two functionally different units working either as bridging units between three Ln3+ cations or as terminal ligands for Ln3+. [LnS8]13− polyhedra form ∞ 1 { [ Ln S 2 / 2 v S 6 / 1 t ] 11 − } ${}_{infty }^{1}left{{[mathit{Ln}{mathrm{S}}_{2/2}^{mathrm{v}}{mathrm{S}}_{6/1}^{mathrm{t}}]}^{11-}right}$ chains propagating along [010], which are separated by Cs+ cations with coordination numbers as high as C.N. = 9, 10 and 11. Surprisingly, the eighth interatomic distance d(Ln–S3) does not follow the lanthanoid contraction, but increases with decreasing ionic radius, changing the coordination polyhedron of Ln3+ from a bicapped to a monocapped trigonal prism upon the transition from Nd to Sm, and causing a structural break in the crystal structure of this series. The results of Raman spectroscopic measurements on single crystals of Cs3La[AsS4]2 have confirmed the presence of [AsS4]3− tetrahedra as structural building blocks.","PeriodicalId":23831,"journal":{"name":"Zeitschrift für Naturforschung B","volume":"17 15","pages":"29 - 38"},"PeriodicalIF":0.0,"publicationDate":"2024-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139455953","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}
J. R. Schmid, Anja Wiesner, P. Voßnacker, Martin Jansen, Sebastian Riedel
Abstract The compounds [Me3N(C6H3(CF3)2)][BF4] and [Me3N(C6H3(CH3)2)][BF4] were synthesized from commercially available starting materials and fully characterized by single-crystal X-ray diffraction, NMR, IR and Raman spectroscopy, as well as mass spectrometry. Both ammonium cations show potential for applications in crystal engineering due to their structure directing properties in the solid state.
摘要 利用市售起始材料合成了[Me3N(C6H3(CF3)2)][BF4]和[Me3N(C6H3(CH3)2)][BF4]化合物，并通过单晶 X 射线衍射、核磁共振、红外光谱和拉曼光谱以及质谱对其进行了全面表征。由于这两种铵阳离子在固态下的结构引导特性，它们在晶体工程中都显示出了应用潜力。
{"title":"[Me3N(C6H3(CF3)2)][BF4] and [Me3N(C6H3(CH3)2)][BF4], as potential synthons for non-covalent supramolecular assembly","authors":"J. R. Schmid, Anja Wiesner, P. Voßnacker, Martin Jansen, Sebastian Riedel","doi":"10.1515/znb-2023-0095","DOIUrl":"https://doi.org/10.1515/znb-2023-0095","url":null,"abstract":"Abstract The compounds [Me3N(C6H3(CF3)2)][BF4] and [Me3N(C6H3(CH3)2)][BF4] were synthesized from commercially available starting materials and fully characterized by single-crystal X-ray diffraction, NMR, IR and Raman spectroscopy, as well as mass spectrometry. Both ammonium cations show potential for applications in crystal engineering due to their structure directing properties in the solid state.","PeriodicalId":23831,"journal":{"name":"Zeitschrift für Naturforschung B","volume":"90 26","pages":"57 - 61"},"PeriodicalIF":0.0,"publicationDate":"2024-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139454398","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}
Josef Maximilian Gerdes, Lars Schumacher, Michael Ryan Hansen, Rainer Pöttgen
Abstract The intermetallic ytterbium compounds YbZnSn, YbPdSn2, YbAuIn2 and their calcium-substituted counterparts Yb0.5Ca0.5ZnSn, Yb0.5Ca0.5PdSn2 and Yb0.5Ca0.5AuIn2 were synthesized by reaction of the elements in sealed tantalum tubes in an induction furnace. The samples were characterized by X-ray powder diffraction. Their static, temperature-dependent solid-state 171Yb NMR spectra exhibit strong positive Knight shifts without any significant temperature dependence. The resonance shifts including anisotropy parameters for the ternary compounds have been determined.
{"title":"A solid-state 171Yb NMR-spectroscopic characterization of selected divalent ytterbium intermetallics","authors":"Josef Maximilian Gerdes, Lars Schumacher, Michael Ryan Hansen, Rainer Pöttgen","doi":"10.1515/znb-2023-0070","DOIUrl":"https://doi.org/10.1515/znb-2023-0070","url":null,"abstract":"Abstract The intermetallic ytterbium compounds YbZnSn, YbPdSn2, YbAuIn2 and their calcium-substituted counterparts Yb0.5Ca0.5ZnSn, Yb0.5Ca0.5PdSn2 and Yb0.5Ca0.5AuIn2 were synthesized by reaction of the elements in sealed tantalum tubes in an induction furnace. The samples were characterized by X-ray powder diffraction. Their static, temperature-dependent solid-state 171Yb NMR spectra exhibit strong positive Knight shifts without any significant temperature dependence. The resonance shifts including anisotropy parameters for the ternary compounds have been determined.","PeriodicalId":23831,"journal":{"name":"Zeitschrift für Naturforschung B","volume":"18 12","pages":"13 - 19"},"PeriodicalIF":0.0,"publicationDate":"2024-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139456895","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}
Abstract The new zinc borate Zn3B7O13(OH) crystallizes trigonally in the space group R3c (no. 161) with the lattice parameters a = 849.76(3), c = 2099.8(2) pm, V = 1.3131(2) nm3, and six formula units per unit cell (Z = 6). It was synthesized at high-pressure/high-temperature conditions in a multianvil device. Single-crystal and powder X-ray diffraction experiments were conducted.
摘要 新型硼酸锌 Zn3B7O13(OH)在空间群 R3c（编号 161）中呈三棱结晶，其晶格参数为 a = 849.76(3)，c = 2099.8(2) pm，V = 1.3131(2) nm3，每个单元格有六个公式单位（Z = 6）。它是在高压/高温条件下，在多管装置中合成的。进行了单晶和粉末 X 射线衍射实验。
{"title":"Synthesis and structure refinement of the zinc hydroxide boracite: Zn3B7O13(OH)","authors":"Raimund Ziegler, Sabrina Jungmann, H. Huppertz","doi":"10.1515/znb-2023-0096","DOIUrl":"https://doi.org/10.1515/znb-2023-0096","url":null,"abstract":"Abstract The new zinc borate Zn3B7O13(OH) crystallizes trigonally in the space group R3c (no. 161) with the lattice parameters a = 849.76(3), c = 2099.8(2) pm, V = 1.3131(2) nm3, and six formula units per unit cell (Z = 6). It was synthesized at high-pressure/high-temperature conditions in a multianvil device. Single-crystal and powder X-ray diffraction experiments were conducted.","PeriodicalId":23831,"journal":{"name":"Zeitschrift für Naturforschung B","volume":"31 7","pages":"51 - 55"},"PeriodicalIF":0.0,"publicationDate":"2024-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139455153","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}
Abstract The solid solutions Eu2Al15(Pt1−xT x )6 with T = Pd, Ir, Au and x = 1/6 were prepared by arc-melting the stoichiometric mixture of the elements, and subsequent annealing. For x = 1/6, all three solid solutions adopt the same structure type as Eu2Al15Pt6 according to powder X-ray diffraction data. Since the platinide Eu2Al15Pt6 exhibits a (3 + 1)D modulated structure (approximant in space group P121/m1), only the averaged hexagonal unit cell (P63/mmc, Sc0.6Fe2Si4.9 type) was refined by the Rietveld method. Scanning electron microscopy in combination with energy-dispersive X-ray spectroscopy (SEM/EDX) showed that the degree of substitution is in line with the weighed amounts. For values of x > 1/6, no phase-pure samples could be obtained. The results of the magnetic susceptibility measurements indicate that the isoelectronic substitution of Pd for Pt lowers the temperature of the first-order valence phase transition from Ttrans = 45 K in Eu2Al15Pt6 to Ttrans = 42 K in Eu2Al15(Pt5/6Pd1/6)6. For Eu2Al15(Pt5/6Ir1/6)6 and Eu2Al15(Pt5/6Au1/6)6 a change in the electronic situation occurs since the Ir substituted compound exhibits one electron less compared to the pristine Pt compound, while Eu2Al15(Pt5/6Au1/6)6 has one additional electron. As a consequence, Eu2Al15(Pt5/6Ir1/6)6 shows a higher valence phase transition temperature of Ttrans = 52 K while for Eu2Al15(Pt5/6Au1/6)6 no such transition is obvious.
摘要 通过电弧熔炼元素的化学计量混合物并随后进行退火，制备了 T = Pd、Ir、Au 和 x = 1/6 的 Eu2Al15(Pt1-xT x )6 固溶体。对于 x = 1/6，根据粉末 X 射线衍射数据，所有三种固溶体都采用与 Eu2Al15Pt6 相同的结构类型。由于铂化物 Eu2Al15Pt6 显示出 (3 + 1)D 调制结构（空间群 P121/m1 的近似值），因此只用里特维尔德法对其平均六边形单胞（P63/mmc，Sc0.6Fe2Si4.9 型）进行了细化。扫描电子显微镜结合能量色散 X 射线光谱法（SEM/EDX）显示，替代程度与称重量一致。当 x 值 > 1/6 时，无法获得相纯样品。磁感应强度测量结果表明，铂对钯的等电子取代降低了一阶价相转变温度，从 Eu2Al15Pt6 中的 Ttrans = 45 K 降至 Eu2Al15(Pt5/6Pd1/6)6 中的 Ttrans = 42 K。Eu2Al15(Pt5/6Ir1/6)6和Eu2Al15(Pt5/6Au1/6)6的电子情况发生了变化，因为与原始铂化合物相比，Ir取代的化合物少了一个电子，而Eu2Al15(Pt5/6Au1/6)6则多了一个电子。因此，Eu2Al15(Pt5/6Ir1/6)6 的价相转变温度较高，为 Ttrans = 52 K，而 Eu2Al15(Pt5/6Au1/6)6 则没有明显的价相转变。
{"title":"Modifying the valence phase transition in Eu2Al15Pt6 by the solid solutions Eu2Al15(Pt1−xT x )6 (T = Pd, Ir, Au; x = 1/6)","authors":"Stefan Engel, Lars Schumacher, Oliver Janka","doi":"10.1515/znb-2023-0072","DOIUrl":"https://doi.org/10.1515/znb-2023-0072","url":null,"abstract":"Abstract The solid solutions Eu2Al15(Pt1−xT x )6 with T = Pd, Ir, Au and x = 1/6 were prepared by arc-melting the stoichiometric mixture of the elements, and subsequent annealing. For x = 1/6, all three solid solutions adopt the same structure type as Eu2Al15Pt6 according to powder X-ray diffraction data. Since the platinide Eu2Al15Pt6 exhibits a (3 + 1)D modulated structure (approximant in space group P121/m1), only the averaged hexagonal unit cell (P63/mmc, Sc0.6Fe2Si4.9 type) was refined by the Rietveld method. Scanning electron microscopy in combination with energy-dispersive X-ray spectroscopy (SEM/EDX) showed that the degree of substitution is in line with the weighed amounts. For values of x > 1/6, no phase-pure samples could be obtained. The results of the magnetic susceptibility measurements indicate that the isoelectronic substitution of Pd for Pt lowers the temperature of the first-order valence phase transition from Ttrans = 45 K in Eu2Al15Pt6 to Ttrans = 42 K in Eu2Al15(Pt5/6Pd1/6)6. For Eu2Al15(Pt5/6Ir1/6)6 and Eu2Al15(Pt5/6Au1/6)6 a change in the electronic situation occurs since the Ir substituted compound exhibits one electron less compared to the pristine Pt compound, while Eu2Al15(Pt5/6Au1/6)6 has one additional electron. As a consequence, Eu2Al15(Pt5/6Ir1/6)6 shows a higher valence phase transition temperature of Ttrans = 52 K while for Eu2Al15(Pt5/6Au1/6)6 no such transition is obvious.","PeriodicalId":23831,"journal":{"name":"Zeitschrift für Naturforschung B","volume":"21 19","pages":"21 - 27"},"PeriodicalIF":0.0,"publicationDate":"2024-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139457917","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}
Thomas Harmening, Samir F. Matar, Constanze Fehse, Steffen Klenner, H. Eckert, Jutta Kösters, Wilma Pröbsting, Stefan Seidel, Rainer Pöttgen
Abstract The TiMnSi2-type (space group Pbam) germanides ScTGe2 (T = Fe, Co, Ru, Rh) were synthesized from the elements by arc-melting. Single crystals were grown by annealing sequences of the arc-melted buttons in an induction furnace. The structures of ScFeGe2, ScRuGe2 and ScRhGe2 were refined from single-crystal X-ray diffraction data. In ScRuGe2, the ruthenium atoms have distorted octahedral germanium coordination (242–268 pm Ru–Ge). Three trans-face-sharing octahedra form a sub-unit which is condensed via common edges in c direction and connected via common corners with four adjacent blocks, forming a three-dimensional [RuGe2 type] substructure. The two crystallographically independent scandium sites have coordination numbers 15 (Sc1@Ge8Ru4Sc3) and 17 (Sc2@Ge7Ru6Sc4). Electronic band structure calculations for ScCoGe2 and ScRuGe2 show a net charge transfer from the scandium to the transition metal and germanium atoms, leading to a description with polyanionic networks Scδ+[TGe2]δ−. The two crystallographically independent Sc sites are easily distinguishable by 45Sc magic-angle spinning (MAS)-NMR spectroscopy. Isotropic chemical shift values and nuclear electric quadrupolar interaction parameters were deduced from an analysis of the triple-quantum (TQ)-MAS NMR spectra. The electric field gradient parameters deduced from these experiments are in good agreement with quantum-chemical calculations using the Wien2k code. Likewise, the two crystallographically independent iron sites in ScFeGe2 could be discriminated in the 57Fe Mößbauer spectra through their isomer shifts and quadrupole splitting parameters: δ = 0.369(1) mm s−1 and ∆EQ = 0.232(2) mm s−1 for Fe1 and δ = 0.375(2) mm s−1 and ∆EQ = 0.435(4) mm s−1 for Fe2 (data at T = 78 K).
{"title":"The germanides ScTGe2 (T = Fe, Co, Ru, Rh) – crystal chemistry, 45Sc solid-state NMR and 57Fe Mössbauer spectroscopy","authors":"Thomas Harmening, Samir F. Matar, Constanze Fehse, Steffen Klenner, H. Eckert, Jutta Kösters, Wilma Pröbsting, Stefan Seidel, Rainer Pöttgen","doi":"10.1515/znb-2023-0068","DOIUrl":"https://doi.org/10.1515/znb-2023-0068","url":null,"abstract":"Abstract The TiMnSi2-type (space group Pbam) germanides ScTGe2 (T = Fe, Co, Ru, Rh) were synthesized from the elements by arc-melting. Single crystals were grown by annealing sequences of the arc-melted buttons in an induction furnace. The structures of ScFeGe2, ScRuGe2 and ScRhGe2 were refined from single-crystal X-ray diffraction data. In ScRuGe2, the ruthenium atoms have distorted octahedral germanium coordination (242–268 pm Ru–Ge). Three trans-face-sharing octahedra form a sub-unit which is condensed via common edges in c direction and connected via common corners with four adjacent blocks, forming a three-dimensional [RuGe2 type] substructure. The two crystallographically independent scandium sites have coordination numbers 15 (Sc1@Ge8Ru4Sc3) and 17 (Sc2@Ge7Ru6Sc4). Electronic band structure calculations for ScCoGe2 and ScRuGe2 show a net charge transfer from the scandium to the transition metal and germanium atoms, leading to a description with polyanionic networks Scδ+[TGe2]δ−. The two crystallographically independent Sc sites are easily distinguishable by 45Sc magic-angle spinning (MAS)-NMR spectroscopy. Isotropic chemical shift values and nuclear electric quadrupolar interaction parameters were deduced from an analysis of the triple-quantum (TQ)-MAS NMR spectra. The electric field gradient parameters deduced from these experiments are in good agreement with quantum-chemical calculations using the Wien2k code. Likewise, the two crystallographically independent iron sites in ScFeGe2 could be discriminated in the 57Fe Mößbauer spectra through their isomer shifts and quadrupole splitting parameters: δ = 0.369(1) mm s−1 and ∆EQ = 0.232(2) mm s−1 for Fe1 and δ = 0.375(2) mm s−1 and ∆EQ = 0.435(4) mm s−1 for Fe2 (data at T = 78 K).","PeriodicalId":23831,"journal":{"name":"Zeitschrift für Naturforschung B","volume":"39 8","pages":"1 - 12"},"PeriodicalIF":0.0,"publicationDate":"2024-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139454889","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}
{"title":"Die Geschichte der Chemie an der Ludwig-Maximilians-Universität München, mit zahlreichen Kurzbiographien von Professoren, die an der LMU gewirkt haben. von Wolfgang Beck","authors":"H. Schmidbaur","doi":"10.1515/znb-2023-0104","DOIUrl":"https://doi.org/10.1515/znb-2023-0104","url":null,"abstract":"","PeriodicalId":23831,"journal":{"name":"Zeitschrift für Naturforschung B","volume":"49 6","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138943765","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}
In the present study, 12-tungestocobaltic acid, H5CoW12O40, was immobilized on nano silica from rice husk (CoW@NSiO2) to develop a novel, efficient, heterogeneous and recyclable nano catalyst for the synthesis of β-enaminones. It is apparent from acidity and cyclic voltammetric measurements that, the catalyst is electroactive and undergoes reversible redox transitions, as well as it is contains strong acid sites and mobile protons. As evidenced from mechanistic investigations, CoW@NSiO2 can catalyze the synthesis of β-enaminones with two simultaneous ways: electron transfer and Brønsted acid mechanisms. In order to confirm the synthesis of enaminones through simultaneous mechanisms of electron transfer and acidity, the model reaction was carried out in the presence of K5Co as an electroactive catalyst and CoW@NSiO2 with electron scavenger as an acid catalyst. The results showed that the reaction proceeded simultaneously through both mechanisms. There is evidence that the electron transfer property of this catalyst is most pronounced in this type of organic reactions. The catalyst demonstrated outstanding performance, and the methodology proved to be versatile, yielding excellent results across a wide range of substrates. It is worth mentioning that aliphatic amines were well-tolerated in the process and produced β-enaminone compounds with excellent yields and short reaction times. Also, reactions with dimedone, a cyclic 1,3-diketone, delivered moderate product yields. Additionally, the catalyst showed remarkable recyclability, maintaining its activity for a minimum of five consecutive cycles without any noticeable decline. Notably, the cyclic voltammetric and acidity measurements revealed that the catalyst’s electron transfer property and Brønsted acidity remained unchanged after five runs.
{"title":"Simultaneous different mechanisms for the efficient synthesis of β-enaminones: 12-tungstocobaltic acid-supported on nano silica as an electron transfer and Brønsted acid nano catalyst","authors":"Mahtab Razlansari, Masoud Kahrizi","doi":"10.1515/znb-2023-0045","DOIUrl":"https://doi.org/10.1515/znb-2023-0045","url":null,"abstract":"In the present study, 12-tungestocobaltic acid, H<jats:sub>5</jats:sub>CoW<jats:sub>12</jats:sub>O<jats:sub>40</jats:sub>, was immobilized on nano silica from rice husk (CoW@NSiO<jats:sub>2</jats:sub>) to develop a novel, efficient, heterogeneous and recyclable nano catalyst for the synthesis of <jats:italic>β</jats:italic>-enaminones. It is apparent from acidity and cyclic voltammetric measurements that, the catalyst is electroactive and undergoes reversible redox transitions, as well as it is contains strong acid sites and mobile protons. As evidenced from mechanistic investigations, CoW@NSiO<jats:sub>2</jats:sub> can catalyze the synthesis of <jats:italic>β</jats:italic>-enaminones with two simultaneous ways: electron transfer and Brønsted acid mechanisms. In order to confirm the synthesis of enaminones through simultaneous mechanisms of electron transfer and acidity, the model reaction was carried out in the presence of K<jats:sub>5</jats:sub>Co as an electroactive catalyst and CoW@NSiO<jats:sub>2</jats:sub> with electron scavenger as an acid catalyst. The results showed that the reaction proceeded simultaneously through both mechanisms. There is evidence that the electron transfer property of this catalyst is most pronounced in this type of organic reactions. The catalyst demonstrated outstanding performance, and the methodology proved to be versatile, yielding excellent results across a wide range of substrates. It is worth mentioning that aliphatic amines were well-tolerated in the process and produced <jats:italic>β</jats:italic>-enaminone compounds with excellent yields and short reaction times. Also, reactions with dimedone, a cyclic 1,3-diketone, delivered moderate product yields. Additionally, the catalyst showed remarkable recyclability, maintaining its activity for a minimum of five consecutive cycles without any noticeable decline. Notably, the cyclic voltammetric and acidity measurements revealed that the catalyst’s electron transfer property and Brønsted acidity remained unchanged after five runs.","PeriodicalId":23831,"journal":{"name":"Zeitschrift für Naturforschung B","volume":"33 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138688084","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}
Jing-Lin Chang, Jun-Feng Wu, Jia-Wei Zhang, Kai Cui, Zhi-Qiang Liu
A Metal-Organic Framework (MOF) based on a tricarboxylic acid ligand (H3L = biphenyl-2,4′,5-tricarboxylic acid), namely [Cd3(L)2(H2O)4] (1), had been prepared and characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction (PXRD), thermogravimetric analyses (TGA), and single-crystal X-ray diffraction. Fluorescence studies showed that 1 has high quenching efficiency for testing acetone and Fe3+ ions in aqueous systems. Therefore, it can be used as a new type of fluorescence probe to detect solvent molecules and metal ions in water.
{"title":"Crystal structure and fluorescence-based sensor properties of a Metal-Organic Framework","authors":"Jing-Lin Chang, Jun-Feng Wu, Jia-Wei Zhang, Kai Cui, Zhi-Qiang Liu","doi":"10.1515/znb-2023-0077","DOIUrl":"https://doi.org/10.1515/znb-2023-0077","url":null,"abstract":"A Metal-Organic Framework (MOF) based on a tricarboxylic acid ligand (H<jats:sub>3</jats:sub>L = biphenyl-2,4′,5-tricarboxylic acid), namely [Cd<jats:sub>3</jats:sub>(L)<jats:sub>2</jats:sub>(H<jats:sub>2</jats:sub>O)<jats:sub>4</jats:sub>] (1), had been prepared and characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction (PXRD), thermogravimetric analyses (TGA), and single-crystal X-ray diffraction. Fluorescence studies showed that 1 has high quenching efficiency for testing acetone and Fe<jats:sup>3+</jats:sup> ions in aqueous systems. Therefore, it can be used as a new type of fluorescence probe to detect solvent molecules and metal ions in water.","PeriodicalId":23831,"journal":{"name":"Zeitschrift für Naturforschung B","volume":" 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138493049","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 synthesis and crystal structure of Zn6B22O39·H2O are described. This new zinc borate was synthesized at 7 GPa and 1523 K in a multianvil device. It crystallizes in the orthorhombic space group Pnma (no. 62) with the lattice parameters a = 818.77(4), b = 768.42(3), c = 1744.82(9) pm, V = 1.09777(9) nm3, and two formula units per unit cell (Z = 2). The structure is closely related to those of M6B22O39·H2O (M = Fe, Co, Ni, Cd) and features non-planar (BO3) units as demonstrated by single-crystal and powder X-ray diffraction techniques.
介绍了Zn6B22O39·H2O的合成及晶体结构。在多砧装置中，在7 GPa和1523 K下合成了新型硼酸锌。它在正交空间群Pnma (no。晶格参数a = 818.77(4)， b = 768.42(3)， c = 1744.82(9) pm, V = 1.09777(9) nm3，单位晶胞两个公式单位(Z = 2)。结构与M 6B22O39·H2O (M = Fe, Co, Ni, Cd)密切相关，单晶和粉末x射线衍射技术证明其具有非平面(BO3)单元。
{"title":"Synthesis and crystal structure of the zinc borate Zn6B22O39·H2O","authors":"Raimund Ziegler, Hubert Huppertz","doi":"10.1515/znb-2023-0089","DOIUrl":"https://doi.org/10.1515/znb-2023-0089","url":null,"abstract":"The synthesis and crystal structure of Zn<jats:sub>6</jats:sub>B<jats:sub>22</jats:sub>O<jats:sub>39</jats:sub>·H<jats:sub>2</jats:sub>O are described. This new zinc borate was synthesized at 7 GPa and 1523 K in a multianvil device. It crystallizes in the orthorhombic space group <jats:italic>Pnma</jats:italic> (no. 62) with the lattice parameters <jats:italic>a</jats:italic> = 818.77(4), <jats:italic>b</jats:italic> = 768.42(3), <jats:italic>c</jats:italic> = 1744.82(9) pm, <jats:italic>V</jats:italic> = 1.09777(9) nm<jats:sup>3</jats:sup>, and two formula units per unit cell (<jats:italic>Z</jats:italic> = 2). The structure is closely related to those of <jats:italic>M</jats:italic> <jats:sub>6</jats:sub>B<jats:sub>22</jats:sub>O<jats:sub>39</jats:sub>·H<jats:sub>2</jats:sub>O (<jats:italic>M</jats:italic> = Fe, Co, Ni, Cd) and features non-planar (BO<jats:sub>3</jats:sub>) units as demonstrated by single-crystal and powder X-ray diffraction techniques.","PeriodicalId":23831,"journal":{"name":"Zeitschrift für Naturforschung B","volume":"27 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2023-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138496447","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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