Metal‐organic frameworks (MOFs) as an efficient and convenient sensing material for environmental pollutants have attracted widespread attention in recent years. Here in, we synthesized a series of lanthanide co‐doping MOFs, EuxTb1‐x‐MOFs (x=0, 0.005, 0.00667, 0.01, 0.02 and 1) under solvothermal conditions. The luminescence colors can be adjusted by changing metal molar mass ratios and altering excitation wavelength. Fortunately, a near white‐light‐emitting material Eu0.01Tb0.99‐MOF was obtained under the excitation at 350 nm, whose CIE coordinates of (0.3444, 0.3409) are very close to standard white light coordinates (0.3333, 0.3333). We further studied the fluorescence sensing performances of Eu‐MOF, Tb‐MOF and Eu0.01Tb0.99‐MOF towards NACs. The results indicate that all MOFs can selectively detect 4‐nitroaniline, 4‐nitrophenol and 2‐nitrophenol with good sensitivity and recyclability.
{"title":"White‐Light‐Emitting Ln‐MOF as Luminescent Probe for Selective Detection of Nitroaromatic Compounds","authors":"Yihui Wang, Xitong Xiao, Jiayi Liu, Zhenghong Dong, Fengqin Wang, Xiaoqing Wang","doi":"10.1002/zaac.202400084","DOIUrl":"https://doi.org/10.1002/zaac.202400084","url":null,"abstract":"Metal‐organic frameworks (MOFs) as an efficient and convenient sensing material for environmental pollutants have attracted widespread attention in recent years. Here in, we synthesized a series of lanthanide co‐doping MOFs, EuxTb1‐x‐MOFs (x=0, 0.005, 0.00667, 0.01, 0.02 and 1) under solvothermal conditions. The luminescence colors can be adjusted by changing metal molar mass ratios and altering excitation wavelength. Fortunately, a near white‐light‐emitting material Eu0.01Tb0.99‐MOF was obtained under the excitation at 350 nm, whose CIE coordinates of (0.3444, 0.3409) are very close to standard white light coordinates (0.3333, 0.3333). We further studied the fluorescence sensing performances of Eu‐MOF, Tb‐MOF and Eu0.01Tb0.99‐MOF towards NACs. The results indicate that all MOFs can selectively detect 4‐nitroaniline, 4‐nitrophenol and 2‐nitrophenol with good sensitivity and recyclability.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141773031","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}
Michael Veith, Tatjana Kirs, Bernd Morgenstern, Volker Huch
Nine different derivatives of piperidino alanes of the general formula (CH2)5N‐AlXY [X=Y= Cl (1), Br (2), I (3); X= (CH2)5N, Y= Cl (4), Br (5), I (6); X=H, Y= Cl (7), Br (8), I (9)] have been synthesized and compared with respect to their structures. All molecules form dimers with an Al2N2 central cycle and aluminum and nitrogen atoms in distorted tetrahedral environments as determined from X‐ray diffraction. The three dihalide derivatives 1, 2 and 3 have C2h (2/m) symmetries in solution of which they maintain the Centro symmetry in the crystal lattice. The bis(piperidino) derivatives 4, 5 and 6 have either C1 (1) symmetry with the bridging piperidino cycles oriented in the same direction (4, 5) or Ci (ī) point symmetry as found for 6 (in solution at least one other isomer is present). Whereas the chlorine derivative 7 has crystallographic Ci (ī) symmetry, the bromine 8 has almost C2 and the iodine 9 crystallographic C2 (2) point symmetry. In solution all derivatives 7, 8, 9 show equilibria between cis (C2) and trans (Ci) isomeric forms (27Al NMR). The longest Al‐N bond lengths within the rings are found for 5 (1.969(4) Å) and the shortest for 8 (1.940(4) Å).
{"title":"Structural Studies of Piperidino‐Alanes with Halide, Amide and Hydride as further Ligands at Aluminum","authors":"Michael Veith, Tatjana Kirs, Bernd Morgenstern, Volker Huch","doi":"10.1002/zaac.202400090","DOIUrl":"https://doi.org/10.1002/zaac.202400090","url":null,"abstract":"Nine different derivatives of piperidino alanes of the general formula (CH2)5N‐AlXY [X=Y= Cl (1), Br (2), I (3); X= (CH2)5N, Y= Cl (4), Br (5), I (6); X=H, Y= Cl (7), Br (8), I (9)] have been synthesized and compared with respect to their structures. All molecules form dimers with an Al2N2 central cycle and aluminum and nitrogen atoms in distorted tetrahedral environments as determined from X‐ray diffraction. The three dihalide derivatives 1, 2 and 3 have C2h (2/m) symmetries in solution of which they maintain the Centro symmetry in the crystal lattice. The bis(piperidino) derivatives 4, 5 and 6 have either C1 (1) symmetry with the bridging piperidino cycles oriented in the same direction (4, 5) or Ci (ī) point symmetry as found for 6 (in solution at least one other isomer is present). Whereas the chlorine derivative 7 has crystallographic Ci (ī) symmetry, the bromine 8 has almost C2 and the iodine 9 crystallographic C2 (2) point symmetry. In solution all derivatives 7, 8, 9 show equilibria between cis (C2) and trans (Ci) isomeric forms (27Al NMR). The longest Al‐N bond lengths within the rings are found for 5 (1.969(4) Å) and the shortest for 8 (1.940(4) Å).","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141773033","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 reactivity of [{SiNDipp}AlK]2, which comprises a formally anionic Al(I) centre, has been examined towards a variety of 1,3‐dienic molecules, including 2,3‐dimethylbutadiene, cyclooctatetraene, anthracene and tetracene. In each case, the alumanyl derivative experiences oxidative addition across the Al(I) centre to provide the corresponding potassium aluminacyclopentene, aluminacyclopropene or aluminanorbornadiene products of [4 + 1] cycloaddition.
{"title":"Polyene and Arene [4 + 1] Cycloaddition at a Seven‐Membered Cyclic Alumanyl","authors":"Michael Stephen Hill, Han-Ying Liu, Mary F. Mahon","doi":"10.1002/zaac.202400125","DOIUrl":"https://doi.org/10.1002/zaac.202400125","url":null,"abstract":"The reactivity of [{SiNDipp}AlK]2, which comprises a formally anionic Al(I) centre, has been examined towards a variety of 1,3‐dienic molecules, including 2,3‐dimethylbutadiene, cyclooctatetraene, anthracene and tetracene. In each case, the alumanyl derivative experiences oxidative addition across the Al(I) centre to provide the corresponding potassium aluminacyclopentene, aluminacyclopropene or aluminanorbornadiene products of [4 + 1] cycloaddition.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141773027","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 Lainer, Christoph Walkner, Nina M. Tasch, Roland C. Fischer, Ana Torvisco, Harald Stueger, Michael Haas
This study focuses on the synthesis of H‐ and MeO‐ functionalized alkali metal hypersilyl borates. Consequently, two distinct silanides were used as polysilane frameworks for our chemical manipulations. Tris(silyl)silanide (1) and tris(trimethoxysilyl)silanide (2) react in the same manner with the BH3 ⋅ SMe2 complex to obtain two new alkali metal hypersilyl borates [(R3Si)3SiBH3M (M=alkali metal; R=H, (3), R=MeO, (4 a–c))] in good to excellent yields. NMR spectroscopy for all compounds and single‐crystal X‐ray crystallography for 3 and 4 a, b enabled a clear structural characterization. Single crystal X‐ray analysis of 3 showed a dimeric structure, where two THF‐molecules and three hydrides from the BH3‐group contribute to the coordination sphere of the lithium atom. Interestingly, crystals suitable for X‐ray analysis of 4 a and 4 b showed a solvent‐free cluster formation, due to the coordination of the MeO groups. Both species form coordination polymers with different coordination modes depending on the nature of the alkali metal. Attempted hydride abstraction reactions of 3 and 4 with various reagents under the formation of the free boranes proceeded unselectively.
本研究的重点是合成 H 原子和 Me 原子官能化的碱金属超硅硼酸盐。因此，我们使用了两种不同的硅烷作为多硅烷框架进行化学处理。三(硅烷基)硅烷化物 (1) 和三(三甲氧基硅烷基)硅烷化物 (2) 与 BH3 ⋅ SMe2 复合物以相同的方式发生反应，得到两种新的碱金属超硅硼酸盐 [(R3Si)3SiBH3M（M=碱金属；R=H，(3)，R=MeO，(4 a-c)）]，收率良好至极佳。通过对所有化合物进行核磁共振光谱分析，以及对 3 和 4 a、b 进行单晶 X 射线晶体分析，可以清楚地确定其结构特征。3 的单晶 X 射线分析表明其具有二聚体结构，其中两个 THF 分子和三个来自 BH3 基团的氢化物构成了锂原子的配位层。有趣的是，适合对 4 a 和 4 b 进行 X 射线分析的晶体显示，由于 MeO 基团的配位，形成了无溶剂簇。根据碱金属的性质，这两种物质形成的配位聚合物具有不同的配位模式。在形成游离硼烷的条件下，尝试用各种试剂对 3 和 4 进行氢化物抽取反应，但反应无选择性地进行。
{"title":"Synthesis and Characterization of Alkali Metal Hypersilyl Borates","authors":"Thomas Lainer, Christoph Walkner, Nina M. Tasch, Roland C. Fischer, Ana Torvisco, Harald Stueger, Michael Haas","doi":"10.1002/zaac.202400054","DOIUrl":"https://doi.org/10.1002/zaac.202400054","url":null,"abstract":"This study focuses on the synthesis of H‐ and MeO‐ functionalized alkali metal hypersilyl borates. Consequently, two distinct silanides were used as polysilane frameworks for our chemical manipulations. Tris(silyl)silanide (1) and tris(trimethoxysilyl)silanide (2) react in the same manner with the BH<jats:sub>3</jats:sub> ⋅ SMe<jats:sub>2</jats:sub> complex to obtain two new alkali metal hypersilyl borates [(R<jats:sub>3</jats:sub>Si)<jats:sub>3</jats:sub>SiBH<jats:sub>3</jats:sub>M (M=alkali metal; R=H, (3), R=MeO, (4 a–c))] in good to excellent yields. NMR spectroscopy for all compounds and single‐crystal X‐ray crystallography for 3 and 4 a, b enabled a clear structural characterization. Single crystal X‐ray analysis of 3 showed a dimeric structure, where two THF‐molecules and three hydrides from the BH<jats:sub>3</jats:sub>‐group contribute to the coordination sphere of the lithium atom. Interestingly, crystals suitable for X‐ray analysis of 4 a and 4 b showed a solvent‐free cluster formation, due to the coordination of the MeO groups. Both species form coordination polymers with different coordination modes depending on the nature of the alkali metal. Attempted hydride abstraction reactions of 3 and 4 with various reagents under the formation of the free boranes proceeded unselectively.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141773026","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}
Single crystal of a thallium‐containing sulfate Tl2Pb(SO4)2 was prepared through hydrothermal crystallization starting from Tl2CO3, Pb(NO3)2 and H2SO4. The crystal structure was solved from single‐crystal X‐ray diffraction data: Tl2Pb(SO4)2 crystallizes in space group R[[EQUATION]]m with lattice parameters of a = 5.5955(2) Å, c = 22.1001(9) Å, and Z = 3, which is also corroborated by Rietveld refinement on X‐ray powder data. The crystal structure can be regarded as [Pb(SO4)2]2‐ sheets intercalated by double layers of Tl+ along the c‐axis. From a mineralogical perspective, Tl2Pb(SO4)2 belongs to the palmierite family and can further be classified within palmierite‐supergroup. Validation of the structure models was carried out utilizing various concepts including Bond Valence (BV), Charge Distribution (CD) and Madelung Part of Lattice Energy (MAPLE). Notably, a contrast in stereochemical activity of 6s2 lone electron pair (LEP) between Tl+ and Pb2+ is interpreted in terms of bonding behaviours as well as Wang‐Liebau Eccentricity (WLE) parameters. Moreover, an extensive investigation into the crystal chemistry of thallium‐containing sulfates was conducted for the first time, focusing on the coordination environment and bonding behaviour of Tl+ and corresponding WLE parameters. A comparative analysis of these structurally related compounds including Tl2Pb(SO4)2, Tl3H(SO4)2, TlBi(SO4)2, TlIn(SO4)2, TlRh(SO4)2, and TlAl(SO4)2 was delineated.
{"title":"On the structure of Tl2Pb(SO4)2 and crystal chemistry of thallium‐containing sulfates","authors":"Pengyun Chen","doi":"10.1002/zaac.202400072","DOIUrl":"https://doi.org/10.1002/zaac.202400072","url":null,"abstract":"Single crystal of a thallium‐containing sulfate Tl2Pb(SO4)2 was prepared through hydrothermal crystallization starting from Tl2CO3, Pb(NO3)2 and H2SO4. The crystal structure was solved from single‐crystal X‐ray diffraction data: Tl2Pb(SO4)2 crystallizes in space group R[[EQUATION]]m with lattice parameters of a = 5.5955(2) Å, c = 22.1001(9) Å, and Z = 3, which is also corroborated by Rietveld refinement on X‐ray powder data. The crystal structure can be regarded as [Pb(SO4)2]2‐ sheets intercalated by double layers of Tl+ along the c‐axis. From a mineralogical perspective, Tl2Pb(SO4)2 belongs to the palmierite family and can further be classified within palmierite‐supergroup. Validation of the structure models was carried out utilizing various concepts including Bond Valence (BV), Charge Distribution (CD) and Madelung Part of Lattice Energy (MAPLE). Notably, a contrast in stereochemical activity of 6s2 lone electron pair (LEP) between Tl+ and Pb2+ is interpreted in terms of bonding behaviours as well as Wang‐Liebau Eccentricity (WLE) parameters. Moreover, an extensive investigation into the crystal chemistry of thallium‐containing sulfates was conducted for the first time, focusing on the coordination environment and bonding behaviour of Tl+ and corresponding WLE parameters. A comparative analysis of these structurally related compounds including Tl2Pb(SO4)2, Tl3H(SO4)2, TlBi(SO4)2, TlIn(SO4)2, TlRh(SO4)2, and TlAl(SO4)2 was delineated.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141773025","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":"Retraction: Porous GdIII‐Organic Framework as a Dual‐Functional Material for Cyanosilylation of Aldehydes and Ablation of Human Liver Cancer Cells","authors":"","doi":"10.1002/zaac.202400105","DOIUrl":"https://doi.org/10.1002/zaac.202400105","url":null,"abstract":"","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141744577","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":"Retraction: Encapsulation of 5‐Fluorouracil in a Copper(II)‐based Porous Metal‐organic Framework: Drug Delivery and Inhibiting Human Spinal Cord Tumor Cells","authors":"","doi":"10.1002/zaac.202400107","DOIUrl":"https://doi.org/10.1002/zaac.202400107","url":null,"abstract":"","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141744575","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":"Retraction: Synthesis, Crystal Structures, and Anti‐cervical Cancer Activity Evaluation of Three Trinuclear Transition Metal(II) Complexes with N,O‐Donor Schiff Base Ligand","authors":"","doi":"10.1002/zaac.202400103","DOIUrl":"https://doi.org/10.1002/zaac.202400103","url":null,"abstract":"","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141744572","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":"Retraction: Two Zinc(II) and Nickel(II)‐based Complexes: Anti Breast Cancer Activity","authors":"","doi":"10.1002/zaac.202400102","DOIUrl":"https://doi.org/10.1002/zaac.202400102","url":null,"abstract":"","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141744576","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":"Retraction: 3D Porous Heterometallic Coordination Polymer for the Detection of Nitroaromatic Explosives and Inhibiting Human Cancer Cells Growth","authors":"","doi":"10.1002/zaac.202400101","DOIUrl":"https://doi.org/10.1002/zaac.202400101","url":null,"abstract":"","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141744573","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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