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Direct Laser Synthesis of Fe2O3 modified TiO2 直接激光合成 Fe2O3 改性二氧化钛
Pub Date : 2024-07-29 DOI: 10.1002/zaac.202400078
V. V. Lennikov, A. Gómez-Herrero, L. A. Angurel, German Francisco de la Fuente, L. C. Otero-Díaz
A very fast, selective CO2 laser line scan direct synthesis method is presented and has been applied here to study phase and defect formation within an irradiated mixture of powdered oxides, as a proof‐of‐principle. A nominal composition interval of 0<x<0.03 was conveniently chosen for the TiO2+xFe2O3 system herein reported. X‐ray diffraction analyses were used to determine the main crystalline phase composition. Thus, for 3% mol. Fe2O3, pseudobrookite crystals were found to coexist with rutile‐type MO2‐δ (M=Ti, Fe) with extended defects. These are composed mainly of (121)r and (132)r crystallographic shear planes (CSP`s), where the r sub‐index refers to the rutile subcell. For samples with a lower Fe2O3 content (2, 1, 0.5% mol) only iron‐doped rutile phases were observed, with complex microstructure arising from the presence of multi‐twinned (011)r and (110)r crystals and isolated and/or ordered CSP`s at short length scale. The diverse microstructures observed in the CO2 laser produced samples correlate with the conditions imposed during the laser treatment, which include intrinsically high solidification rates and steep temperature gradients.
本文介绍了一种非常快速的选择性 CO2 激光线扫描直接合成方法,并将其作为原理验证,用于研究粉末氧化物辐照混合物中相和缺陷的形成。本文报告的 TiO2+xFe2O3 系统的标称成分区间为 0<x<0.03。X 射线衍射分析用于确定主要晶相组成。因此,对于 3% mol.Fe2O3,假勃罗克石晶体与具有扩展缺陷的金红石型 MO2-δ(M=Ti、Fe)共存。这些晶体主要由 (121)r 和 (132)r 晶体剪切面(CSP`s)组成,其中 r 子索引指的是金红石子晶胞。对于 Fe2O3 含量较低(2、1、0.5% mol)的样品,只观察到掺铁的金红石相,由于存在多孪晶 (011)r 和 (110)r 晶体以及短长度尺度上孤立和/或有序的 CSP`s,因此微观结构复杂。在二氧化碳激光生产的样品中观察到的多种微观结构与激光处理过程中施加的条件有关,其中包括固有的高凝固速率和陡峭的温度梯度。
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引用次数: 0
Unraveling strong supramolecular assembly of a novel pyrene based Hg(II)‐complex: Insights from Hirshfeld surface, FMO and molecular electrostatic potential (MEP) analyses 揭示新型芘基 Hg(II)-complex 的强超分子组装:Hirshfeld 表面、FMO 和分子静电位 (MEP) 分析的启示
Pub Date : 2024-07-29 DOI: 10.1002/zaac.202400074
SAUGATA KONAR, Shibashis Halder, Yeasin Sikdar, Mohd Afzal, Mridula Guin
A rare pyrene‐based coordination compound of Hg(II) [Hg(L) 2 ] ( 1 ) (where, HL = 2‐((Pyren‐1‐ylmethylene)amino)benzenethiol) was synthesized and characterized by single crystal X‐ Ray diffraction (SC‐XRD) analysis. Crystallographic analysis revealed that complex 1 has seesaw geometry with HL coordinated as a bidentate ligand to a metal ion. The role of weak forces like π∙∙∙π and CH∙∙∙π interactions in influencing the self‐assembly process appears to be of importance. The electronic structure of the complex was predicted using DFT calculations with mixed basis set. DFT calculated structural parameters are in good agreement with the experimentally obtained parameters from XRD. Molecular reactivity and stability of the complex has been assessed through frontier molecular orbital analysis. Evaluation of molecular electrostatic potential (MEP) displaying the electrophilic and nucleophilic reactivity sites. The Hirshfeld surface analysis clearly indicates CH∙∙∙π interaction and π∙∙∙π stacking interactions are responsible to extend the supramolecular network of the complex. Analysis of the finger print plots suggest that H∙∙∙H and H∙∙∙C contacts are major interaction for stabilizing the molecular crystal.
通过单晶 X 射线衍射(SC-XRD)分析,合成了一种罕见的芘基配位化合物 Hg(II) [Hg(L) 2 ] ( 1 ) (其中,HL = 2-((Pyren-1-ylmethylene)amino)benzenethiol)。晶体分析表明,复合物 1 具有跷跷板几何形状,HL 作为双齿配体与金属离子配位。π∙∙∙π和CH∙∙∙π相互作用等弱作用力对自组装过程的影响似乎非常重要。使用混合基集的 DFT 计算预测了该复合物的电子结构。DFT 计算得出的结构参数与 XRD 实验得出的参数十分吻合。通过前沿分子轨道分析评估了复合物的分子反应性和稳定性。分子静电位(MEP)评估显示了亲电和亲核反应位点。Hirshfeld 表面分析清楚地表明,CH∙∙∙π 相互作用和 π∙∙∙π 堆积相互作用是扩展复合物超分子网络的原因。指纹图谱分析表明,H∙∙∙H 和 H∙∙∙C 接触是稳定分子晶体的主要相互作用。
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引用次数: 0
Structures of Large Tin(IV) Oxo Clusters 大型锡(IV)氧化物团簇的结构
Pub Date : 2024-07-25 DOI: 10.1002/zaac.202400058
Ulrich Schubert
The article reviews and categorizes the structures of tin oxo clusters with nuclearities ≥6 and compares them with oxo clusters of the other group 4 and 14 metals. Basic construction principles of the cluster core are worked out by comparing the different cluster types and by identifying smaller building blocks. The comparison also shows how the different cluster types are influenced by the interplay between the ligands which stabilize the cluster core and the bridging oxygen atoms.
文章对核度≥6 的锡氧化簇结构进行了回顾和分类,并将其与其他第 4 组和第 14 组金属的氧化簇进行了比较。通过比较不同的簇类型和识别较小的构件,得出了簇核的基本构造原理。比较还显示了稳定簇核的配体与桥接氧原子之间的相互作用对不同簇类型的影响。
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引用次数: 0
Front Cover: (Z. Anorg. Allg. Chem. 13‐14/2024) 封面: (Z. Anorg. Allg. Chem. 13-14/2024)
Pub Date : 2024-07-25 DOI: 10.1002/zaac.202481301
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引用次数: 0
White‐Light‐Emitting Ln‐MOF as Luminescent Probe for Selective Detection of Nitroaromatic Compounds 白光发光 Ln-MOF 作为选择性检测硝基芳香族化合物的发光探针
Pub Date : 2024-07-24 DOI: 10.1002/zaac.202400084
Yihui Wang, Xitong Xiao, Jiayi Liu, Zhenghong Dong, Fengqin Wang, Xiaoqing Wang
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.
近年来,金属有机框架(MOFs)作为一种高效便捷的环境污染物传感材料受到广泛关注。在此,我们在溶热条件下合成了一系列镧系元素共掺杂 MOFs--EuxTb1-x-MOFs(x=0、0.005、0.00667、0.01、0.02 和 1)。可以通过改变金属摩尔质量比和激发波长来调整发光颜色。幸运的是,在 350 纳米波长的激发下,我们得到了一种近白光发光材料 Eu0.01Tb0.99-MOF,其 CIE 坐标(0.3444,0.3409)与标准白光坐标(0.3333,0.3333)非常接近。我们进一步研究了 Eu-MOF、Tb-MOF 和 Eu0.01Tb0.99-MOF 对 NAC 的荧光传感性能。结果表明,所有 MOFs 都能选择性地检测 4-硝基苯胺、4-硝基苯酚和 2-硝基苯酚,并具有良好的灵敏度和可回收性。
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引用次数: 0
Structural Studies of Piperidino‐Alanes with Halide, Amide and Hydride as further Ligands at Aluminum 以卤化物、酰胺和氢化物作为铝的进一步配体的哌啶烷结构研究
Pub Date : 2024-07-22 DOI: 10.1002/zaac.202400090
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).
我们合成了通式为 (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)]的九种不同的哌啶烷衍生物,并对它们的结构进行了比较。根据 X 射线衍射测定,所有分子都形成二聚体,具有 Al2N2 中心循环,铝原子和氮原子处于扭曲的四面体环境中。三种二卤化物衍生物 1、2 和 3 在溶液中具有 C2h (2/m) 对称性,它们在晶格中保持了 Centro 对称性。双(哌啶基)衍生物 4、5 和 6 要么具有 C1 (1) 对称性,桥接的哌啶基循环方向相同(4、5),要么像 6 一样具有 Ci (ī) 点对称性(在溶液中至少存在另一种异构体)。氯衍生物 7 具有晶体学上的 Ci (ī) 点对称性,溴衍生物 8 几乎具有 C2 点对称性,碘衍生物 9 具有晶体学上的 C2 (2) 点对称性。在溶液中,所有衍生物 7、8 和 9 都显示出顺式(C2)和反式(Ci)异构体之间的平衡(27Al NMR)。环内 Al-N 键长度最长的是 5(1.969(4) Å),最短的是 8(1.940(4) Å)。
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引用次数: 0
Polyene and Arene [4 + 1] Cycloaddition at a Seven‐Membered Cyclic Alumanyl 多烯和烯烃在七元环丙氨酰的 [4 + 1] 环加成反应
Pub Date : 2024-07-22 DOI: 10.1002/zaac.202400125
Michael Stephen Hill, Han-Ying Liu, Mary F. Mahon
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.
我们研究了[{SiNDipp}AlK]2 对各种 1,3-二烯分子(包括 2,3-二甲基丁二烯、环辛四烯、蒽和四蒽)的反应性,[{SiNDipp}AlK]2 包含一个形式上为阴离子的 Al(I)中心。在每种情况下,铝酰衍生物都会通过铝(I)中心发生氧化加成,从而提供相应的铝环戊烯钾、铝环丙烯钾或铝降冰片二烯钾的 [4 + 1] 环加成产物。
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引用次数: 0
Synthesis and Characterization of Alkali Metal Hypersilyl Borates 碱金属超硅硼酸盐的合成与表征
Pub Date : 2024-07-22 DOI: 10.1002/zaac.202400054
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。
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引用次数: 0
On the structure of Tl2Pb(SO4)2 and crystal chemistry of thallium‐containing sulfates 论 Tl2Pb(SO4)2 的结构和含铊硫酸盐的晶体化学性质
Pub Date : 2024-07-22 DOI: 10.1002/zaac.202400072
Pengyun Chen
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.
从 Tl2CO3、Pb(NO3)2 和 H2SO4 开始,通过水热结晶法制备了含铊硫酸盐 Tl2Pb(SO4)2 的单晶。根据单晶 X 射线衍射数据解析了晶体结构:Tl2Pb(SO4)2 晶体的空间群为 R[[方程]]m,晶格参数为 a = 5.5955(2)埃,c = 22.1001(9)埃,Z = 3。该晶体结构可视为沿 c 轴由双层 Tl+夹层的[Pb(SO4)2]2-薄片。从矿物学角度来看,Tl2Pb(SO4)2 属于棕榈岩家族,并可进一步归入棕榈岩超群。利用各种概念,包括键价(BV)、电荷分布(CD)和马德隆晶格能(MAPLE),对结构模型进行了验证。值得注意的是,Tl+ 和 Pb2+ 之间 6s2 孤电子对(LEP)的立体化学活性对比是通过成键行为以及 Wang-Liebau 偏心率(WLE)参数来解释的。此外,还首次对含铊硫酸盐的晶体化学进行了广泛研究,重点是 Tl+ 的配位环境和成键行为以及相应的 WLE 参数。对这些结构相关的化合物进行了比较分析,包括 Tl2Pb(SO4)2、Tl3H(SO4)2、TlBi(SO4)2、TlIn(SO4)2、TlRh(SO4)2 和 TlAl(SO4)2。
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引用次数: 0
Retraction: Porous GdIII‐Organic Framework as a Dual‐Functional Material for Cyanosilylation of Aldehydes and Ablation of Human Liver Cancer Cells 撤稿:多孔钆Ⅲ-有机框架作为醛的氰硅烷化和人类肝癌细胞消融的双功能材料
Pub Date : 2024-07-19 DOI: 10.1002/zaac.202400105
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引用次数: 0
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