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Synthesis of 2,2,3,3‐Tetraphenyl‐5,5,6,6,7,7,8,8‐octamethyl‐2,3,5,6,7,8‐hexasilabicyclo[2.2.2]octane – a Phenyl‐substituted Silicon‐containing Cage 2,2,3,3-Tetraphenyl-5,5,6,6,7,7,8,8-octamethyl-2,3,5,6,7,8-hexasilabicyclo[2.2.2]octane - a Phenyl-substituted Silicon-containing Cage 的合成
Pub Date : 2024-07-11 DOI: 10.1002/zaac.202400115
Koichi Sato, Takahiro Sasamori
Molecular cages that contain silicon are highly versatile and stable materials with great potential for various scientific and technological applications due to their ability to form stable three‐dimensional frameworks. The synthesis of 2,2,3,3,5,5,6,6,7,7,8,8‐dodecamethyl‐2,3,5,6,7,8‐hexasilabicyclo[2.2.2]octane has already been reported and its modifications at the CH moiety have been demonstrated to afford varied functionality. Here, we present the synthesis and characterization of 2,2,3,3‐tetraphenyl‐5,5,6,6,7,7,8,8‐octamethyl‐2,3,5,6,7,8‐hexasilabicyclo[2.2.2]octane, which is a phenyl‐substituted analogue of such a silicon‐containing cage. The Ph‐substituted Si‐containing cage exhibits a low‐lying LUMO due to the hyper‐conjugation including Si–Si, Si–C σ*‐orbitals, and π(phenyl)‐orbitals, which results in a remarkable bathochromic shift in the UV‐vis absorption spectrum.
含硅的分子笼由于能够形成稳定的三维框架,因此是用途广泛且非常稳定的材料,在各种科学和技术应用领域具有巨大潜力。2,2,3,3,5,5,6,6,7,7,8,8- 十二甲基-2,3,5,6,7,8-六硅杂双环[2.2.2]辛烷的合成已有报道,其 CH 分子的改性已被证明可提供不同的功能性。在这里,我们介绍了 2,2,3,3- 四苯基-5,5,6,6,7,7,8,8-八甲基-2,3,5,6,7,8-六硅杂双环[2.2.2]辛烷的合成和表征,它是这种含硅笼的苯基取代类似物。由于 S-Si、S-C σ*-轨道和 π(苯基)-轨道的超共轭作用,Ph-取代的含硅笼子显示出低洼的 LUMO,从而导致紫外-可见吸收光谱发生显著的浴色偏移。
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引用次数: 0
UoC‐11: An Interpenetrating MOF from Fluorinated BTB Ligands and a 1‐D Mg Based SBU UoC-11:氟化 BTB 配体与一维镁基 SBU 的互穿 MOF
Pub Date : 2024-07-09 DOI: 10.1002/zaac.202400089
Uwe Ruschewitz, Sean S. Sebastian, Finn P. Dicke
A new MOF, named UoC‐11 (UoC = University of Cologne, [Mg4(3F‐BTB)2(OAc)2(DMF)6] · DMF), based on a fluorinated BTB (4,4′,4″‐benzene‐1,3,5‐triyl‐tris‐(benzoate)) derivative and Mg cations was synthesized incorporating additional acetate anions. Its crystal structure was determined from single crystal X‐ray diffraction data (P21/c, Z = 4). It consists of one‐dimensional Mg‐SBUs (strands), interconnected perpendicularly by tritopic linkers forming a dense two‐fold interpenetrating 3D network. Thus, only very small voids are formed which are fully occupied by the solvent. After activation at 150 °C (24 hours), no meaningful N2 adsorption was observed. Compared to the Ca and Sr analogues UoC‐9, UoC‐11 does not exhibit a crystal sponge behaviour. Thermal analysis (TGA) shows a release of all solvent molecules up to ~280 °C and the decomposition of the framework starts above 300 °C.
以氟化 BTB(4,4′,4″-苯-1,3,5-三基-(苯甲酸酯))衍生物和镁阳离子为基础,结合额外的醋酸阴离子,合成了一种新的 MOF,命名为 UoC-11(UoC = 科隆大学,[Mg4(3F-BTB)2(OAc)2(DMF)6] - DMF)。根据单晶 X 射线衍射数据(P21/c,Z = 4)确定了其晶体结构。它由一维 Mg-SBU(链)组成,通过三位连接体垂直相互连接,形成一个致密的两层相互渗透的三维网络。因此,只有很小的空隙被溶剂完全占据。在 150 °C 下活化(24 小时)后,没有观察到明显的 N2 吸附现象。与钙和锶类似物 UoC-9 相比,UoC-11 没有表现出晶体海绵的行为。热分析(TGA)显示,所有溶剂分子在约 280 ° C 的温度下都会释放出来,框架在 300 ° C 以上开始分解。
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引用次数: 0
Application Potential of pnp‑switching Semiconductors pnp 开关半导体的应用潜力
Pub Date : 2024-07-08 DOI: 10.1002/zaac.202400066
Philipp Deng, Matthias Hoffmann, Tom Nilges
Materials with tunable properties are often in the focus of materials science. Up to this point four different semiconducting materials and substitution variants have been found that are capable of switching between p‐ and n‐type conduction by a simple change in temperature. In this review, we illustrate previous findings of these pnp‐switching materials and current developments in functional implementations. While in the past decade, the scientific focus was primarily on discovering new materials that possess this intriguing switching effect, recently the first devices were successfully constructed and tested. Using the compounds, Ag18Cu3Te11Cl3 and AgCuS, that exhibit the pnp‐switching behaviour at approximately room temperature and 364 K, respectively, two single‐material diodes were developed and characterized. The approach for inducing this effect is denoted and the fundamental principles for realizing these devices are summarized.
具有可调特性的材料往往是材料科学的焦点。到目前为止,已经发现了四种不同的半导体材料和替代变体,它们能够通过简单的温度变化在 p 型和 n 型传导之间切换。在这篇综述中,我们将介绍这些 pnp 开关材料的前人研究成果以及目前在功能实现方面的发展情况。在过去的十年中,科学界的主要关注点是发现具有这种奇妙开关效应的新材料,而最近则成功构建并测试了首批器件。Ag18Cu3Te11Cl3 和 AgCuS 分别在室温和开氏 364 度左右的条件下表现出 pnp 开关行为,利用这两种化合物,我们开发出了两种单材料二极管,并对其进行了表征。文中指出了诱导这种效应的方法,并总结了实现这些器件的基本原理。
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引用次数: 0
Front Cover: (Z. Anorg. Allg. Chem. 11‐12/2024) 封面: (Z. Anorg. Allg. Chem. 11-12/2024)
Pub Date : 2024-07-06 DOI: 10.1002/zaac.202481101
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引用次数: 0
Ruthenium‐Catalyzed Hydrosilylation of Aldehydes with Hydrooligosilanes 钌催化的氢寡硅烷醛氢硅烷化反应
Pub Date : 2024-07-06 DOI: 10.1002/zaac.202400122
Ken-ichiro Kanno, Yasuhiro Sunaga, Soichiro Kyushin
Ruthenium‐catalyzed hydrosilylation of aldehydes with hydrooligosilanes is reported. Among the examined ruthenium catalysts, RuH2(CO)(PPh3)3 gave the best results. The reactions proceed with the Si–Si bonds preserved to afford the corresponding alkoxyoligosilanes in good yields. A series of aryl aldehydes with an electron‐withdrawing group is applicable, whereas those with an electron‐donating group are not suitable for the reaction. Mechanistic considerations suggest that the key points for the preservation of the Si–Si bonds are the formation of zero‐valent ruthenium species and the efficient coordination of the aldehyde to the ruthenium center prior to the oxidative addition of the Si–H bond.
报告了钌催化的醛与羟基硅烷的氢硅化反应。在所研究的钌催化剂中,RuH2(CO)(PPh3)3 的效果最好。反应在保留 Si-Si 键的情况下进行,以良好的收率得到相应的烷氧基寡硅烷。一系列带有取电子基团的芳基醛适用于该反应,而带有供电子基团的芳基醛则不适合该反应。机理分析表明,Si-Si 键得以保留的关键点在于零价钌物种的形成,以及在 Si-H 键氧化加成之前醛与钌中心的有效配位。
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引用次数: 0
On the Thermal Dimorphy of the Strontium Perrhenate Sr[ReO4]2 论珀尔铼酸锶 Sr[ReO4]2 的热二态性
Pub Date : 2024-06-27 DOI: 10.1002/zaac.202400045
Maurice Conrad, Sebastian Bette, Robert E. Dinnebier, Thomas Schleid
Hygroscopic single crystals of a new hexagonal high‐temperature modification of Sr[ReO4]2 were prepared from a melt of Sr[ReO4]2 ⋅ H2O and SrCl2 ⋅ 6 H2O. The structure analysis of the obtained crystals by X‐ray diffraction revealed that the title compound crystallizes in the ThCd[MoO4]3‐type structure with the hexagonal space group P63/m and the lattice parameters a=1023.81(7) pm and c=646.92(4) pm (c/a=0.632) for Z=2 in its quenchable high‐temperature form. Two crystallographically independent Sr2+ cations are coordinated by oxygen atoms forming either octahedra or tricapped trigonal prisms, whereas the Re7+ cations are found in the centers of discrete tetrahedral meta‐perrhenate units [ReO4]. Temperature‐dependent in‐situ PXRD studies of dry powder samples of Sr[ReO4]2 exhibited its thermal dimorphy with a phase‐transition temperature at 500–550 °C from literature‐known m‐Sr[ReO4]2 into the newly discovered h‐Sr[ReO4]2 (hexagonal).
利用 Sr[ReO4]2 ⋅ H2O 和 SrCl2 ⋅ 6 H2O 的熔体制备了 Sr[ReO4]2 新型六方高温修饰吸湿单晶。通过 X 射线衍射对所获得晶体的结构分析表明,标题化合物在可淬火的高温形态下结晶为 ThCd[MoO4]3 型结构,六方空间群为 P63/m,Z=2 时的晶格参数 a=1023.81(7) pm 和 c=646.92(4) pm (c/a=0.632)。两个晶体学上独立的 Sr2+ 阳离子由氧原子配位,形成八面体或三顶三棱柱,而 Re7+ 阳离子则位于离散的四面体元亨酸单元 [ReO4]- 的中心。对 Sr[ReO4]2 干粉样品进行的温度依赖性原位 PXRD 研究表明,Sr[ReO4]2 从文献中已知的 m-Sr[ReO4]2 到新发现的 h-Sr[ReO4]2(六方)的相变温度为 500-550 ℃,具有热二态性。
{"title":"On the Thermal Dimorphy of the Strontium Perrhenate Sr[ReO4]2","authors":"Maurice Conrad, Sebastian Bette, Robert E. Dinnebier, Thomas Schleid","doi":"10.1002/zaac.202400045","DOIUrl":"https://doi.org/10.1002/zaac.202400045","url":null,"abstract":"Hygroscopic single crystals of a new hexagonal high‐temperature modification of Sr[ReO<jats:sub>4</jats:sub>]<jats:sub>2</jats:sub> were prepared from a melt of Sr[ReO<jats:sub>4</jats:sub>]<jats:sub>2</jats:sub> ⋅ H<jats:sub>2</jats:sub>O and SrCl<jats:sub>2</jats:sub> ⋅ 6 H<jats:sub>2</jats:sub>O. The structure analysis of the obtained crystals by X‐ray diffraction revealed that the title compound crystallizes in the ThCd[MoO<jats:sub>4</jats:sub>]<jats:sub>3</jats:sub>‐type structure with the hexagonal space group <jats:italic>P</jats:italic>6<jats:sub>3</jats:sub>/<jats:italic>m</jats:italic> and the lattice parameters <jats:italic>a</jats:italic>=1023.81(7) pm and <jats:italic>c</jats:italic>=646.92(4) pm (<jats:italic>c</jats:italic>/<jats:italic>a</jats:italic>=0.632) for <jats:italic>Z</jats:italic>=2 in its quenchable high‐temperature form. Two crystallographically independent Sr<jats:sup>2+</jats:sup> cations are coordinated by oxygen atoms forming either octahedra or tricapped trigonal prisms, whereas the Re<jats:sup>7+</jats:sup> cations are found in the centers of discrete tetrahedral <jats:italic>meta</jats:italic>‐perrhenate units [ReO<jats:sub>4</jats:sub>]<jats:sup>−</jats:sup>. Temperature‐dependent <jats:italic>in‐situ</jats:italic> PXRD studies of dry powder samples of Sr[ReO<jats:sub>4</jats:sub>]<jats:sub>2</jats:sub> exhibited its thermal dimorphy with a phase‐transition temperature at 500–550 °C from literature‐known m‐Sr[ReO<jats:sub>4</jats:sub>]<jats:sub>2</jats:sub> into the newly discovered h‐Sr[ReO<jats:sub>4</jats:sub>]<jats:sub>2</jats:sub> (hexagonal).","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141506915","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}
引用次数: 0
Synthesis and crystal structures of novel group 6B metal carbonyl complexes with N‐(4‐methyl‐2‐ pyridinyl)‐P,P‐diphenylphosphinous amide ligand 新型 6B 族金属羰基配合物与 N-(4-甲基-2-吡啶基)-P,P-二苯基膦酰胺配体的合成及晶体结构
Pub Date : 2024-06-25 DOI: 10.1002/zaac.202400075
Harbi Tomah AL-Masri, Suzan Mohammed Alrawashdeh, Akram Ali Almejled, Ziad moussa
The reaction of N‐(4‐methyl‐2‐pyridinyl)‐P,P‐diphenylphosphinous amide ligand 4‐Me‐C5H3N‐2‐NH(PPh2) (1) with M(CO)6 (M = Cr, Mo, W) in refluxing toluene afforded a mononuclear group 6B metal tetracarbonyls [M(CO)4{1‐κ2P,N}] (M = Cr(2), Mo(3), W(4) ). Complexes 2–4 were characterized by multinuclear NMR (1H, 13C and 31P NMR) and IR spectroscopy, and their structures were also determined by single crystal X‐ray diffraction. 2 and 4 represent the first examples of structurally characterized complexes of such ligands with group 6B metal carbonyls.
在回流甲苯中,N-(4-甲基-2-吡啶基)-P,P-二苯基膦酰胺配体 4-Me-C5H3N-2-NH(PPh2) (1) 与 M(CO)6(M = Cr、Mo、W)反应,得到单核 6B 族金属四碳化物 [M(CO)4{1-κ2P,N}] (M = Cr(2)、Mo(3)、W(4) )。通过多核核磁共振(1H、13C 和 31P NMR)和红外光谱对 2-4 号络合物进行了表征,并通过单晶 X 射线衍射确定了它们的结构。2 和 4 是此类配体与 6B 族金属羰基形成的具有结构特征的络合物的首例。
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引用次数: 0
The peculiar molecular [(IF5)6(HF2)4]4− anion of the compound K4[(IF5)6(HF2)4] 化合物 K4[(IF5)6(HF2)4]的特殊分子[(IF5)6(HF2)4]-阴离子
Pub Date : 2024-06-25 DOI: 10.1002/zaac.202400085
Björn Koch, Tim Florian Graubner, Florian Kraus
K4[(IF5)6(HF2)4] was obtained from the reaction of K[HF2] with liquid IF5. The compound was analyzed by single crystal and powder X‐ray diffraction, Raman spectroscopy, and quantum‐chemical calculations. It contains the largest molecular IF5/HF2− complex anion known so far. Surprisingly, the crystal structure of the A4B compound can be related to the Hg4Pt structure type.
K4[(IF5)6(HF2)4] 是由 K[HF2] 与液体 IF5 反应得到的。该化合物通过单晶和粉末 X 射线衍射、拉曼光谱和量子化学计算进行了分析。它含有迄今已知的最大分子 IF5/HF2- 复合物阴离子。令人惊讶的是,A4B 化合物的晶体结构与 Hg4Pt 结构类型有关。
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引用次数: 0
Practicality and Compatibility of Cd(II) Coordination Polymer as Luminescent Sensor in Selective and Sensitive Detection of 3‐Nitrotyrosine Biomarker 镉(II)配位聚合物作为发光传感器选择性灵敏检测 3-硝基酪氨酸生物标记物的实用性和兼容性
Pub Date : 2024-06-25 DOI: 10.1002/zaac.202400065
Jingyao Yang, Feiyu Lu, Wencui Li, Lu Zhang, Jingrui Yin, Mohd. Muddassir, Liming Fan
Based on the mixed ligands of 1,4‐bis(2,4,6‐tricarboxylpyrid‐5‐yl)benzene (H6BTPB) and 1,4‐bis(imidazol‐1‐yl)benzene (bib), a new cadmium(II) coordination polymer with the molecular formula of {[Cd(bib)(μ2‐H2O)(H2O)2](H4BTPB)0.5(bib)0.5}n (CdCP) was constructed under solvothermal condition, and displayed a 3D supramolecular structure expanded by the hydrogen bonds between the 1D [Cd(bib)(μ2‐H2O)(H2O)2]n ladder chain and the guests. Profiting from its superior stability and inherent luminescence, the prepared CdCP dispalyed great potential as a highly sensitive and selective luminescent sensor in trace detection of 3‐NT biomarker in both water and real bodily fluids through the luminescence quenching effects, with the Ksv and LODs being 2.408×105 M‐1 and 30.3 nM in water, 2.230×105 M‐1 and 44.7 nM in diluted urine, 2.249×105 M‐1 and 43.9 nM in diluted serum, respectively. Subsequent mechanism studies indicated the synergistic effect of internal filtering effect, photo‐induced electron transfer, and fluorescence resonance energy transfer determining the luminescence quenching response of CdCP towards 3‐NT biomarker.
基于1,4-双(2,4,6-三羧基吡啶-5-基)苯(H6BTPB)和1,4-双(咪唑-1-基)苯(bib)的混合配体,在溶热条件下构建了分子式为{[Cd(bib)(μ2-H2O)(H2O)2](H4BTPB)0.5(bib)0.5}n(CdCP),并通过 1D [Cd(bib)(μ2-H2O)(H2O)2]n 梯链与客体之间的氢键扩展出三维超分子结构。利用其优越的稳定性和固有的发光特性,制备的 CdCP 通过发光淬灭效应,在痕量检测水和真实体液中的 3-NT 生物标记物时,具有作为高灵敏度和高选择性发光传感器的巨大潜力,其 Ksv 和 LOD 分别为 2.在水中的 Ksv 和 LOD 分别为 2.408×105 M-1 和 30.3 nM,在稀释尿液中的 Ksv 和 LOD 分别为 2.230×105 M-1 和 44.7 nM,在稀释血清中的 Ksv 和 LOD 分别为 2.249×105 M-1 和 43.9 nM。随后的机理研究表明,CdCP 对 3-NT 生物标记物的发光淬灭反应是由内部过滤效应、光诱导电子传递和荧光共振能量转移协同作用决定的。
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引用次数: 0
In celebration of the 60th birthday of Rhett Kempe 庆祝瑞特-肯普 60 岁生日
Pub Date : 2024-06-25 DOI: 10.1002/zaac.202400124
Birgit Weber, Sven Rau
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引用次数: 0
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