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Can Solventless Reactions Sometimes Succeed When Solvent-Mediated Reactions Fail? A Second Case Study for Cu(I) and Ag(I) Complexes of Divergently Bridging Diimines without or with Fluorinated Azolates 当溶剂介导的反应失败时,无溶剂反应有时能成功吗?不含氟偶氮酸盐或含氟偶氮酸盐的发散桥接二亚胺的Cu(I)和Ag(I)配合物的第二个案例研究
IF 5.4 3区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2020-09-29 DOI: 10.1080/02603594.2020.1770738
Ruaa M. Almotawa, Christopher Hu, A. Cimino, V. Nesterov, M. Omary, Manal A. Rawashdeh-Omary
ABSTRACT This paper provides the fifth manifestation of a new tradition by which the editors of Comments on Inorganic Chemistry wish to lead by example, whereby we start publishing original research content that, nonetheless, preserves the Journal’s identity as a niche for critical discussion of contemporary literature in inorganic chemistry (For the previous manifestations, see: Comments Inorg. Chem. 2018, 38, 1–35; 2019, 39, 1–26; 2019, 39, 188–215; 2020, 40, 1–24.) Herein, synthetic details, solid-state structures, and photophysical properties of a group of silver(I) and copper(I) complexes are described. Two silver-based coordination polymers have been obtained: {[3,5-(CF3)2Pz]2(bpp)Ag2}∞ (1) and {[3,5-(CF3)2Pz][5-(C6F5)Ttz](bpp)Ag}∞ (2) – constructed from bent 1,3-bis(4-pyridyl)propane (bpp), 3,5-bis(trifluoromethyl)pyrazole ([3,5-(CF3)2Pz]H) and 5-pentafluorophenyl-tetrazole ([5-(C6F5)Ttz]H) in order to inspect the influence of mixed ligands on the resulting silver-based coordination complexes. The structure of 1 shows a distorted trigonal planar geometry with both the bpp and [3,5-(CF3)2Pz] ligands binding to the silver atom. The silver in 2 shows an uncommon interaction with the three different ligands. Also, two different geometries including distorted tetrahedral and distorted trigonal were presented for two different silver atoms. An interesting result was obtained for the Cu(I) coordination polymer {[Cu(bpp)2][BF4]}∞ (3) which was successfully synthesized in a solventless reaction but not a solvent-mediated reaction, hence manifesting a “green” chemistry route. The structure of 3 shows an ideal tetrahedral geometry similar to that for the silver analogue, {[Ag(bpp)2][BF4]}∞ (3a), published previously, whereas herein we obtained the same product with the same crystal structure via a more facile conventional synthetic route. All four complexes show bpp ligand-centered green emissions at ambient and cryogenic temperatures. Finally, a commentary is added to contrast the solventless vs solvent-mediated reactions in both this investigation and a precedent thereof by the same corresponding author’s group (Inorg. Chem. 2018, 57, 9962–9976), whereby reactions proceeded successfully only via the solventless route through mechanical grinding herein and spontaneous sublimation by vapor diffusion from the solid-state of one reactant to another yet nonvolatile reactant in the literature precedent, respectively. Graphical Abstract
本文提供了新传统的第五种表现形式,《无机化学评论》的编辑们希望以此为榜样,由此我们开始发表原创的研究内容,尽管如此,仍保留了《无机化学评论》作为当代无机化学文献批判性讨论的定位(关于之前的表现形式,请参见:评论网站)。化学,2018,38,1-35;2019, 39, 1-26;2019, 39, 188-215;2020, 40, 1-24。本文描述了一组银(I)和铜(I)配合物的合成细节、固态结构和光物理性质。为了考察混合配体对银基配位配合物的影响,得到了两个银基配位聚合物:{[3,5-(CF3)2Pz]2(bpp)Ag2}∞(1)和{[3,5-(CF3)2Pz][5-(C6F5)Ttz](bpp)Ag}∞(2)-由弯曲的1,3-二(4-吡啶基)丙烷(bpp), 3,5-二(三氟甲基)吡唑([3,5-(CF3)2Pz]H)和5-五氟苯四唑([5-(C6F5)Ttz]H)组成。1的结构呈现出扭曲的三角形平面几何,bpp和[3,5-(CF3)2Pz]配体都与银原子结合。2中的银与三种不同的配体表现出不同寻常的相互作用。同时,对两种不同的银原子,提出了畸变四面体和畸变三角形两种不同的几何形状。Cu(I)配位聚合物{[Cu(bpp)2][BF4]}∞(3)在无溶剂反应中成功合成,而不是在溶剂介导的反应中成功合成,从而实现了“绿色”化学路线。3的结构表现出与先前发表的银类似物{[Ag(bpp)2][BF4]}∞(3a)相似的理想四面体几何形状,而本文通过更简单的常规合成路线获得了具有相同晶体结构的相同产物。这四种配合物在常温和低温下均表现出以bpp配体为中心的绿色辐射。最后,一个评论被添加到对比无溶剂和溶剂介导的反应在这两个调查和先例的相同的相应作者的组(Inorg)。化学,2018,57,9962-9976),其中仅通过无溶剂途径(通过机械研磨)和通过蒸汽扩散从一种反应物的固态到另一种非挥发性反应物的自发升华,分别在文献先例中成功进行反应。图形抽象
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引用次数: 0
The Effect of Hydrothermal Synthesis Parameters on the Formation of Sodium Bismuth Titanate 水热合成参数对钛酸铋钠生成的影响
IF 5.4 3区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2020-09-23 DOI: 10.1080/02603594.2020.1813728
E. A. Reshetnikova, I. V. Lisnevskaya, Ekaterina A. Zalyubovskaya, V. Butova, A. Soldatov
ABSTRACT We report the effect of various Bi:Ti ratios x:1 (x = 0.5–3) on the phase formation of sodium-bismuth titanate Na0.5Bi0.5TiO3 (NBT) during hydrothermal synthesis (230°С, 3 MPa, 96 h) from titanium oxide and bismuth hydroxide in 20 M NaOH solution. It was shown that single-phase ceramics with perovskite structure could be obtained at x = 0.5–0.9 using the hot-pressing technique (1025°С, 60 MPa, 1 h). At x = 1, hydrothermal synthesis results in single-phase samples, while, after sintering, the admixture of Na2Ti3O7 was detected. At x = 2 and 3, samples contained admixtures after hydrothermal synthesis. The x–value does not significantly affect the composition of perovskite-like products despite the excess of bismuth in the system. The chemical composition of the samples with x = 0.5–0.9 corresponds to the general formula Na0.60–0.69Bi0.40–0.31TiO2.9–2.81δ0.10–0.19 (where δ represents vacancies in oxygen sublattice). The Bi3+ content in the samples is underestimated due to the solubility of its hydroxide in a 20 M alkali solution. The properties of ceramics are not significantly affected by x values, and materials exhibit following average characteristics: electrical resistivity 1.3 × 109 Ohm∙cm, tanδ = 0.15, Кр = 0.1, d31 = 6.7 and d33 = 9.5 pC/N, g31 = 2.34 and g33 = 3 mV∙m/N.
摘要本文报道了不同Bi:Ti比x:1 (x = 0.5-3)对钛酸钠-铋酸钠Na0.5Bi0.5TiO3 (NBT)在20 M NaOH溶液中水热合成(230°С, 3 MPa, 96 h)相形成的影响。结果表明,在x = 0.5 ~ 0.9的温度下(1025°С, 60 MPa, 1 h),热压技术可以得到具有钙钛矿结构的单相陶瓷。在x = 1时,水热合成得到单相样品,烧结后检测到Na2Ti3O7的掺入。在x = 2和3时,样品中含有水热合成后的外加剂。尽管系统中存在过量的铋,但x值对类钙钛矿产品的组成没有显著影响。x = 0.5 ~ 0.9时样品的化学组成为:Na0.60-0.69Bi0.40-0.31TiO2.9-2.81δ0.10-0.19(其中δ为氧亚晶格空位)。由于氢氧化物在20 M碱溶液中的溶解度,样品中的Bi3+含量被低估。陶瓷的性能不受x值的显著影响,材料的平均电阻率为1.3 × 109欧姆∙cm, tanδ = 0.15, Кр = 0.1, d31 = 6.7和d33 = 9.5 pC/N, g31 = 2.34和g33 = 3 mV∙m/N。
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引用次数: 4
Recent Advances in Nanocomposite Luminescent Metal-Organic Framework Sensors for Detecting Metal Ions 金属离子探测纳米复合发光金属-有机框架传感器的研究进展
IF 5.4 3区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2020-09-04 DOI: 10.1080/02603594.2020.1805319
S. Kanan, Ahmed Malkawi
ABSTRACT Metal-organic frameworks (MOFs) are of great interest to researchers in chemistry and material science due to their various chemical and physical properties, which include high surface area, augmented adsorption/desorption kinetics, biocompatibility, and functional tunability. The structurally diverse 1-D, 2-D, and 3-D metal-organic frameworks have found applications in chemical sensing and several other fields, such as energy applications, biomedicine, and catalysis. In this review article, we address recent research advances in the use of metal-organic-framework-based nanocomposite materials as luminescent sensors for detecting various metal ions in aqueous biological and environmental samples. Graphical Abstract
金属有机框架(mof)由于其具有各种化学和物理性质,包括高表面积、增强的吸附/解吸动力学、生物相容性和功能可调性,引起了化学和材料科学研究人员的极大兴趣。结构多样的1-D、2-D和3-D金属有机框架已经在化学传感和其他几个领域得到了应用,如能源应用、生物医学和催化。本文综述了金属-有机-骨架基纳米复合材料作为发光传感器用于检测生物和环境样品中各种金属离子的最新研究进展。图形抽象
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引用次数: 24
An Investigation of How Nitrogen Monoxide (NO) and Nitrogen Dioxide (NO2) Are Produced in Oxidations by Nitric Acid (HNO3) 硝酸(HNO3)氧化过程中产生一氧化氮(NO)和二氧化氮(NO2)的机理研究
IF 5.4 3区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2020-09-03 DOI: 10.1080/02603594.2020.1803296
A. Mousavi
ABSTRACT In oxidations by nitric acid (HNO3), such as the dissolution of gold (Au) in aqua regia, mixtures of nitrogen monoxide (NO) and nitrogen dioxide (NO2) are produced. In this article, the exact processes through which these two nitrogen oxides are produced were discussed. It was shown that in the processes of dissolution in HNO3 or aqua regia, NO2 is never a direct product of oxidations by HNO3. It was also explained that in such processes, NO2 is always produced from HNO3 and NO reacting. Further, the effect of the concentration of HNO3 was discussed in light of thermodynamic calculations. Graphical Abstract
在硝酸(HNO3)氧化过程中,如金(Au)在王水中的溶解,会产生一氧化氮(NO)和二氧化氮(NO2)的混合物。本文讨论了生产这两种氮氧化物的具体过程。结果表明,在HNO3或王水的溶解过程中,NO2不是HNO3氧化的直接产物。同时解释了在这些过程中,总是由HNO3和NO反应产生NO2。进一步从热力学计算的角度讨论了HNO3浓度的影响。图形抽象
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引用次数: 1
Advances in Organometallic Chemistry, Volume 71 有机金属化学进展,第71卷
IF 5.4 3区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2020-06-12 DOI: 10.1080/02603594.2020.1771702
B. Belete
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引用次数: 1
Solid Acid Catalysts for Biodiesel Production 用于生物柴油生产的固体酸催化剂
IF 5.4 3区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2020-05-07 DOI: 10.1080/02603594.2020.1755273
Tarun F. Parangi, M. Mishra
ABSTRACT Biodiesel belongs to the class of renewable and sustainable fuel sources receiving more attention as a rapidly growing field with higher potential than other energy sources. The main shortcoming of biodiesel production is the high cost of the production process and the catalytic system. The present contribution aims to briefly review and evaluate the performance of solid acid catalysts (SACs) focused on biodiesel production through esterification and transesterification. The review article gives insight into the prime catalytic characteristics that can be modified in an economical and eco-friendly way to reduce overall cost of fuel products on an industrial scale. The advantages and disadvantages of the used catalytic systems are discussed and compared with their catalytic activity and stability.
生物柴油作为一种发展迅速、潜力巨大的可再生和可持续能源,越来越受到人们的关注。生物柴油生产的主要缺点是生产工艺和催化系统成本高。本文旨在简要回顾和评价固体酸催化剂(SACs)在酯化和酯交换生物柴油生产中的性能。这篇综述文章深入探讨了主要的催化特性,这些特性可以通过经济和环保的方式进行修改,从而在工业规模上降低燃料产品的总体成本。讨论了常用催化体系的优缺点,并对其催化活性和稳定性进行了比较。
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引用次数: 20
Metal/Organosilicon Complexes: Structure, Reactivity, and Considerations for Catalysis 金属/有机硅配合物:结构、反应性和对催化的考虑
IF 5.4 3区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2020-04-16 DOI: 10.1080/02603594.2020.1737026
Matthew T. Whited, B. Taylor
ABSTRACT Complexes featuring metal–silicon bonds play a key role in many catalytic and stoichiometric transformations. As such, it is important to understand the underlying electronic structures of such units and the reactivity patterns they engender, which in many cases differ substantially from well-known patterns for metal–carbon bonds. This review seeks to provide a framework for understanding reactivity of metal/organosilicon units, focusing specifically on considerations for catalysis, similarities and differences between M–C and M–Si chemistry, and possibilities for M/Si cooperative catalysis. Graphical abstract
具有金属-硅键的配合物在许多催化和化学计量转化中起着关键作用。因此,了解这些单元的潜在电子结构和它们产生的反应模式是很重要的,在许多情况下,它们与众所周知的金属-碳键模式有很大的不同。这篇综述旨在为理解金属/有机硅单元的反应性提供一个框架,特别关注催化的考虑,M - c和M - Si化学的异同,以及M/Si协同催化的可能性。图形抽象
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引用次数: 16
Crystallography of Reactive Intermediates 反应中间体结晶学
IF 5.4 3区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2020-04-10 DOI: 10.1080/02603594.2020.1747054
Anuvab Das, Gerard P Van Trieste, D. Powers
ABSTRACT Metal–ligand (M–L) multiply bonded complexes hold a central place in inorganic chemistry and catalysis: From fundamental and historical perspectives, these species have played a critical role in the articulation of important bonding principles (i.e. the vanadyl ion in the development of molecular orbital theory); from a practical perspective, these species are critical intermediates in a variety of chemical reactions (i.e. N2 and O2 reduction, H2O oxidation, and C–H functionalization). For many high-valent, early metal complexes, overlap of ligand-based electrons with vacant π-symmetry orbitals leads to strong M–L multiple bonds. The stability of these species enables straightforward characterization with a suite of standard spectroscopic and diffraction-based experiments. Mid- and late-transition metal complexes, with attendant higher d-electron counts, often support more reactive M–L multiply bonded fragments. The reactivity of these species simultaneously renders them attractive intermediates for catalysis but challenging synthetic targets to observe and characterize. A number of important strategies have been advanced to enable experimental characterization of mid- to late-metal–ligand multiply bonded species. Synthetic manipulation of the coordination geometry and ligand donicity, as well as introduction of sterically encumbering ligands, have each emerged as powerful methods to tame the inherent reactivity of kinetically labile M–L multiple bonds. While these efforts have resulted in families of well-characterized complexes and provided critical insights regarding structure and bonding, the synthetic derivatization required to stabilize M–L fragments of interest often obviates the substrate functionalization activity relevant to catalysis. Photochemical synthesis of reactive species provides a conceptually attractive strategy to generate reactive M–L fragments under conditions compatible with time-resolved or cryogenic steady-state characterization, and photogeneration has enabled observation of a number of reactive M–L fragments. The suite of tools available to characterize photogenerated reactive species is often more limited than typical for kinetically stabilized complexes and structural characterization is typically not possible. Recently, photocrystallographic experiments, in which reactive M–L multiply bonded intermediates are generated within single-crystal matrices, have been advanced as a strategy to interrogate the structures of reactive intermediates in C–H functionalization. This Comment describes the historical antecedents to these experiments, highlights examples of photocrystallographic characterization of reactive intermediates, and discusses future opportunities. Graphical Abstract
金属配体(M-L)多重键配合物在无机化学和催化中占有中心地位:从基础和历史的角度来看,这些物种在重要的键合原理(即钒基离子在分子轨道理论的发展中)的表达中发挥了关键作用;从实际应用的角度来看,这些物质是各种化学反应(即N2和O2还原,H2O氧化和C-H功能化)的关键中间体。对于许多高价早期金属配合物,配体电子与空π-对称轨道的重叠导致了强的M-L多重键。这些物种的稳定性可以通过一套标准的光谱和衍射实验来直接表征。中期和晚期过渡金属配合物,伴随着更高的d电子计数,通常支持更活跃的M-L多重键片段。这些物种的反应性同时使它们成为有吸引力的催化中间体,但对观察和表征合成目标具有挑战性。一些重要的策略已经提出,使实验表征中晚期金属配体多键物种。对配位几何和配体构型的合成操纵,以及引入立体阻碍配体,都已成为驯服动力学不稳定的M-L多键固有反应性的有力方法。虽然这些努力已经产生了表征良好的配合物家族,并提供了有关结构和键合的关键见解,但稳定感兴趣的M-L片段所需的合成衍生化通常会消除与催化相关的底物功能化活性。反应性物质的光化学合成提供了一种概念上有吸引力的策略,可以在与时间分辨或低温稳态表征相容的条件下生成反应性M-L片段,并且光化学合成已经能够观察到许多反应性M-L片段。可用于表征光生成反应物质的工具套件通常比典型的动力学稳定配合物更有限,结构表征通常是不可能的。近年来,在单晶基质中生成反应性M-L多键中间体的光晶体实验已经被提出,作为一种研究反应性中间体在碳氢官能化中的结构的策略。这篇评论描述了这些实验的历史先例,强调了反应中间体的光晶体表征的例子,并讨论了未来的机会。图形抽象
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引用次数: 7
Strategies to Improve Electrical and Ionic Conductivities of Metal–Organic Frameworks 提高金属-有机骨架电导率和离子电导率的策略
IF 5.4 3区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2020-03-03 DOI: 10.1080/02603594.2019.1704738
M. A. Gordillo, S. Saha
ABSTRACT Owing to their highly ordered crystalline structures and ease of introducing different electroactive meta ions and ligands, metal–organic frameworks (MOFs) have emerged as promising electrical and ion conducting materials. In this minireview, we highlighted recent advances in guest-induced electronic and ionic conductivity of MOFs, which are otherwise insulators or poor conductors. Examples of conductivity enhancement upon guest-induced framework oxidation or reduction, π-donor/acceptor stack formation, crosslinking of coordinatively unsaturated nodes, and binding of mobile Li+ and Mg2+ with the MOFs are discussed. Graphical abstract
由于其高度有序的晶体结构和易于引入不同的电活性元离子和配体,金属有机框架(mof)已成为一种有前途的导电和离子导电材料。在这篇小型综述中,我们重点介绍了mof(否则是绝缘体或不良导体)的客体诱导电子和离子电导率的最新进展。讨论了客体诱导框架氧化或还原、π-供体/受体堆叠形成、配位不饱和节点交联以及移动Li+和Mg2+与mof的结合等增强电导率的例子。图形抽象
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引用次数: 8
Photocatalysis with Transition Metal Based Photosensitizers 过渡金属基光敏剂的光催化作用
IF 5.4 3区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2020-03-03 DOI: 10.1080/02603594.2019.1694517
J. Shon, Thomas S. Teets
ABSTRACT Photocatalysis under visible-light irradiation has many applications in organic synthesis and solar fuels. Out of the many photosensitizers that have been used in photocatalysis applications, metal-based photosensitizers are most prominent, given their excellent tunability and performance. In this review, different categories of metal-based photosensitizers are summarized and their function in photocatalytic reactions is described. There are also examples of recently developed photocatalytic applications using these photosensitizers. Graphical abstract
可见光照射下的光催化在有机合成和太阳能燃料中有着广泛的应用。在许多用于光催化应用的光敏剂中,金属基光敏剂以其优异的可调性和性能而最为突出。本文综述了不同类型的金属基光敏剂及其在光催化反应中的作用。最近也有使用这些光敏剂开发光催化应用的例子。图形抽象
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引用次数: 29
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