Journal of Molecular Structure最新文献_第10页

A study on complexation of Zn(II) salts with 4-aryl-2-(pyridin-2-yl)quinolines: The influence of anions on the complex structures and their luminescent properties 锌（II）盐与 4-芳基-2-（吡啶-2-基）喹啉的络合研究：阴离子对配合物结构及其发光特性的影响

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2024-11-01 DOI: 10.1016/j.molstruc.2024.140526

Nguyen Hien , Nguyen Nhat Khanh , Van Thong Pham , Tran Ngoc Dung , Hoang Tuan Duong , Nguyen Hoang Giang , Nguyen Duc Anh , Luc Van Meervelt , Le Thi Hong Hai

A novel ligand, 6‑methoxy-4-(4-methoxyphenyl)-2-(pyridin-2-yl)quinoline (PQ) was synthesized and studied for its interaction with ZnX₂.nH₂O (X: Cl^-, OAc^-,

{NO}_{3}^{-}

) to form three complexes of the type [Zn(X₂)(PQ)(H₂O)_n] (Zn1-Zn3) with high yields, ranging from 75 to 94 %. The structures of Zn1–Zn3 were fully characterized using ESI mass spectrometry, IR and ¹H NMR spectroscopy, and single-crystal X-ray diffraction (for Zn1 and Zn3). Spectroscopic analyses revealed that Spectroscopic analyses revealed that the central atom Zn(II) in Zn1, Zn2, and Zn3 has the coordination numbers of 4, 5, and 6, respectively. In these complexes, Zn(II) coordinates with the PQ ligand through its two nitrogen atoms, while the remaining coordination sites are occupied by anions such as Cl^-, OAc,

{NO}_{3}^{-}

, or by H₂O. The results also indicate that the optical properties of the Zn(II) complexes depend not only on the primary organic ligand QP but also on the secondary inorganic ligands. In THF, the complexes Zn1 and Zn3, which contain chlorido and nitrato ligands exhibit intense fluorescence blue emissions at 443 and 462 nm with quantum yields of 0.66 and 0.70, respectively. Although the complex Zn2 has the weakest emission in THF, it exhibited the strongest blue emission intensity in solid state. In addition, computational studies provided insights into the structural and electronic properties, showing a strong correlation with experimental data. The calculated absorption and emission spectra were promarily based on the transition between HOMO and LUMO (π-π*) with high oscillator strength.

合成了一种新型配体 6-甲氧基-4-(4-甲氧基苯基)-2-(吡啶-2-基)喹啉 (PQ)，并研究了它与 ZnX2.nH2O （X：Cl-、OAc-、NO3-）的相互作用，从而形成了三种类型的[Zn(X2)(PQ)(H2O)n]（Zn1-Zn3）配合物，产率高达 75% 至 94%。利用 ESI 质谱、红外和 1H NMR 光谱以及单晶 X 射线衍射（Zn1 和 Zn3）对 Zn1-Zn3 的结构进行了全面鉴定。光谱分析显示，Zn1、Zn2 和 Zn3 中的中心原子 Zn（II）的配位数分别为 4、5 和 6。在这些配合物中，Zn（II）通过其两个氮原子与 PQ 配体配位，而其余的配位位点则被 Cl-、OAc、NO3- 等阴离子或 H₂O 所占据。研究结果还表明，Zn(II) 配合物的光学性质不仅取决于主有机配体 QP，还取决于次无机配体。在 THF 中，含有氯配体和硝基配体的配合物 Zn1 和 Zn3 在 443 和 462 纳米波长处发出强烈的蓝色荧光，量子产率分别为 0.66 和 0.70。虽然复合物 Zn2 在四氢呋喃中的发射强度最弱，但在固态下却表现出最强的蓝色发射强度。此外，计算研究深入揭示了其结构和电子特性，并与实验数据显示出很强的相关性。计算得出的吸收光谱和发射光谱主要基于高振荡强度的 HOMO 和 LUMO（π-π*）之间的转变。

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引用次数: 0

Precise synthesis of cyclopropyl methyl ketone via proton transfer of 5-chloro-2-pentanone driven by hydrogen bonds 通过氢键驱动 5-Cloro-2-pentanone 质子转移精确合成环丙基甲基酮

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2024-11-01 DOI: 10.1016/j.molstruc.2024.140564

Qianqian Xing , Xiaoliang Jia , Shiyu Jia , Yongqin Qi , Yuqi Wang , Yingxiong Wang , Xianglin Hou

The traditional synthesis methods of cyclopropyl methyl ketone (CPMK) have some disadvantages such as low yield, slow reaction rate and unclear catalytic mechanism. To solve these problems, a new strategy is developed to synthesize CPMK from 5‑chloro-2-pentanone (CPE) using 1,8-diazabicyclo[5.4.0]undec‑7-ene (DBU). Experiment results show that the yield of CPMK reached a maximum of 96.5 % in DBU at 40 °C for 30min. The mechanism study shows that the hydrogen bond between DBU and CPE is the key to drive the deprotonation and cyclization of CPE. The hydrogen bond is formed between the N atom on C = N of DBU and the α-H on the methylene group associated with the carbonyl group on CPE. The catalyst DBU is converted into [DBUH]⁺Cl⁻, which can be reclaimed and recycled completely. The density functional theory (DFT) calculation confirmed the existence of molecular hydrogen bonds and proved that the hydrogen bond driving force is the key to the reaction. The hydrogen bond driven mechanism provides a new idea for the basic research of cyclization reaction.

环丙基甲基酮（CPMK）的传统合成方法存在收率低、反应速率慢、催化机理不明确等缺点。为了解决这些问题，研究人员开发了一种新策略，利用 1,8-二氮杂双环[5.4.0]十一碳-7-烯（DBU）从 5-氯-2-戊酮（CPE）合成 CPMK。实验结果表明，在 DBU 中，温度为 40 °C，时间为 30 分钟，CPMK 的产率最高可达 96.5%。机理研究表明，DBU 和 CPE 之间的氢键是驱动 CPE 发生去质子化和环化反应的关键。氢键是在 DBU 的 C = N 上的 N 原子和 CPE 上与羰基相关的亚甲基上的α-H 之间形成的。催化剂 DBU 转化为[DBUH]+Cl-，可以完全回收和循环利用。密度泛函理论（DFT）计算证实了分子氢键的存在，并证明氢键驱动力是反应的关键。氢键驱动机理为环化反应的基础研究提供了新思路。

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引用次数: 0

The role of intra and intermolecular interactions on the conformational dynamics of 2-halo-1-phenylpropanols: Structure and solvent effects 分子内和分子间相互作用对 2-卤代-1-苯基丙醇构象动力学的作用：结构和溶剂效应

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2024-11-01 DOI: 10.1016/j.molstruc.2024.140493

Camila Botin Francisco , Fernanda Franco Dourado , Cleverton de Souza Fernandes , Gisele de Freitas Gauze , Ernani Abicht Basso

Experimental and theoretical ³J_H_H scalar coupling constants allowed the identification of the conformational landscape of erythro (eX) and threo (tX) 2-halo-1-phenylpropanols (halo = F, Cl, and Br). NMR scalar coupling constants captured dynamics of the OC-C-X dihedral and OH rotameric states, in a dynamic and solvent-dependent equilibrium. The erythro series revealed a particular halogen-dependent equilibrium, which showed different sensitivity to the media, especially in acetone, where the eF populations were completely shifted. At the same time, threo showed a highly solvent-sensitive equilibrium. NBO calculations showed the importance of electron delocalization over steric and electrostatic effects to stabilize the preferred synclinal conformer in both diastereomers. A Principal Component Analysis (PCA) on the NBO stabilization energies pointed to a complex mixture of electronic delocalization happening simultaneously. Hyperconjugative interactions are significant, but they are not the only important effect. Non-covalent interactions were also identified through NCI surfaces. Hydrogen bonds and intramolecular C-X···π and CH···π interactions were proved to act differently in the two diastereomers, affecting their equilibria in different ways. Nuclear Overhauser (NOE) NMR experiments point to an intramolecular CH···π contact, while ¹H NMR of the aromatic hydrogens evidence an intermolecular effect of acetone and DMSO on the phenyl ring. DFT with explicit solvation shows a solvent shell favoring intermolecular CH···π contacts, in agreement with the experiments. This thorough analysis revealed that intra- and intermolecular factors contribute to the preference for the synclinal conformer in the studied compounds.

通过实验和理论 3JHH 标量耦合常数，确定了赤式（eX）和苏式（tX）2-卤代-1-苯基丙醇（卤代 = F、Cl 和 Br）的构象格局。核磁共振标量耦合常数捕捉到了 OC-C-X 二面体和羟基旋转态的动态，处于一种动态的、依赖于溶剂的平衡状态。赤藓系列显示了一种特殊的卤素依赖性平衡，它对介质的敏感性不同，尤其是在丙酮中，eF 种群完全偏移。与此同时，苏氨酸显示出对溶剂高度敏感的平衡。NBO 计算表明，在稳定两种非对映异构体的优选同环构象方面，电子析出的重要性超过了立体效应和静电效应。对 NBO 稳定化能量进行的主成分分析（PCA）表明，同时发生的电子脱定位作用是一种复杂的混合作用。超共轭相互作用非常重要，但并不是唯一的重要影响。通过 NCI 表面还发现了非共价相互作用。氢键和分子内的 C-X-π 和 CH-π 相互作用在两种非对映异构体中的作用不同，以不同的方式影响着它们的平衡。核奥弗斯（NOE）核磁共振实验表明了分子内的 CH---π 接触，而芳香族氢的 1H 核磁共振则证明了丙酮和 DMSO 对苯环的分子间作用。明确溶解的 DFT 显示，溶剂壳有利于分子间 CH---π 接触，这与实验结果一致。这项全面的分析表明，分子内和分子间因素导致了所研究化合物的合成构象的偏好。

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引用次数: 0

Homogeneous and heterogeneous ionic liquids catalyze CO2 cycloaddition reaction 均相和异相离子液体催化二氧化碳环化反应

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2024-11-01 DOI: 10.1016/j.molstruc.2024.140534

Jian-Fei Sun , Yu-Jin Qin , Yong-Liang Zhang , Zhan-You Sa , Jie Liu , Yu-Hua Wang , Chun-Yuan Wang , Qing-Lei Tan

The synthesis of cyclic carbonates, which are essential solvents for lithium-ion batteries, through the cycloaddition of carbon dioxide (CO₂) and epoxides, and further ester exchange with methanol to form linear carbonates has always been one of the effective ways for CO₂ resource utilization. In this work, the kinetics and reactor technology selection of ionic liquids as catalysts for CO₂ conversion were analyzed from the perspective of process systems engineering. Firstly, ethanol (EtOH) was used as the solvent, and 1‑butyl‑3-methylimidazolium bromide ([Bmim] Br) was used to catalyze the CO₂ cycloaddition reaction in a batch reactor. The effect of reaction conditions on the kinetic performance of synthesizing propylene carbonate (PC) was studied. Secondly, a supported polyelectrolyte liquid membrane was designed and prepared, and a continuous ionic liquid membrane reactor was established for the continuous catalytic reaction of CO₂ and epichlorohydrin (PO). The performance of the continuous catalytic reaction was studied and compared with batch reaction experiments. Based on the results of kinetic experiments, the reaction order of the reaction rate equation and the activation energy in the reaction system were determined. Finally, under the premise of achieving high PC yield goals and optimizing process conditions, a dual zone dynamic modeling was conducted on the batch reactor to guide the comprehensive evaluation of technology, economy, and environment under uncertain conditions, laying the foundation for the pilot scale clean production of high-value chemicals synthesized by chemical conversion of CO₂.

一直以来，通过二氧化碳（CO2）与环氧化物的环加成反应合成环状碳酸盐，再与甲醇进行酯交换生成线性碳酸盐，是锂离子电池的重要溶剂，也是二氧化碳资源利用的有效途径之一。本研究从过程系统工程的角度分析了离子液体作为二氧化碳转化催化剂的动力学和反应器技术选择。首先，以乙醇（EtOH）为溶剂，在间歇反应器中使用 1-丁基-3-甲基溴化咪唑鎓（[Bmim] Br）催化 CO2 环加成反应。研究了反应条件对合成碳酸丙烯酯（PC）动力学性能的影响。其次，设计并制备了支撑型聚电解质液体膜，建立了连续离子液体膜反应器，用于 CO2 与环氧氯丙烷（PO）的连续催化反应。研究了连续催化反应的性能，并与间歇反应实验进行了比较。根据动力学实验结果，确定了反应速率方程的反应阶次和反应体系中的活化能。最后，在实现 PC 高收率目标和优化工艺条件的前提下，对间歇反应器进行了双区动态建模，指导不确定条件下的技术、经济和环境综合评价，为二氧化碳化学转化合成高值化学品的中试规模清洁生产奠定了基础。

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引用次数: 0

Preparation and characterization of a new nanocomposite, Genista Scorpius fibers/Poly (diallyldimethylammonium chloride)/zero valent silver: Application to the catalytic reduction of hazardous azo dyes in water 新型纳米复合材料 Genista Scorpius 纤维/聚（二烯丙基二甲基氯化铵）/零价银的制备与表征：应用于催化还原水中的有害偶氮染料

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2024-11-01 DOI: 10.1016/j.molstruc.2024.140573

Raoudha Soury , Mahjoub Jabli , Ahmed Al Otaibi , Sahar Y. Rajeh

Biomass residues constitute a source of polymeric fibers, chemicals, biofuels, nanocomposites, etc. Their versatile physico-chemical characteristics and their aptitude to be chemically functionalized justify their employment in several domains. In the present study, Genista Scorpius fibers were used as a starting cellulosic substrate, functionalized with Poly (diallyldimethylammonium chloride), and zero valent silver nanoparticles. Several analytical methods including, SEM, FTIR, XRD, and TGA/DTG were used to analyze the chemical composition, morphological features, crystallinity, and thermal behavior of the studied samples. SEM analysis displayed the wide dispersion of the zero valent silver nanoparticles onto Genista surface. The XRD peaks observed at 2 thetas = 30.8°, 38.5°, and 44.2° confirmed the presence of zero valent silver nanoparticles onto the functionalized fibers surface. Highest residual masses were observed for the functionalized Genista fibers (46.46 %-50.04 %) compared to virgin fibers (17.37 %). The nanocomposites were more thermally stable than the virgin material. The nanocomposites were further investigated, as catalysts, for the catalytic reduction of Eriochrome Black T and Naphthol blue black B in aqueous suspension using sodium borohydride (NaBH₄) as a reducing agent. Several experimental conditions influencing the catalytic reduction including NaBH₄ concentration, initial dyes concentrations, time of reaction, and bath temperature were discussed. Eriochrome and Naphthol solutions were completely decolorized under the following optimum conditions: time = 8 min, pH = 6, NaBH₄ =1 M, C₀ = 40 mg/L, and T = 50 °C. The catalytic degradation of the azo dye solutions was analyzed using, zero-, first- and second-order reaction kinetics. The calculated activation energies were equal to 58.53 kj mol⁻¹ and 57.47 kj mol⁻¹ for Eriochrome and Naphthol solutions, respectively. These small values confirmed the efficiency of the use of the prepared nanocomposites in water purification.

生物质残渣是聚合纤维、化学品、生物燃料、纳米复合材料等的来源。它们多变的物理化学特性和化学功能化的能力为其在多个领域的应用提供了理由。在本研究中，Genista Scorpius 纤维被用作起始纤维素基质，并用聚（二烯丙基二甲基氯化铵）和零价银纳米粒子进行功能化。研究人员采用了多种分析方法，包括扫描电子显微镜、傅立叶变换红外光谱、X 射线衍射和 TGA/DTG 分析所研究样品的化学成分、形态特征、结晶度和热行为。扫描电镜分析表明，零价银纳米粒子广泛分散在 Genista 表面。在 2 thetas = 30.8°、38.5° 和 44.2°处观察到的 XRD 峰证实了功能化纤维表面存在零价纳米银颗粒。与原始纤维（17.37%）相比，功能化 Genista 纤维的残余质量最高（46.46%-50.04%）。纳米复合材料的热稳定性优于原始材料。研究人员进一步研究了纳米复合材料作为催化剂，使用硼氢化钠（NaBH4）作为还原剂，在水悬浮液中催化还原铬黑 T 和萘酚蓝黑 B 的情况。讨论了影响催化还原的几个实验条件，包括 NaBH4 浓度、初始染料浓度、反应时间和水浴温度。在以下最佳条件下，曙红和萘酚溶液完全脱色：时间 = 8 分钟，pH = 6，NaBH4 = 1 M，C0 = 40 mg/L，T = 50 °C。使用零阶、一阶和二阶反应动力学分析了偶氮染料溶液的催化降解。计算得出的胭脂红和萘酚溶液的活化能分别为 58.53 kj mol-1 和 57.47 kj mol-1。这些小数值证实了所制备的纳米复合材料在水净化中的使用效率。

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引用次数: 0

Synthesis, structure, spectral and Hirshfeld surface analysis of bis((pyridin-1-ium-4-yl)methanaminium) hexahalostannate(IV) dihalide 双((吡啶-1-鎓-4-基)甲铵)六卤代锡烷酸(IV)二卤化物的合成、结构、光谱和希尔施菲尔德表面分析

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2024-10-31 DOI: 10.1016/j.molstruc.2024.140546

P.K. Kodamboev , I.I. Abdullaev , A.B. Ibragimov , Y.Y. Yakubov , N. Vijayan , C. Balakrishnan

Single crystals of the newly synthesized organic-inorganic hybrid salts, namely bis((pyridin-1-ium-4-yl)methanaminium) hexachlorostannate(IV) dichloride (1) and bis((pyridin-1-ium-4-yl)methanaminium) hexabromostannate(IV) dibromide (2), were successfully grown and subsequently subjected to detailed characterization using single-crystal X-ray diffraction analysis. The experimental XRD patterns exhibit sharp and high-intensity peaks, attesting to the high crystallinity and structural integrity of the synthesized compounds. The band gaps of the hybrid materials can be effectively tuned by altering the halide ion, as evidenced by the different band gaps of 4.21 eV for compound (1) and 2.93 eV for compound (2). Photoluminescence investigations reveal that both compounds emit fluorescence in the solid state at room temperature. Additionally, bond valence sum calculations have verified that tin possesses a formal oxidation state of +4. Examination of intermolecular interactions and crystal packing through Hirshfeld surface analysis.

新合成的有机-无机杂化盐，即双((吡啶-1-ium-4-yl)甲铵)六氯锡酸(IV)二氯化物(1)和双((吡啶-1-ium-4-yl)甲铵)六溴锡酸(IV)二溴化物(2)的单晶成功生长，随后利用单晶 X 射线衍射分析进行了详细表征。实验 X 射线衍射图显示出尖锐和高强度的峰值，证明了合成化合物的高结晶度和结构完整性。化合物（1）的带隙为 4.21 eV，化合物（2）的带隙为 2.93 eV。光致发光研究表明，这两种化合物在室温下的固态中都会发出荧光。此外，键价和计算还验证了锡的形式氧化态为 +4。通过 Hirshfeld 表面分析研究了分子间的相互作用和晶体堆积。

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引用次数: 0

Development of colorimetric probe using robust zinc-MOF and its consistent melamine sponge composite: Instantaneous N3–, La3+ sensing and degradation applications 利用坚固的锌-MOF 及其一致的三聚氰胺海绵复合材料开发比色探针：瞬时 N3-、La3+ 传感和降解应用

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2024-10-31 DOI: 10.1016/j.molstruc.2024.140560

Vibhav Shukla , Nazrul Haq , Kafeel Ahmad Siddiqui

The crystalline sponge method (CSM), which involves soaking a target molecule into a crystalline metal-organic framework (MOF), offers a promising approach by eliminating the need for high-quality single crystals of the target compound. To broaden the scope of compounds that can be analyzed using CSM, it is essential to investigate various MOFs. In this study, we focused on evaluating the potential of a zinc-based MOF, specifically [Zn₃(Cei)₂((Bimb)₃] (Zinc-MOF), as a CSM host. We successfully synthesized and thoroughly characterized Zinc-MOF. Additionally, we developed a Zinc-MOF@melamine sponge (Zinc-MOF@MS) composite, which exhibited significant photocatalytic activity by degrading hazardous organic dyes such as Rose Bengal (RB) and Crystal Violet (CV), achieving degradation efficiencies of 98.95 % and 92.51 %, respectively, after 120 min of exposure to visible sunlight. The luminescent properties of the Zinc-MOF were also explored, demonstrating strong luminescent emission and excellent chemical stability. Furthermore, Zinc-MOF showed remarkable sensing capabilities, selectively detecting La³⁺ cations and N₃⁻ anions in aqueous solutions through luminescence quenching.

结晶海绵法（CSM）是一种将目标分子浸泡到结晶金属有机框架（MOF）中的方法，无需目标化合物的高质量单晶体，是一种很有前途的方法。为了扩大可使用 CSM 分析的化合物范围，有必要研究各种 MOF。在本研究中，我们重点评估了锌基 MOF（特别是 [Zn3(Cei)2((Bimb)3]（Zinc-MOF））作为 CSM 宿主的潜力。我们成功合成了 Zinc-MOF，并对其进行了全面表征。此外，我们还开发了一种 Zinc-MOF@melamine sponge（Zinc-MOF@MS）复合材料，它在降解玫瑰红（RB）和水晶紫（CV）等有害有机染料方面表现出显著的光催化活性，在可见光下暴露 120 分钟后，降解效率分别达到 98.95 % 和 92.51 %。此外，还对锌-MOF 的发光特性进行了研究，结果表明，锌-MOF 具有强烈的发光发射和出色的化学稳定性。此外，Zinc-MOF 还显示出卓越的传感能力，它能通过发光淬灭选择性地检测水溶液中的 La³⁺ 阳离子和 N₃- 阴离子。

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引用次数: 0

Versatile biological activities of thiosemicarbazones and their metal complexes 硫代氨基甲酸盐及其金属配合物的多种生物活性

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2024-10-31 DOI: 10.1016/j.molstruc.2024.140511

Syeda Bakhtawar Zahra , Ajmal Khan , Nadeem Ahmed , Maham Rafique , Lamia Fatima , Imtiaz Khan , Javid Hussain , Sana Khalid , Hanan A. Ogaly , Mesaik M. Ahmed , Ahmed Al-Harrasi , Zahid Shafiq

One of the most crucial objectives in medicinal chemistry is the development of innovative and beneficial bioactive compounds with various biological activities. Thiosemicarbazone, which serves as a valuable precursor in synthesizing pharmaceutical compounds also acts as a chelating agent and forms complexes with transition metals. They demonstrate remarkable medicinal properties and seem advantageous in terms of generating less toxic and more potent medications. These complexes possess a broad range of biological activities, including antimicrobial, antiviral, anticancer, and antioxidant, and are used as enzyme inhibitory agents. This review summarizes recent works providing detailed information on the synthesis, characterization, and biological evaluation of several thiosemicarbazones and their metal complexes. Examining various metal complexes with distinct medicinal properties and structural characteristics this review aims to understand the diverse biological potential for therapeutic applications. This work aims to illuminate the potential of these compounds in pioneering innovative treatment modalities across diverse domains by developing knowledge about the structural characteristics that determine their various biological effects. The literature cited in this review covers a comprehensive period of research and development on thiosemicarbazones and their metal complexes, spanning a period of 17 years from 2006 to 2023, reflecting the evolution and current state of research in this field.

药物化学最重要的目标之一是开发具有各种生物活性的创新型有益生物活性化合物。硫代氨基脲是合成药物化合物的重要前体，也可作为螯合剂与过渡金属形成络合物。它们具有卓越的药用特性，在生成毒性更低、药效更强的药物方面似乎更具优势。这些复合物具有广泛的生物活性，包括抗菌、抗病毒、抗癌和抗氧化，并可用作酶抑制剂。本综述总结了近期的研究成果，详细介绍了几种硫代氨基甲酸盐及其金属配合物的合成、表征和生物学评价。本综述研究了具有不同药用特性和结构特征的各种金属配合物，旨在了解其在治疗应用方面的各种生物潜力。这项工作旨在通过了解决定其各种生物效应的结构特征，阐明这些化合物在不同领域开拓创新治疗模式的潜力。本综述引用的文献涵盖了从 2006 年到 2023 年这 17 年间有关硫代氨基甲酸及其金属复合物的全面研究和开发，反映了该领域研究的演变和现状。

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引用次数: 0

Synthesis and characterization of silica-supported cobalt acylpyrazolone complex and its catalytic performance in ethylbenzene oxidation 二氧化硅支撑的酰基吡唑酮钴络合物的合成和表征及其在乙苯氧化中的催化性能

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2024-10-31 DOI: 10.1016/j.molstruc.2024.140513

Grishma Vala , Rajendrasinh N. Jadeja , Aditya A. Puranik , Ray J. Butcher

A novel β-diketone-containing acylpyrazolone (2-(3-chlorophenyl)-3‑hydroxy-5-methyl-2,3-dihydro-1H-pyrazole-4-yl) (4-nitrophenyl) methanone [HL^C] ligand and its cobalt complex [Co(HL^C)₂(H₂O)₂] were synthesized and characterized. A silica-supported cobalt complex was synthesized as a heterogeneous catalyst to investigate the cobalt complex's catalytic activity. The characterization techniques used for the synthesized compounds are CHN analysis, SC-XRD, FT-IR, TGA, DRS spectra, BET and BJH measurements, ICP-MS, XPS, powder XRD and SEM. Without any solvent, the cobalt complex catalytic impact on the oxidation of ethylbenzene was investigated with tert‑butyl hydroperoxide (70 % TBHP) as an oxidant. The catalyst exhibited good conversion (88 % conversion) and selectivity (83 % acetophenone) in the oxidation of ethylbenzene. The catalyst shows no leaching occurred under the reaction conditions because it is stable and reusable for further reaction.

合成并表征了一种新的含β-二酮酰基吡唑酮（2-(3-氯苯基)-3-羟基-5-甲基-2,3-二氢-1H-吡唑-4-基）（4-硝基苯基）甲酮[HLC]配体及其钴络合物[Co(HLC)2(H2O)2]。为了研究钴络合物的催化活性，还合成了一种二氧化硅支撑的钴络合物作为异相催化剂。合成化合物的表征技术包括 CHN 分析、SC-XRD、FT-IR、TGA、DRS 光谱、BET 和 BJH 测量、ICP-MS、XPS、粉末 XRD 和 SEM。在不使用任何溶剂的情况下，以叔丁基过氧化氢（70% TBHP）为氧化剂，研究了钴络合物对乙苯氧化的催化作用。催化剂在乙苯氧化过程中表现出良好的转化率（88% 转化率）和选择性（83% 苯乙酮）。该催化剂在反应条件下没有发生浸出现象，因为它很稳定，可重复用于进一步反应。

引用次数: 0

Enhanced phase transition temperature achieved by CH3/H substitution in Sn-based perovskite 通过 CH3/H 取代提高锡基过氧化物的相变温度

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2024-10-31 DOI: 10.1016/j.molstruc.2024.140535

Yinan Zhang , Zhuoer Cai , Jian Chen , Xiu-Ni Hua , Baiwang Sun

Organic-inorganic hybrid phase transition materials have garnered significant attention due to their excellent properties and broad applications in energy storage, temperature control switches, and optoelectronic devices. The regulation of the phase transition temperature (T_c) is necessary as it determines the properties and applications of materials. (TMTBA)₂SnBr₆ (1) (TMTBA = N,N,N-trimethyl‑tert-butylammonium) was synthesized, featuring the T_c around 225 K and then (DMTBA)₂SnBr₆ (2) (DMTBA = N,N-dimethyl‑tert-butylaminium) was obtained. Progressively, the 2 exhibited a great enhancement of T_c at 404 K, with a ΔT_c reaching up to 179 K. Single-crystal structure analysis confirmed that 1 underwent isomorphic phase transitions, with the space groups of Pnma. In contrast, 2 underwent an order-disorder phase transition, and the space group changed from the low-temperature phase of I2/c to high-temperature phase of

R \bar{3}

. What's more, the semiconductor properties and optical band gap of the materials were also investigated, 2.59 eV for 1 and 2.65 eV for 2. It is believed that this work can enrich the field of phase transition materials and provide some guidance for the regulation of T_c.

有机-无机杂化相变材料因其优异的性能以及在能量储存、温度控制开关和光电设备方面的广泛应用而备受关注。相变温度（Tc）的调节非常必要，因为它决定了材料的性能和应用。(TMTBA)2SnBr6 (1)（TMTBA = N,N,N-三甲基叔丁基铵）被合成出来，其相变温度约为 225 K，然后得到了 (DMTBA)2SnBr6 (2)（DMTBA = N,N-二甲基叔丁基铵）。单晶结构分析证实，1 发生了同构相变，空间群为 Pnma。相反，2 发生了有序-无序相变，空间群从 I2/c 的低温相变为 R3¯ 的高温相。此外，还研究了材料的半导体性质和光带隙，1 为 2.59 eV，2 为 2.65 eV。相信这项工作能丰富相变材料领域的研究，并为调控 Tc 提供一些指导。

{"title":"Enhanced phase transition temperature achieved by CH3/H substitution in Sn-based perovskite","authors":"Yinan Zhang , Zhuoer Cai , Jian Chen , Xiu-Ni Hua , Baiwang Sun","doi":"10.1016/j.molstruc.2024.140535","DOIUrl":"10.1016/j.molstruc.2024.140535","url":null,"abstract":"<div><div>Organic-inorganic hybrid phase transition materials have garnered significant attention due to their excellent properties and broad applications in energy storage, temperature control switches, and optoelectronic devices. The regulation of the phase transition temperature (T<sub>c</sub>) is necessary as it determines the properties and applications of materials. (TMTBA)<sub>2</sub>SnBr<sub>6</sub> (<strong>1</strong>) (TMTBA = <em>N,N,N</em>-trimethyl‑tert-butylammonium) was synthesized, featuring the T<sub>c</sub> around 225 K and then (DMTBA)<sub>2</sub>SnBr<sub>6</sub> (<strong>2</strong>) (DMTBA = <em>N,N</em>-dimethyl‑<em>tert</em>-butylaminium) was obtained. Progressively, the <strong>2</strong> exhibited a great enhancement of T<sub>c</sub> at 404 K, with a ΔT<sub>c</sub> reaching up to 179 K. Single-crystal structure analysis confirmed that <strong>1</strong> underwent isomorphic phase transitions, with the space groups of <em>Pnma</em>. In contrast, <strong>2</strong> underwent an order-disorder phase transition, and the space group changed from the low-temperature phase of <em>I</em>2/<em>c</em> to high-temperature phase of <span><math><mrow><mi>R</mi><mover><mn>3</mn><mo>¯</mo></mover></mrow></math></span>. What's more, the semiconductor properties and optical band gap of the materials were also investigated, 2.59 eV for <strong>1</strong> and 2.65 eV for <strong>2</strong>. It is believed that this work can enrich the field of phase transition materials and provide some guidance for the regulation of T<sub>c</sub>.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1322 ","pages":"Article 140535"},"PeriodicalIF":4.0,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142659670","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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