Polyhedron最新文献_第2页

Polyoxometalates ionic liquids based magnetic nanocomposites as an efficient heterogeneous catalysts for oxidation of thiobenzoic acid and dibenzothiophene by employing RP-HPLC-UV 利用 RP-HPLC-UV 将基于聚氧化金属离子液体的磁性纳米复合材料作为氧化硫代苯甲酸和二苯并噻吩的高效异相催化剂

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-11-16 DOI: 10.1016/j.poly.2024.117311

Roman Jaffar , Najla AlMasoud , Khurram Shahzad Munawar , Sana Rauf , Taghrid S. Alomar , Hafiz Muhammad Asif , Zeinhom M. El-Bahy , Hameed Ullah , Saifullah

Sulfur compounds need to be effectively rejected from fuel to maintain a clean environment. The removal of sulfur compounds from thiocompounds has received increased attention due to the negative environmental and industrial consequences of sulfur emissions. We examine the effectiveness of polyoxometalate (POM) ionic liquid-based nanocomposites as catalysts for the oxidative desulfurization of thiobenzoic acid and other sulfur-containing chemicals. Na-POMIL@NCP and Cr-POMIL@NCP were synthesized and thoroughly characterized using a variety of analytical techniques, including Fourier-transform infrared spectroscopy (FT-IR), UV–visible spectroscopy, powder X-ray diffraction (P-XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), fluorescence spectroscopy, and vibrating sample magnetometer (VSM). POMIL-based nanocomposites with Fe₃O₄@SiO₂ exhibit both catalytic activity and adsorption capability. To evaluate sulfur removal efficiency and investigate the transformation paths of the thio compounds, high-performance liquid chromatography (HPLC) was performed at 33 °C using a C18 column with an acetonitrile–water mobile phase (1:1 ratio). The catalytic conversion of thiobenzoic acid and dibenzothiophene occurs at temperature, oxidant O/S ratio and catalyst concentration were investigated to determine the best catalyst for a given process. Under moderate conditions, this work proposes a cost-effective and ecologically acceptable approach for thiobenzoic acid (TB) and dibenzothiophene (DBT) production employing H₂O₂ as an oxidant and Na-POMIL@NCP and Cr-POMIL@NCP as heterogeneous catalysts. They are highly effective for oxidizing sulfur compounds included in diesel to lower the sulfur levels of fuel. This study provides to the development of innovative materials for ecologically friendly sulfur removal applications.

为了保持环境清洁，需要有效地去除燃料中的硫化合物。由于硫排放对环境和工业造成的负面影响，从硫代化合物中去除硫化合物的研究受到越来越多的关注。我们研究了聚氧化金属（POM）离子液体基纳米复合材料作为催化剂对硫代苯甲酸和其他含硫化学品进行氧化脱硫的有效性。研究人员合成了 Na-POMIL@NCP 和 Cr-POMIL@NCP，并使用多种分析技术对其进行了全面表征，包括傅立叶变换红外光谱（FT-IR）、紫外-可见光谱、粉末 X 射线衍射（P-XRD）、扫描电子显微镜（SEM）、粉末 X 射线衍射（P-XRD）和傅立叶变换红外光谱（FT-IR）、扫描电子显微镜 (SEM)、能量色散 X 射线光谱仪 (EDX)、热重分析 (TGA)、差示扫描量热仪 (DSC)、荧光光谱仪和振动样品磁力计 (VSM)。基于 POMIL 的 Fe3O4@SiO2 纳米复合材料同时具有催化活性和吸附能力。为了评估硫的去除效率并研究硫代化合物的转化路径，在 33 °C下使用C18色谱柱和乙腈-水流动相（1:1）进行了高效液相色谱分析。研究了硫代苯甲酸和二苯并噻吩的催化转化温度、氧化剂 O/S 比率和催化剂浓度，以确定特定工艺的最佳催化剂。在中等条件下，本研究提出了一种具有成本效益且生态上可接受的硫代苯甲酸（TB）和二苯并噻吩（DBT）生产方法，该方法采用 H2O2 作为氧化剂，Na-POMIL@NCP 和 Cr-POMIL@NCP 作为异相催化剂。它们对氧化柴油中的硫化合物以降低燃料中的硫含量非常有效。这项研究为开发生态友好型脱硫应用的创新材料提供了思路。

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引用次数: 0

New complexes of [5,10,15,20-(tetraphenylporphyrin)] and dichloride (5,10,15,20-tetraphenylporphyrinato) antimony(V) hexachloridoantimonate(V) functionalized with polyethyleneimine: Synthesis, characterization, and application in Eriochrome Black T adsorption from water 聚乙烯亚胺官能化的[5,10,15,20-（四苯基卟啉）]和二氯化（5,10,15,20-四苯基卟啉）锑（V）六氯锑酸（V）新配合物：合成、表征及在 Eriochrome Black T 水吸附中的应用

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-11-16 DOI: 10.1016/j.poly.2024.117305

Raoudha Soury , Mahjoub Jabli , Mabrouka El Oudi , Khalaf M. Alenezi , Ahmed Al Otaibi , Fahad Abdulaziz , Hind A. AlGhamdi , Amor Bchetnia

In the current work, new complexes namely [5,10,15,20 (tetraphenylporphyrin)] /Polyethyleneimine (H₂TPP-PEI) and Dichlorido(5,10,15,20-tetraphenylporphyrinato)antimony(V) hexachloridoantimonate(V)/Polyethyleneimine ([Sb(TPP)Cl₂][SbCl₆]-PEI) were successfully prepared and characterized. The prepared compounds were thoroughly analysed using ¹H NMR, UV, XRD, XRF, TGA-DTA, SEM, and EDAX. SEM analysis showed that the addition of polyethyleneimine to the porphyrin core clearly changed the morphological properties. The optical gap values were calculated using the tauc plot method and were equal to 1.877, 2.030, 1.862, and 2.017 eV for H₂TPP, [Sb(TPP)Cl₂] [SbCl₆], H₂TPP-PEI and ([Sb(TPP)Cl₂][SbCl₆]-PEI), respectively. The existence of sharp peaks at 2θ between 16° and 80° displayed the crystalline nature of the prepared porphyrinic compounds. The change in thermal decompositions for H₂TPP, [Sb(TPP)Cl₂][SbCl₆], H₂TPP-PEI and ([Sb(TPP)Cl₂][SbCl₆]-PEI) revealed that the addition of polyethyleneimine to porphyrin affected the thermal characteristics. The prepared complexes were, further, investigated for the adsorption of Eriochrome Black T (an anionic dye) from water. Highest adsorption capacities were accomplished using [Sb(TPP)(Cl₂)]-PEI (164 mg/g) and H₂TPP-PEI (82 mg/g) under the following experimental conditions (pH = 5, temperature = 19 °C, time = 60 min). However, the adsorption capacities remains poor for H₂TPP and Sn(TPP)(Cl₂). The adsorption data complied well with pseudo second order, Freundlich, and Temkin equations. Overall, the adsorption results had confirmed that polyethyleneimine functionalized porphyrins could be used as a proficient adsorbent of anionic dyes from water.

本研究成功制备了[5,10,15,20（四苯基卟啉）]/聚乙烯亚胺（H2TPP-PEI）和二氯（5,10,15,20-四苯基卟啉）锑（V）六氯锑酸（V）/聚乙烯亚胺（[Sb(TPP)Cl2][SbCl6]-PEI）新配合物，并对其进行了表征。使用 1H NMR、UV、XRD、XRF、TGA-DTA、SEM 和 EDAX 对制备的化合物进行了全面分析。扫描电镜分析表明，在卟啉核心中添加聚乙烯亚胺明显改变了其形态特性。通过陶氏图法计算得出，H2TPP、[Sb(TPP)Cl2] [SbCl6]、H2TPP-PEI 和 ([Sb(TPP)Cl2][SbCl6]-PEI) 的光隙值分别为 1.877、2.030、1.862 和 2.017 eV。在 16° 和 80° 之间的 2θ 处存在尖锐的峰值，这表明所制备的卟啉化合物具有结晶性质。H2TPP、[Sb(TPP)Cl2][SbCl6]、H2TPP-PEI 和（[Sb(TPP)Cl2][SbCl6]-PEI）的热分解变化表明，在卟啉中加入聚乙烯亚胺会影响热特性。研究人员还进一步研究了制备的复合物对水中 Eriochrome Black T（一种阴离子染料）的吸附能力。在以下实验条件下（pH = 5、温度 = 19 °C、时间 = 60 分钟），[Sb(TPP)(Cl2)]-PEI（164 毫克/克）和 H2TPP-PEI（82 毫克/克）的吸附容量最高。然而，H2TPP 和 Sn(TPP)(Cl2) 的吸附容量仍然很低。吸附数据完全符合伪二阶、Freundlich 和 Temkin 方程。总之，吸附结果证实了聚乙烯亚胺官能化卟啉可用作水中阴离子染料的有效吸附剂。

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引用次数: 0

Synthesis of tetraphenylphosphonium/polysulfide hybrids and their temperature-induced switchable WORM/flash electrical memory behavior 四苯基膦/多硫化物混合物的合成及其温度诱导的可切换 WORM/flash 电存储器行为

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-11-15 DOI: 10.1016/j.poly.2024.117301

Zhaoxun Lian, Ning Zhao

The development of innovative non-volatile storage materials is essential for the progression of next-generation high-performance storage devices. In this study, a hybrid material (Ph₄P)₂S₇ was synthesized, and single crystal structure analysis demonstrated that the organic tetraphenylphosphonium cation (Ph)₄P⁺ adopts a regular tetrahedral conformation and forms one-dimensional chains through CH···π interactions. The (S₇)^2- anion, characterized by quasi-bicentric symmetry and a right-handed helical cluster, is confined within the one-dimensional quantum well established by the (Ph)₄P⁺ cation chain in the organic matrix. A device composed of FTO/(Ph₄P)₂S₇/Ag was fabricated through spin-coating, demonstrating remarkable temperature-induced switchable binary write-once-read-many-times (WORM)/Flash electrical memory behavior. At room temperature, the material demonstrated nonvolatile binary WORM-type resistance switching behavior with a switching ratio of 1.95 × 10³ and an onset voltage of 1.01 V. Conversely, at 150 °C, it transits into binary Flash-type resistance switching behavior characterized by current ratio of 3.34 × 10² and onset/reset voltages of 1.05/−1.99 V. The mechanism underlying binary resistive switching is identified as spatial charge-limited charge capture. Furthermore, the observed reversible transition between WORM- and Flash- type electrical memory behavior at elevated temperatures can be attributed to lattice expansion of the (Ph)₄P⁺ cations at high temperatures, resulting in denser packing of organic molecules and deeper trapping potential wells for electrons within the active layer. This study provides theoretical insights into developing novel high-performance information storage materials.

创新型非易失性存储材料的开发对于下一代高性能存储设备的发展至关重要。本研究合成了一种混合材料 (Ph4P)2S7，单晶结构分析表明有机四苯基鏻阳离子 (Ph)4P+ 采用规则的四面体构象，并通过 CH---π 相互作用形成一维链。(S7)2- 阴离子具有准双心对称性和右手螺旋簇的特点，被限制在有机基质中由 (Ph)4P+ 阳离子链建立的一维量子阱内。通过旋涂技术制造出了一种由 FTO/(Ph4P)2S7/Ag 组成的器件，该器件在温度诱导下具有显著的可切换二元写入-一次读取-多次写入（WORM）/闪存电记忆行为。在室温下，该材料表现出非易失性二进制 WORM 型电阻开关行为，开关比为 1.95 × 103，起始电压为 1.01 V。反之，在 150 ℃ 时，它过渡到二进制闪存型电阻开关行为，电流比为 3.34 × 102，起始/复位电压为 1.05/-1.99 V。此外，在高温下观察到的 WORM 型和闪存型电子存储器行为之间的可逆转换可归因于 (Ph)4P+ 阳离子在高温下的晶格膨胀，从而导致有机分子堆积更密集，活性层内的电子捕获势阱更深。这项研究为开发新型高性能信息存储材料提供了理论依据。

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引用次数: 0

Sensitivity of pure and Ni-decorated boron nitride B12N12 nanocages toward CH4, H2S, and N2 biogases: A DFT study 纯氮化硼和镍装饰的 B12N12 纳米笼对 CH4、H2S 和 N2 生物气体的敏感性：DFT 研究

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-11-14 DOI: 10.1016/j.poly.2024.117302

Tamer H.A. Hasanin , Manar H.A. Hamad , Nayra A.M. Moussa , Asmaa M.M. Mahmoud , Mohamed Y. El-Sayed , Al-shimaa S.M. Rady , Mahmoud A.A. Ibrahim

The sensitivity of pure and Ni-decorated boron nitride (B₁₂N₁₂) nanocages toward CH₄, H₂S, and N₂ biogases was adequately unveiled by employing versatile density functional theory (DFT) calculations. In this regard, the Gas∙∙∙B₁₂N₁₂ and ∙∙∙Ni@B₁₂N₁₂ complexes were studied within all possible configurations. Based on the energetic quantities, the Ni@B₁₂N₁₂ nanocage exhibited higher sensitivity than the pure one toward the investigated gases. Among all studied complexes, the H₂S∙∙∙Ni@B₁₂N₁₂ complex exhibited the most favorable adsorption (E_ads) and interaction (E_int) energies with values of –29.25 and –29.46 kcal/mol, respectively. According to the outlines of the quantum theory of atoms in molecules (QTAIM) and noncovalent interaction (NCI) index analyses, the closed-shell nature of the interactions within the investigated complexes was ensured. Substantial alterations in the molecular orbitals distribution patterns of pure and Ni-decorated B₁₂N₁₂ nanocages were observed, announcing the occurrence of the adsorption process within the investigated complexes. The obtained negative values of thermodynamic parameters ensured the spontaneous exothermic nature of the investigated Ni-decorated complexes. Upon density of states (DOS) analysis, the influence of adsorbed gases on the electronic characteristics of the pure and Ni-decorated B₁₂N₁₂ nanocages was highlighted. According to the emerging findings, the pure and Ni-decorated B₁₂N₁₂ nanocages are promising sensing materials for biogas components, especially CH₄, H₂S, and N₂ gases.

通过采用多功能密度泛函理论（DFT）计算，充分揭示了纯氮化硼（B12N12）纳米笼和镍装饰氮化硼（B12N12）纳米笼对 CH4、H2S 和 N2 生物气体的敏感性。在这方面，研究了所有可能构型中的 Gas∙∙∙B12N12 和 ∙∙∙Ni@B12N12 复合物。根据能量量，Ni@B12N12 纳米笼对所研究气体的灵敏度高于纯纳米笼。在所有研究的复合物中，H2S∙∙∙Ni@B12N12 复合物的吸附能（Eads）和相互作用能（Eint）最高，分别为 -29.25 和 -29.46 kcal/mol。根据分子中原子的量子理论（QTAIM）和非共价相互作用（NCI）指数分析，所研究复合物内部的相互作用具有闭壳性质。观察到纯 B12N12 纳米络合物和镍装饰 B12N12 纳米络合物的分子轨道分布模式发生了重大变化，这表明在所研究的络合物中存在吸附过程。所获得的热力学参数负值确保了所研究的镍装饰复合物具有自发放热的性质。通过状态密度（DOS）分析，吸附气体对纯 B12N12 纳米笼和镍装饰纳米笼电子特性的影响得到了强调。根据新的研究结果，纯的和镍装饰的 B12N12 纳米笼是很有前途的生物气体成分（尤其是 CH4、H2S 和 N2 气体）传感材料。

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引用次数: 0

Self-assembly of tetra nuclear lanthanide (Pr, Nd) hydroxo clusters with functionalized β-diketone: Experimental and theoretical studies 四核镧系元素（镨、钕）羟基团簇与官能化β-二酮的自组装：实验和理论研究

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-11-14 DOI: 10.1016/j.poly.2024.117306

Ananda Kumar Jami , Pilli V.V.N. Kishore , Venkatesan Srinivasadesikan , Bharat Kumar Tripuramallu , Maddina Sreenivasa Rao

Reaction of LnCl₃·6H₂O (Ln = Pr, Nd) with functionalized β-Diketone {ortho-hydroxydibenzoylmethane (HO-DBM)} in 1:2 ratio in methanol and in presence of triethylamine (excess) as base yielded two tetra nuclear lanthanide hydroxo clusters of composition [Ln₄(O-DBM)₄(HO-DBM)₄(µ₃-OH)₂][Et₃NH]₂.3CH₂Cl₂, (Ln = Pr (1), Nd (2)). The clusters 1 and 2 has been structurally characterized by single crystal X-ray diffraction. A one-dimensional supramolecular chain is observed in the solid state structure (2), where dichloromethane solvent molecules are linked to the phenyl rings of adjacent diketone linkers through CH⋯π and Cl⋯π interactions. Theoretical studies support the stability of structure (2), with calculated geometric parameters aligning with experimental findings.

LnCl3-6H2O（Ln = Pr、Nd）与功能化β-二酮{正羟基二苯甲酰基甲烷（HO-DBM）}以 1:2 的比例在甲醇中并在三乙胺（过量）作为碱存在的情况下反应，生成了两个四核镧系氢氧簇，其组成为[Ln4(O-DBM)4(HO-DBM)4(µ3-OH)2][Et3NH]2。3CH2Cl2，（Ln = Pr (1)，Nd (2)）。通过单晶 X 射线衍射，对团簇 1 和 2 进行了结构表征。在固态结构 (2) 中观察到一条一维超分子链，其中二氯甲烷溶剂分子通过 CH⋯π 和 Cl⋯π 相互作用连接到相邻二酮连接体的苯基环上。理论研究支持结构 (2) 的稳定性，计算得出的几何参数与实验结果一致。

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引用次数: 0

A simple and highly selective chalcone fluorescent chemical sensor for the detection of tryptophane 用于检测色氨酸的简单、高选择性查尔酮荧光化学传感器

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-11-13 DOI: 10.1016/j.poly.2024.117303

Yuting Liu , Zixu Zhang , Dawei Yin , Yukai Huang , Ying Liu , Jinze Li , Ruilin Zheng

In this study, 1-ferrocenyl-3-(2-hydroxyphenyl) allyl ketone (probe A) was synthesized using a solvent-free method in conjunction with solid-phase grinding and employed as a probe for the detection of tryptophan (Trp). The probe exhibits selective recognition of Trp as evidenced by UV–Vis and fluorescence spectra. In complex scenarios, the probe’s recognition of Trp remains unaffected by both the presence of interfering substances and the duration of exposure. A pH range of 8 to 12 is found to be optimal for the detection of Trp. Job’s curve analysis revealed that the binding ratio between the probe and Trp is 1:1. Based on the Benesi-Hildebrand equation, the binding constant for the interaction between probe A and Trp is calculated to be 1.5 × 10⁷ M⁻¹. The detection limit for Trp was determined to be 9.55 × 10⁻⁵ M. The sensing mechanism of the probe for Trp was elucidated through ¹H NMR and FT-IR analyses.

本研究采用固相研磨和无溶剂方法合成了 1-二茂铁基-3-（2-羟基苯基）烯丙基酮（探针 A），并将其用作检测色氨酸（Trp）的探针。紫外可见光谱和荧光光谱证明，该探针对 Trp 具有选择性识别能力。在复杂的情况下，探针对 Trp 的识别不受干扰物质存在和暴露时间长短的影响。检测 Trp 的最佳 pH 值范围为 8 至 12。约伯曲线分析表明，探针与 Trp 的结合率为 1:1。根据 Benesi-Hildebrand 方程计算，探针 A 与 Trp 之间的结合常数为 1.5 × 107 M-1。通过 1H NMR 和 FT-IR 分析，阐明了探针对 Trp 的感应机制。

引用次数: 0

Oxidation of alcohols to carbonyl compounds with H2O2 in water catalyzed by polyoxometalate-based hyper-crosslinked ionic polymer 聚氧化金属基超交联离子聚合物催化水中 H2O2 将醇氧化为羰基化合物

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-11-12 DOI: 10.1016/j.poly.2024.117300

Yuwan Yang , Jianan Yang , Yongjian Qiu , Lin Lei , Songlin Ye , Enqi Xu , Yaju Chen

The oxidation reaction involving hydrogen peroxide (H₂O₂) in water is of great attraction in fundamental research and industrial application, but there is still a long way to go. Herein, a new hybrid catalyst PW@Py-HIP was successfully synthesized by immobilization of phosphotungstic anions onto/into the pyridinium-based hyper-crosslinked ionic polymer using a post-synthetic strategy. This facile synthetic method afforded heterogeneous catalyst with a large specific surface area of 428.7 m²·g⁻¹ and stable polymeric skeleton. The amphiphilic PW@Py-HIP exhibited remarkable catalytic activity and quantitative selectivity for the oxidation of alcohols into carbonyl compounds with H₂O₂ in water. The turnover frequency (TOF) and turnover number (TON) values reached 1088.9 h⁻¹ and 4083.3, respectively. Owing to its good heterogeneous nature, PW@Py-HIP can be recycled for six times without significant loss of activity. The developed catalytic system confirmed to be beneficial toward the synthesis of related carbonyl compounds from various alcohols with appreciable conversions.

过氧化氢（H2O2）在水中的氧化反应在基础研究和工业应用方面具有极大的吸引力，但仍有很长的路要走。本文采用后合成策略，将磷钨酸阴离子固定在吡啶基超交联离子聚合物上/内，成功合成了新型杂化催化剂 PW@Py-HIP。这种简便的合成方法得到了具有 428.7 m2-g-1 大比表面积和稳定聚合物骨架的异相催化剂。两亲性 PW@Py-HIP 在水中用 H2O2 将醇氧化成羰基化合物的过程中表现出显著的催化活性和定量选择性。其翻转频率（TOF）和翻转次数（TON）值分别达到了 1088.9 h-1 和 4083.3。由于具有良好的异质性，PW@Py-HIP 可以循环使用六次而不会明显丧失活性。经证实，所开发的催化系统有利于从各种醇合成相关的羰基化合物，且转化率可观。

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引用次数: 0

Novel conjugated 5-pyridin-2-ylmethylidene 2-thio-4H-imidazol-4-ones and their complexes with copper(II) chloride 新型共轭 5-吡啶-2-基亚甲基 2-硫代-4H-咪唑-4-酮及其与氯化铜（II）的配合物

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-11-09 DOI: 10.1016/j.poly.2024.117295

Anna V. Berezina , Viktor A. Tafeenko , Artem V. Semykin , Anna A. Moiseeva , Xuimei Bai , Alexander V. Finko , Alisa P. Chernyshova , Nikolai V. Zyk , Elena K. Beloglazkina

Three novel 2-thio-4H-imidazol-4-ones containing conjugated five, six- or seven-membered S,N-heterocycle and pyridin-2-ylmethylidene moiety (L) were synthesized by two-step reaction sequence starting from 2-thiohydantion. The ligand structures were confirmed by ¹H NMR, ¹³C NMR and HRMS. The reactions of the ligands L with copper chloride dihydrate give the complexes of LCuCl₂ composition. Copper coordination compounds with 6-(pyridin-2-ylmethylidene)-2,3-dihydroimidazo[2,1-b][1,3]thiazol-5(6H)-one (L1) and 2-(pyridin-2-ylmethylidene)-6,7-dihydro-5H-imidazo[2,1-b][1,3]thiazin-3(2H)-one (L2) were characterized by the X-ray data, demonstrating the distorted tetrahedral copper coordination environment. It was shown that the presence in the ligand L1 of a five-membered thiazolidine ring fused with imidazolone leads to a significant change in the geometric characteristics of the complex: an increase in the Cu-S distance and the flattening of copper coordination polyhedron. Both synthesized complexes were evaluated using cyclic voltammetry and demonstrated the quasi-reversible reduction of Cu(II) at ∼ −0.25 V. Testing of the antibacterial activity on the reporter strains E. coli ΔtolC pDualrep2 (AmpR) and E. coli lptDmut pDualrep2 (KanR) showed a lower activity of the synthesized copper-containing complexes compared to the complexes of similar ligand that did not have an additional condensed ring in its structure.

从 2-硫代氢开始，通过两步反应顺序合成了三种新型 2-硫代-4H-咪唑-4-酮，它们含有共轭的五元、六元或七元 S,N-杂环和吡啶-2-基亚甲基（L）。配体结构通过 1H、13C NMR 和 HRMS 得到确认。配体 L 与二水氯化铜反应生成 LCuCl2 成分的配合物。通过 X 射线数据对 6-(吡啶-2-基亚甲基)-2,3-二氢咪唑并[2,1-b][1,3]噻唑-5(6H)-酮（L1）和 2-(吡啶-2-基亚甲基)-6,7-二氢-5H-咪唑并[2,1-b][1,3]噻嗪-3(2H)-酮（L2）的铜配位化合物进行了表征，显示出畸变的四面体铜配位环境。研究表明，配体 L1 中存在一个与咪唑啉酮融合的五元噻唑烷环会导致配合物的几何特征发生显著变化：Cu-S 间距增加，铜配位多面体变平。使用循环伏安法对合成的这两种配合物进行了评估，结果表明，在 ∼ -0.25 V 的电压下，铜（II）发生了准可逆还原。对报告菌株大肠杆菌 ΔtolC pDualrep2 (AmpR) 和大肠杆菌 lptDmut pDualrep2 (KanR) 的抗菌活性测试表明，与结构中没有额外缩合环的类似配体的配合物相比，合成的含铜配合物的活性较低。

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引用次数: 0

Synthesis, crystal structure and sulphide ion sensing study of a Cu(II) complex of aroyl hydrazone 甲酰腙的 Cu(II) 复合物的合成、晶体结构和硫离子传感研究

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-11-09 DOI: 10.1016/j.poly.2024.117294

Moumita Chakraborty , Antu Mondal , Anwesha Ghosh , Alakananda Mahapatra , Tapan Kumar Mondal , Shyamal Kumar Chattopadhyay

Herein, we report a Cu(II) complex {[Cu^II(HL)(H₂O)₂]Cl} of a benzoylhydrazone Schiff base ligand (4-((2-benzoylhydrazineylidene)methyl)-3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-1-ium chloride) (H₂L). The molar conductance in solution, magnetic susceptibility, ESI-MS and EPR spectroscopy have been performed to justify the structure of the complex. The solid-state structure of the complex has also been solved by single crystal X-ray diffractometry. Cu(II) centre is penta-coordinated with imine-N, phenoxide-O and deprotonated amide-O donor of the ligand and two H₂O molecules occupying the coordination sphere forming a distorted square pyramidal geometry (τ = 0.32). We have studied the anion sensing property of the complex by monitoring the changes in the UV–Vis and fluorescence spectra of the complex in aqueous Tris-HCl buffer medium with incremental addition of various anions as tetrabutylammonium/sodium salts. The complex shows appreciable sensitivity toward sulphide ion, among various other anions, with association constant (K_b) for binding of the complex with S²⁻ and lowest detection limit (L.O.D) value of 6.87 × 10⁴ M⁻¹ and 6.9 × 10⁻⁷ M, respectively. Thus, the complex can be used as an efficient S²⁻ probe. The mechanism of sensing is found to be displacement of the fluorescent ligand from the Cu(II) complex by the sulphide ion.

在此，我们报告了苯甲酰肼席夫碱配体（4-((2-苯甲酰肼亚基)甲基)-3-羟基-5-(羟甲基)-2-甲基吡啶-1-氯化铵）（H2L）的铜（II）配合物{[CuII(HL)(H2O)2]Cl}。对该复合物进行了溶液摩尔电导、磁感应强度、ESI-MS 和 EPR 光谱分析，以证明其结构的合理性。此外，还通过单晶 X 射线衍射仪解决了该复合物的固态结构问题。Cu(II) 中心与配体的亚胺-N、氧化酚-O 和去质子化的酰胺-O 给体呈五配位，两个 H2O 分子占据配位层，形成扭曲的正方金字塔几何结构 (τ = 0.32)。我们研究了该配合物的阴离子传感特性，方法是在水性 Tris-HCl 缓冲介质中，以四丁基铵盐/钠盐的形式逐步加入各种阴离子，监测配合物紫外可见光谱和荧光光谱的变化。该复合物对硫离子和其他各种阴离子都非常敏感，与 S2- 结合的关联常数（Kb）和最低检测限（L.O.D）值分别为 6.87 × 104 M-1 和 6.9 × 10-7 M。因此，该复合物可用作高效的 S2- 探针。感应机制是硫离子将荧光配体从 Cu(II) 复合物中置换出来。

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引用次数: 0

Supramolecular architectures, Hirshfeld surfaces analysis, spectroscopic, computational and photovoltaic properties of nickel(II) binary and ternary complexes of N-phenethyl-iminodiacetate (2-) chelate N-苯乙基-亚氨基二乙酸酯（2-）螯合物的镍（II）二元和三元配合物的超分子结构、Hirshfeld 表面分析、光谱、计算和光伏特性

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2024-11-07 DOI: 10.1016/j.poly.2024.117284

D.K. Patel , D. Choquesillo-Lazarte , A. Castiñeiras , J. Niclós-Gutiérrez

The bluish-green color nickel(II) binary and/or ternary compounds have been isolated from the solution of stoichiometric reaction between Ni(II) hydroxy-carbonate and N-phenethyl-iminodiacetic acid (H₂pheida) chelating ligand in aqueous media with compound (2); [Ni(pheida)(Him)₃]·4H₂O and without imidazole compound (1); [Ni(pheida)(H₂O)₃]. The crystal pattern of binary compound [Ni(pheida)(H₂O)₃] (1) differs from the related tetra-hydrated ternary complex of [Ni(pheida)(Him)₃]·4H₂O (2) can be attributed to the presence of stronger N-(Him) spacer of imidazole ligand. The compounds reported herein, have been characterized by means of elemental analysis, FTIR, UV–vis, TGA and X-ray crystallography. Moreover, the distinctive inter-molecular forces particularly H-bonding interactions, 2D fingerprint plots and supramolecular architecture have been studied using Hirshfeld surface analysis. The nickel(II) binary and ternary complexes (1) and (2) show distorted octahedral geometry around the Ni(II) ion of the type 1 + 2 + 2 + 1 imposed by 3d⁸ electronic configuration with degenerate fully and half occupied t_2g⁶ and e_g² orbitals respectively. The higher John-Teller distortion has been observed for complex (2) than that of complex (1). The IDA arm of chelate adopted fac-NO₂ conformation in both complexes (1) and (2). Moreover, the photovoltaic properties as semiconducting nature for ligand and their corresponding Ni(II) complexes were estimated using Tauc’s equation, αhν = A(hν-E_g)^r, where r = ½ for indirect and 2 for direct electronic transitions through UV–vis absorption data. The indirect and direct electronic transition bandgap (E_g) calculated for complex (1) is 2.0 and 3.07 eV respectively. Similarly, 2.55 and 4.39 eV respectively measured for complex (2).

羟基碳酸镍（II）和 N-苯乙基-亚氨基二乙酸（H2pheida）螯合配体在水介质中与化合物（2）[Ni(pheida)(Him)3]-4H2O 和不含咪唑化合物（1）[Ni(pheida)(H2O)3]发生化学反应，从溶液中分离出蓝绿色的镍（II）二元和/或三元化合物。二元化合物[Ni(pheida)(H2O)3](1)的晶体形态不同于相关的四水三元复合物[Ni(pheida)(Him)3]-4H2O(2)，这可归因于咪唑配体中存在较强的 N-(Him)间隔。本文报告的化合物已通过元素分析、傅立叶变换红外光谱、紫外可见光、热重分析和 X 射线晶体学等方法进行了表征。此外，还利用 Hirshfeld 表面分析法研究了独特的分子间作用力，特别是 H 键相互作用、二维指纹图谱和超分子结构。镍（II）二元和三元配合物（1）和（2）显示出围绕镍（II）离子的 1 + 2 + 2 + 1 型扭曲八面体几何结构，该几何结构由 3d8 电子构型施加，分别具有退化的全占和半占 t2g6 和 eg2 轨道。与络合物（1）相比，络合物（2）的约翰-泰勒畸变更高。在复合物（1）和（2）中，螯合物的 IDA 臂都采用了 fac-NO2 构象。此外，通过紫外可见吸收数据，利用陶氏方程（αhν = A(hν-Eg)r，其中 r = ½ 表示间接电子转变，2 表示直接电子转变）估算了配体及其相应 Ni(II) 复合物作为半导体的光伏特性。计算得出的复合物 (1) 的间接和直接电子转变带隙（Eg）分别为 2.0 和 3.07 eV。同样，复合物 (2) 的测量值分别为 2.55 和 4.39 eV。

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引用次数: 0