Inorganica Chimica Acta最新文献_第6页

Multifunctional behavior of alkaline selenite oxo-fluoro compounds, investigated by DFT for green tech applications 碱性亚硒酸盐含氧氟化合物的多功能化行为及其在绿色技术中的应用

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2026-04-01 Epub Date: 2025-12-27 DOI: 10.1016/j.ica.2025.123046

Nawishta Jabeen , Ali Yaqoob , Ahmad Hussain , Aseel Smerat , Mohamed A. Nassan , Nidhal Ben Khedher

DFT based simulations have been performed to investigate the structural, optoelectronics, thermodynamics and mechanical properties of double anionic structured (alkaline selenite oxo-fluoro) compounds (XSeO₃F where X = Y, Sc, La and Lu), which can present their potentials for the green energy applications. The choice of metallic cationic replacements within these structures is greatly influenced their dynamics stability and the ionic character. Among these compounds, SeO₃ counterpart is responsible for enhanced optical characteristics. All these compounds have presented wide indirect band gaps from 3.31 eV to 3.93 eV, followed by high values of optical properties like absorption (10⁵ cm⁻¹), optical conductivity (3 fs⁻¹–5 fs⁻¹). Moreover, no transparency is observed for the incident radiations range from 0 eV to 10 eV, which is confirmed by the values ε₁(ω) > 0, and n(ω) > 1. Reflectivity remains as low as 10 % within the visible region of incident light which is followed by low loss of dissipated energy within the compounds. Lower value of zero-point energy 0.767 eV for LuSeO₃F shows less vibrational frequencies indicating more stability as compared to other compounds. The convergence of heat capacity near the Dulong-Petit limit (74.9 cal/cell. K) reveals the thermal resistance showing potentials for high temperature electronics devices. Ductile nature has been confirmed for XSeO₃F (X = Y, Sc, and Lu) compounds by Poisson's and Pugh's ratios, but LaSeO₃F compound has demonstrated the more unique auxetic nature. These results suggest that alkaline selenite based oxo-fluoro compounds possess promising potential for next generation green technologies such as optoelectronic, tendon cells, and sustainable energy conversion devices.

基于DFT的模拟研究了双阴离子结构（碱性亚硒酸盐含氧氟）化合物（XSeO3F，其中X = Y, Sc， La和Lu）的结构，光电子学，热力学和力学性能，从而展示了它们在绿色能源应用中的潜力。这些结构中金属阳离子置换的选择对其动力学稳定性和离子特性有很大影响。在这些化合物中，SeO3对应物负责增强光学特性。所有化合物均具有3.31 eV至3.93 eV的宽间接带隙，并具有较高的光学性质，如吸收（105 cm−1），光学电导率（3 fs−1 ~ 5 fs−1）。此外，在0 ~ 10 eV的入射辐射范围内，没有观察到透明现象，这可以通过ε1(ω) >； 0和n(ω) >； 1得到证实。在入射光的可见区域内，反射率保持低至10%，其次是化合物内耗散能量的低损失。与其他化合物相比，LuSeO3F的零点能量为0.767 eV，振动频率更低，稳定性更高。在Dulong-Petit极限（74.9 cal/cell）附近的热容收敛。K)表示显示高温电子器件电位的热阻。XSeO3F （X = Y, Sc, Lu）化合物的延展性通过泊松比和Pugh比得到了证实，但LaSeO3F化合物表现出了更独特的塑性。这些结果表明，碱性亚硒酸盐基含氧氟化合物在下一代绿色技术（如光电、肌腱细胞和可持续能量转换装置）方面具有很大的潜力。

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引用次数: 0

A proton-conducting nickel(II) hydrogen-bonded organic framework assembled from mixed bipyridyl-organodisulfonic ligands 由混合联吡啶-有机二磺酸配体组装的质子导电镍（II）氢键有机骨架

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2026-04-01 Epub Date: 2025-12-29 DOI: 10.1016/j.ica.2025.123049

Feng-Li Chen , Ao-Na Sun , Xing-Yi Yu , Jiong Yang , Dong Shao

A nickel(II) hydrogen-bonded-organdisulfonate framework, [Ni(bpy)(H₂O)₄][bpds]·4H₂O (NiHOF-101, bpy = 2,2’-Bipyridyl, H₂bpds = 4,4’-Biphenyldisulfonic acid) was synthesized and characterized in terms of structure, magnetic, and proton conduction properties. Crystallographic analysis reveals a three-dimensional hydrogen-bonded network stabilized by charge-assisted OH⋯O interactions involving coordinated and lattice water molecules with sulfonate groups. Magnetic measurements indicate the high-spin state of the Ni²⁺ ion showing easy-axis magnetic anisotropy with the D value being −13.7 cm⁻¹. However, the NiHOF displayed non-single-ion magnet behavior. Ac impedance spectroscopy indicated this NiHOF is a superionic proton conductor with the highest measured conductivity being 3.24 × 10⁻³ S cm⁻¹ at 60 °C under 95 % relative humility through a Grotthuss mechanism. Structural analysis reveals abundant coordinated and lattice water molecules interacting with well-oriented sulfonate groups should be responsible for the highly efficient proton transport. This work highlights a potential strategy for constructing supramolecular solid state proton conductors (SSPCs) through mixed bipyridyl-organodisulfonic ligands.

合成了一种镍（II）氢键有机二磺酸盐骨架[Ni(bpy)(H2O)4][bpds]·4H2O （NiHOF-101, bpy = 2,2′-联吡啶基，H2bpds = 4,4′-联苯二磺酸），并对其结构、磁性和质子传导性能进行了表征。晶体学分析揭示了一个由电荷辅助OH⋯O相互作用稳定的三维氢键网络，涉及配位和晶格水分子与磺酸基。磁测量表明，高自旋态的Ni2+离子表现出易轴磁各向异性，D值为−13.7 cm−1。然而，NiHOF表现出非单离子磁铁行为。交流阻抗谱表明，该NiHOF是一种超离子质子导体，在60 °C、95 %相对低温条件下，通过Grotthuss机制测得的最高电导率为3.24 × 10−3 S cm−1。结构分析表明，大量的配位和点阵水分子与取向良好的磺酸基相互作用是质子高效输运的原因。这项工作强调了通过混合联吡啶-有机二磺酸配体构建超分子固态质子导体（SSPCs）的潜在策略。

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引用次数: 0

Synthesis of gas-phase, group II metal hydride cations using preparative tandem mass spectrometry 制备串联质谱法合成气相II族金属氢化物阳离子

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2026-03-01 Epub Date: 2025-12-18 DOI: 10.1016/j.ica.2025.123043

Madeline R. Handel , Samuel J. Lenze , Lucas G. Fuller , Theodore A. Corcovilos , Michael J. van Stipdonk

Interest in Main Group metal hydrides remains high because of their potential use as hydrogen storage materials and as green catalysts. However, the high reactivity of metal hydrides along with the solvent effects and complex equilibria of condensed phase studies makes study of their intrinsic chemistry a challenge. In principle, the challenge can be overcome by using ion preparation methods such as collision-induced dissociation to synthesize species within the relatively inert gas-phase environment of ion-trapping mass spectrometers. In this study, preparative (ion trap) tandem mass spectrometry (PTMSⁿ) was used to generate a series of binary, gas-phase metal hydride cations. In particular, we show that the relatively inert environment of a quadrupole ion trap permits (a) the synthesis of discrete, group II metal hydride cations, [MetH]⁺ (Met = Ca, Sr, Ba) and (b) allows for monitoring of intrinsic reactions with neutral species such as H₂O and CH₂Cl₂. When exposed to H₂O, the [MetH]⁺ cations undergo a hydrolysis reaction to form the respective cationic, metal hydroxides. When allowed to react with CH₂Cl₂, two reaction pathways are observed, one leading to formation of [Met(CHCl₂)]⁺ (with elimination of neutral H₂) and the other producing [MetCl]⁺ (by elimination of CH₃Cl). The reactions to generate the [MetH]⁺ cations, and the ion-molecule reactions with H₂O and CH₂Cl₂, were modeled using density functional theory (DFT) and 2nd – order Moller-Plesset (MP2) calculations to provide optimized structures of reactants, intermediates, products and transition states. In general, the computed enthalpies and free energies for the reactions are in good qualitative agreement with the experimental outcomes.

由于其作为储氢材料和绿色催化剂的潜在用途，人们对主族金属氢化物的兴趣仍然很高。然而，金属氢化物的高反应活性、溶剂效应和复杂的缩合相平衡研究给其内在化学的研究带来了挑战。原则上，可以通过使用离子制备方法，如碰撞诱导解离，在离子捕获质谱仪的相对惰性气相环境中合成物种来克服这一挑战。本研究采用制备（离子阱）串联质谱法（PTMSn）生成了一系列二元气相金属氢化物阳离子。特别是，我们证明了相对惰性的四极离子阱环境允许(a)合成离散的，II族金属氢化物阳离子，[甲基]+ (Met = Ca, Sr, Ba)和(b)允许监测与中性物质如H2O和CH2Cl2的固有反应。当暴露于H2O时，[甲基]+阳离子发生水解反应，形成各自的阳离子金属氢氧化物。当允许与CH2Cl2反应时，观察到两个反应途径，一个导致形成[Met(CHCl2)]+（消除中性H2），另一个产生[MetCl]+（消除CH3Cl）。利用密度泛函理论（DFT）和二阶Moller-Plesset （MP2）计算，对生成[甲基]+阳离子的反应以及H2O和CH2Cl2的离子-分子反应进行了建模，以优化反应物、中间体、产物和过渡态的结构。总的来说，计算出的反应焓和自由能与实验结果在定性上是一致的。

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引用次数: 0

Synthesis, photophysicochemical and electrochemical properties of new peripheral tetra-substituted Zn(II) phthalocyanines bearing quinoline groups 含喹啉基团的新型外周四取代Zn（II）酞菁的合成、光物理化学和电化学性能

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2026-03-01 Epub Date: 2025-12-14 DOI: 10.1016/j.ica.2025.123040

Barış Seçkin Arslan , Nagihan Öztürk , Mehmet Nebioğlu , İlkay Şişman

This study focuses on the synthesis of novel zinc phthalocyanines containing tetra-((6,7,8-trimethoxytetrazolo[1,5-a]quinolin-4-yl)methoxy) and tetra-((2,5,6,7-tetramethoxyquinolin-3-yl)methoxy) substituents and the investigation of their photodynamic therapy (PDT) properties. Two novel phthalonitrile derivatives bearing trimethoxytetrazolo (5a) and tetramethoxy (5b) quinoline moieties and their corresponding peripherally substituted zinc(II) phthalocyanine complexes (BIM8 and BIM9) were synthesized. The molecular structures of these compounds were verified by FT-IR, NMR, UV–Vis spectroscopy, and mass spectrometry. The photophysical, photochemical, and electrochemical properties of the zinc phthalocyanines were systematically investigated to evaluate their potential application in PDT. Compared to BIM8, BIM9 exhibited superior photochemical performance, including a high singlet oxygen quantum yield (ɸ_Δ = 0.89), negligible aggregation tendency, sufficient fluorescence emission for imaging purposes, and notable photostability. These results demonstrate that BIM9 is a promising photosensitizer candidate for PDT.

本文研究了含四-（（6,7,8-三甲氧基四唑[1,5-a]喹啉-4-基）甲氧基）和四-（2,5,6,7-四甲基喹啉-3-基）甲氧基)取代基的新型酞菁锌的合成及其光动力治疗（PDT）性能的研究。合成了两种含有三甲氧基四唑（5a）和四甲氧基（5b）喹啉基团的新型酞腈衍生物及其相应的外周取代锌（II）酞菁配合物（BIM8和BIM9）。这些化合物的分子结构通过FT-IR、NMR、UV-Vis光谱和质谱进行了验证。系统地研究了酞菁锌的光物理、光化学和电化学性能，以评价其在PDT中的应用潜力。与BIM8相比，BIM9表现出优异的光化学性能，包括高单线态氧量子产率（h Δ = 0.89），可忽略的聚集倾向，足够成像的荧光发射以及显著的光稳定性。这些结果表明，BIM9是一种很有前途的PDT光敏剂。

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引用次数: 0

Carboxylated benzo and pyrazine annulated PV corrolazines. I. Synthesis, spectral-luminescence and acid-base properties of octaethyl esters 羧基苯并吡嗪环吡啶。一、辛乙酯的合成、光谱发光及酸碱性质

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2026-03-01 Epub Date: 2025-11-29 DOI: 10.1016/j.ica.2025.123000

Dmitriy A. Lazovskiy , Ekaterina S. Gnedina , Ivan A. Nikitin , Hailong Wang , Pavel A. Stuzhin

Ethyl octaesters of phthalocyanine bearing eight carboxy-groups, [^EstPcH₂] (3), and its pyrazine fused analogue [^EstTPyzPAH]₂ (4) were synthesized by melting of corresponding dicarbonitriles in presence of sodium hydroxide or ethoxide. Reaction of these macrocycles with PBr₃ in pyridine leads to contraction of the porphyrazine macrocycle and formation of the corresponding P^V corrolazines, isolated as oxophosphorus(V) and dihydroxidophosphorus(V) complexes, [^EstTBzCAP=O] (5) and [^EstTPyzCAP(OH)₂] (6). Fusion of electron-withdrawing pyrazine rings increases the NH acidity of the porphyrazine macrocycle leading to easy deprotonation of 4 and decreases the basicity of meso‑nitrogens – all of them can be protonated in 5 and only one in 6. Combination of electron-deficient pyrazine rings and electron-withdrawing COOEt groups leads to enhanced singlet oxygen generating ability not only by corrolazine 6, but also by dianionic form of porphyrazine 4 (Ф_Δ = 0.58 and 0.32, respectively). The obtained octaethyl esters can be considered as precursors for water-soluble octacarboxylated derivatives and building blocks for design of organic frameworks.

通过在氢氧化钠或乙氧基存在下将相应的二腈熔化，合成了含有8个羧基的酞菁八酯[EstPcH2](3)及其吡嗪融合类似物[EstTPyzPAH]2(4)。这些大环与PBr3在吡啶中的反应导致卟啉大环收缩并形成相应的PV腐蚀嗪，分离为氧磷(V)和二羟基磷(V)配合物，[EstTBzCAP=O](5)和[EstTPyzCAP(OH)2](6)。吸电子吡嗪环的融合增加了卟啉大环的NH酸度，导致4容易去质子化，并降低了中位氮的碱度——所有中位氮都能在5中质子化，而在6中只有一个。缺乏电子的吡嗪环与吸电子的COOEt基团结合，不仅可以增强腐蚀嗪6的单线态产氧能力，还可以增强重阴离子形式的卟啉嗪4的单线态产氧能力（ФΔ = 0.58和0.32）。所得到的辛乙酯可以被认为是水溶性八羧基化衍生物的前体和设计有机框架的构建块。

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引用次数: 0

A straightforward approach for synthesizing vanadium-doped 2D MoSe2 as cathode in high-energy lithium-ion supercapacitors 一种在高能锂离子超级电容器中合成掺钒二维MoSe2作为阴极的直接方法

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2026-03-01 Epub Date: 2025-12-11 DOI: 10.1016/j.ica.2025.123038

Souvik Naskar, Ishita Naskar, Karan Kumar Gupta, Chung-Hsin Lu

A simple hydrothermal and calcination procedure was used to synthesize 2D‑vanadium-doped MoSe₂ nanosheets (V-MoSe₂ NSs) with good control over shape and crystallinity in this study. Se removal from the VMo structure was assessed by p-XRD, FE-SEM, EDAX, and FE-TEM. The findings demonstrate that the crystal phase and textural characteristics alter as a result of physical parameter adjustment. The V-MoSe₂ in the two-electrode system was found to have a specific capacitance of 369 F g⁻¹, which is higher than that of the pristine MoSe₂ (P-MoSe₂) electrode. The assembled lithium-ion supercapacitor (LISC) also exhibits impressive electrochemical performance, possessing an energy density of 479 Wh kg⁻¹ and a power density of 8.7 kW kg⁻¹, with good cycling stability and 88 % capacitance retention after 5000 cycles. The novelty of this work lies in the rational incorporation of vanadium into the MoSe₂ lattice to engineer its electronic structure and surface properties, which effectively enhances charge storage capability and ion diffusion kinetics. The increase in the electrochemical performance of V-MoSe₂ was due to its distinctive nanosheet-like morphology, which features a high specific surface area, low charge transfer resistance, and reduced ion diffusion resistance. This study displays a practical scheme for a combination of electrodes made of the metallic element vanadium and selenide.

本研究采用简单的水热和煅烧工艺合成了形状和结晶度可控的二维掺钒MoSe₂纳米片（V-MoSe₂NSs）。采用p-XRD、FE-SEM、EDAX和FE-TEM等方法对VMo结构的Se去除率进行了评价。结果表明，物理参数的调整会改变晶体的相和织构特征。在两电极体系中，V-MoSe 2的比电容为369 F g−1，高于原始MoSe 2 （P-MoSe 2）电极。组装的锂离子超级电容器（LISC）也表现出令人印象深刻的电化学性能，其能量密度为479 Wh kg - 1，功率密度为8.7 kW kg - 1，具有良好的循环稳定性，循环5000次后电容保持率为88%。这项工作的新颖之处在于将钒合理地结合到MoSe₂晶格中，以设计其电子结构和表面性质，有效地提高了电荷存储能力和离子扩散动力学。V-MoSe₂电化学性能的提高是由于其独特的纳米片状形貌，具有高比表面积，低电荷转移电阻和降低离子扩散阻力。这项研究展示了一种实用的方案，即由金属元素钒和硒化物制成的电极组合。

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引用次数: 0

Targeting and bioimaging of human lung cancer cells via Heteroleptic iridium complexes 异效铱复合物对人肺癌细胞的靶向和生物成像研究

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2026-03-01 Epub Date: 2025-11-26 DOI: 10.1016/j.ica.2025.123009

Özlem Altsoy , Özlem Biçen Ünlüer , Filiz Yilmaz , Sibel Emir Diltemiz , Deniz Hür , Arzu Ersöz , Ridvan Say

Two bis-cyclometalated iridium complexes [Ir(ppyCF₃)₂(MAA)] (ppyCF₃: 2-(4-trifluoromethylphenyl)pyridine; MAA: methacryloylamino acid) have been synthesized and characterized by ¹H NMR, ¹³C NMR, ¹⁹F NMR, UV–Vis and FT-IR spectroscopy. The potential of the synthesized Ir(III) complexes as bioimaging agents was examined through their interaction with transferrin receptors in cells. The iridium complexes were attached to the transferrin protein via electron transfer using the tyrosine or tryptophan groups in the MAA ligand. This interaction enhances intracellular targeting and imaging efficiency, thereby expanding the potential applications of Ir(III) complexes in biological systems. In our study, we obtained two different types of biomaterials by interacting Ir(III) complexes with transferrin. The first type is iridium-transferrin cross-linked conjugates (Ir-Tf), and the second type is nano-structured iridium-transferrin cross-linked polymers (nanoIr-Tf). Our findings demonstrate that [Ir(ppyCF₃)₂(MATyr)]-Tf and nano[Ir(ppyCF₃)₂(MATyr)]-Tf show promise as efficient bioimaging agents. When interacting with both cancerous and normal lung cells, these complexes displayed robust fluorescence emission, enabling precise imaging and visualization. Notably, the complexes selectively localized within the cytoplasm of cancer cells, highlighting their potential for targeted imaging.

两种双环金属化铱配合物[Ir(ppyCF3)2(MAA)] (ppyCF3: 2-（4-三氟甲基苯基）吡啶；合成了甲基丙烯酰氨基酸（MAA: methacryloylamino acid），并用1H NMR、13C NMR、19F NMR、UV-Vis和FT-IR对其进行了表征。通过与细胞内转铁蛋白受体的相互作用，研究了合成的Ir（III）复合物作为生物显像剂的潜力。铱配合物利用MAA配体中的酪氨酸或色氨酸基团通过电子转移与转铁蛋白结合。这种相互作用增强了细胞内靶向和成像效率，从而扩大了Ir（III）复合物在生物系统中的潜在应用。在我们的研究中，我们通过Ir（III）配合物与转铁蛋白相互作用获得了两种不同类型的生物材料。第一类是铱-转铁蛋白交联缀合物（Ir-Tf），第二类是纳米结构的铱-转铁蛋白交联聚合物（nanoIr-Tf）。我们的研究结果表明，[Ir(ppyCF3)2(MATyr)]-Tf和纳米[Ir(ppyCF3)2(MATyr)]-Tf有望成为高效的生物显像剂。当与癌细胞和正常肺细胞相互作用时，这些复合物显示出强大的荧光发射，从而实现精确的成像和可视化。值得注意的是，这些复合物选择性地定位于癌细胞的细胞质中，突出了它们在靶向成像方面的潜力。

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引用次数: 0

Synthetic strategy, structural aspects and biological applications of multinuclear cadmium complexes using salen type N2O2 donor ligands and N2O2O2′ donor compartmental ligands: A review salen型N2O2给体配体和N2O2O2给体区室配体多核镉配合物的合成策略、结构及生物学应用综述

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2026-03-01 Epub Date: 2025-12-13 DOI: 10.1016/j.ica.2025.123029

Puspendu Middya , Siddhartha Majhi , Shouvik Chattopadhyay

Cadmium(II) complexes with salen- and salpn-type Schiff base ligands have gained increasing attention for their structural versatility, diverse coordination geometries, and notable biological potential. This review summarizes recent advances in their synthesis, spectral and structural characterization, and bioactivity. The flexible coordination of Cd(II) and the chelating nature of Schiff bases promote the formation of di- and polynuclear architectures, often stabilized by bridging ligands. Structural insights from X-ray studies and their correlation with antimicrobial, antifungal, anticancer, and enzyme-inhibitory activities are discussed. Despite cadmium's inherent toxicity, rational ligand design has yielded complexes with enhanced bioactivity and reduced cytotoxicity. Key challenges and prospects for developing Cd(II) Schiff base complexes as therapeutic and functional materials are also highlighted.

镉（II）配合物与salen型和salp型希夫碱配体因其结构的多功能性、不同的配位几何和显著的生物学潜力而越来越受到关注。本文综述了其合成、光谱和结构表征以及生物活性方面的研究进展。Cd（II）的灵活配位和席夫碱的螯合性质促进了二核和多核结构的形成，通常通过桥接配体来稳定。本文讨论了x射线研究的结构见解及其与抗菌、抗真菌、抗癌和酶抑制活性的关系。尽管镉具有固有的毒性，但合理的配体设计已经产生了具有增强生物活性和降低细胞毒性的复合物。重点介绍了开发Cd（II）希夫碱配合物作为治疗材料和功能材料的主要挑战和前景。

引用次数: 0

Pyrazolylimine complexes Ni(II) – Precatalysts for the synthesis branched polyethylene 吡唑亚胺配合物Ni(II) -合成支化聚乙烯的预催化剂

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2026-03-01 Epub Date: 2025-11-25 DOI: 10.1016/j.ica.2025.123002

Daniele Saracheno , Anton O. Vikhrov , Roman V. Rassokhin , Vladislav A. Tuskaev , Svetlana Ch. Gagieva , Svetlana A. Aksenova-Soloveva , Mikhail I. Buzin , Boris M. Bulychev

Seven new and one previously described pyrazolylimine complex NiBr₂ with aryl substituents exhibiting different electronic effects on the imine carbon atom were synthesized and characterized. It was shown that the obtained compounds are effective catalysts for ethylene polymerization in the presence of diethylaluminum chloride (DEAC).

The influence of the electronic properties of the R substituents on the catalytic performance of the complexes was systematically investigated. A clear correlation between ligand electron-donating or -withdrawing character and both polymer molecular weight and catalytic activity was observed, providing insight into the electronic factors governing the efficiency of these nickel-based systems.

合成了7个新的和1个已知的具有芳基取代基的吡唑亚胺配合物NiBr2，它们在亚胺碳原子上具有不同的电子效应。结果表明，所得化合物是二乙基氯化铝（DEAC）存在下乙烯聚合的有效催化剂。系统地研究了R取代基的电子性质对配合物催化性能的影响。观察到配体的供电子或吸电子特性与聚合物分子量和催化活性之间存在明显的相关性，从而深入了解控制这些镍基体系效率的电子因素。

引用次数: 0

Thiosemicarbazone complexes of nickel, palladium and platinum: catalytic application for CN cross-coupling reaction in water 镍、钯、铂的硫代氨基脲配合物在水中CN交叉偶联反应中的催化应用

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2026-03-01 Epub Date: 2025-12-07 DOI: 10.1016/j.ica.2025.123030

Sayanti Datta , Anushri Chandra , Samaresh Bhattacharya

Reaction of imidazole-2-carbaldehyde thiosemicarbazone (H₂L; where H₂ depicts the two dissociable protons, the imidazole NH proton and the SH proton) with Ni(ClO₄)₂·6H₂O in presence of triphenylphosphine yielded a complex of type [Ni^II(HL)(PPh₃)]ClO₄ (where HL represents mono-anionic ligand via SH proton dissociation). Similar reaction of the thiosemicarbazone with [M(PPh₃)₂Cl₂] (where M = Pd or Pt) afforded complexes with the general formula [M^II(L)(PPh₃)] (where L depicts fully deprotonated di-anionic ligand). Solid state crystal structures of all the three complexes have been determined by X-ray crystallography. The thiosemicarbazone ligand is found to serve as a N,N,S-donor in all three complexes. These complexes show intense absorptions in the visible and ultraviolet region, the origin of which has been probed through DFT and TDDFT calculations. Redox properties of the complexes have also been studied by cyclic voltammetry. All the three complexes were applied as catalyst for Buchwald-type CN cross-coupling between aryl halides and secondary amines to generate bio-active molecules. Out of the three complexes, the nickel and palladium complexes are found to be very promising for the CN cross-coupling reaction. The observed catalysis was possible in water as solvent, without any additive, and under relatively mild condition. This type of green and cost-effective protocol for the CN bond formation appears to be limited in the literature.

在三苯基膦存在下，咪唑-2-乙醛硫代氨基脲（H2L；其中H2表示两个可解离质子，咪唑NH质子和SH质子）与Ni(ClO4)2·6H2O反应生成[NiII(HL)(PPh3)]ClO4型配合物（其中HL表示通过SH质子解离的单阴离子配体）。硫代氨基脲与[M(PPh3)2Cl2]（其中M = Pd或Pt）的类似反应产生了通式[MII(L)(PPh3)]的配合物（其中L表示完全去质子化的二阴离子配体）。用x射线晶体学测定了这三种配合物的固态晶体结构。硫代氨基脲配体在这三种配合物中都是N，N， s给体。这些配合物在可见和紫外区表现出强烈的吸收，其起源已通过DFT和TDDFT计算进行了探讨。用循环伏安法研究了配合物的氧化还原性质。这三种配合物均作为催化剂用于芳基卤化物与仲胺之间的buchwald型CN交联，生成具有生物活性的分子。在这三种配合物中，镍和钯配合物在CN交叉偶联反应中很有前景。所观察到的催化作用在水为溶剂，不添加任何添加剂，在相对温和的条件下是可能的。这种绿色和具有成本效益的CN键形成方案在文献中似乎是有限的。

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引用次数: 0