Inorganica Chimica Acta最新文献_第4页

Phenoxido and azido bridged Schiff base coordinated dinuclear Ni(II) complexes: Syntheses, crystal structure and DFT calculation 苯氧基和叠氮基桥接希夫碱配位双核Ni（II）配合物：合成、晶体结构和DFT计算

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2026-05-01 Epub Date: 2026-01-19 DOI: 10.1016/j.ica.2026.123085

Manas Kumar Mahish , Dama Saren , Michael Bodensteiner , Ennio Zangrando , Subal Chandra Manna

Two dinuclear Ni(II) complexes, [Ni₂(L¹)₂(N₃)₂(H₂O)] (1) and [Ni₂(L²)₂(N₃)_1.675(NO₃)_0.325(H₂O)] (2) (where HL¹ = 2-[(2-ethylamino-ethylimino)-methyl]-6-methoxy-phenol; HL² = 2-ethoxy-6-[(2-ethylamino-ethylimino)-methyl]-phenol) have been synthesized and structurally characterized by single crystal X-ray diffraction, UV–visible, IR, and mass spectroscopic studies. The diffraction study showed comparable structure for the two dinuclear complexes with the two metals exhibiting a distorted octahedral geometry but with a different chemical environment, built by a N₄O₂ set for Ni1 and N₃O₃ for Ni2. One ligand acts as tetradentate bridging the metals Ni1 and Ni2 with phenolate oxygen, while the other Schiff base is tridentate chelating Ni2 only. In addition, the metals are bridged by a μ1,1-azide, and Ni1 completes the coordination sphere though a terminal N azide and an aquo O atom. Complexes 1 and 2 form 1D supra-molecular network through H-bonding interactions. As complement of experimental investigations, density functional theory (DFT) calculations were performed using B3LYP method and LanL2MB basis set. The results show that complex 1 has a slightly higher HOMO-LUMO energy gap in comparison to complex 2. Calculated values of chemical potential and electronegativity are comparable for both the complexes. Complexes 1 and 2 show fluorescence emission with lifetimes of 0.23766 ns and 0.21073 ns, respectively.

两个双核Ni（II）配合物，[Ni2(L1)2(N3)2(H2O)](1)和[Ni2(L2)2(N3)1.675(NO3)0.325(H2O)](2)(其中HL1 = 2-[（2-乙基氨基-乙基氨基）-甲基]-6-甲氧基苯酚；合成了HL2 = 2-乙氧基-6-[（2-乙基氨基-乙基氨基）-甲基]-苯酚)，并通过单晶x射线衍射、紫外-可见、红外和质谱研究对其进行了结构表征。衍射研究表明，两种金属的双核配合物具有相似的结构，两种金属表现出扭曲的八面体几何形状，但具有不同的化学环境，由N4O2为Ni1而N3O3为Ni2构建。一种配体与酚酸氧作为四齿桥接Ni1和Ni2，而另一种席夫碱仅为三齿螯合Ni2。此外，金属被μ1,1-叠氮化物桥接，Ni1通过末端N叠氮化物和水合O原子完成配位球。配合物1和2通过氢键相互作用形成一维超分子网络。作为实验研究的补充，采用B3LYP方法和LanL2MB基集进行密度泛函理论（DFT）计算。结果表明，配合物1的HOMO-LUMO能隙略高于配合物2。两种配合物的化学势和电负性的计算值具有可比性。配合物1和2的荧光发射寿命分别为0.23766 ns和0.21073 ns。

{"title":"Phenoxido and azido bridged Schiff base coordinated dinuclear Ni(II) complexes: Syntheses, crystal structure and DFT calculation","authors":"Manas Kumar Mahish , Dama Saren , Michael Bodensteiner , Ennio Zangrando , Subal Chandra Manna","doi":"10.1016/j.ica.2026.123085","DOIUrl":"10.1016/j.ica.2026.123085","url":null,"abstract":"<div><div>Two dinuclear Ni(II) complexes, [Ni2(L1)2(N3)2(H2O)] (1) and [Ni2(L2)2(N3)1.675(NO3)0.325(H2O)] (2) (where HL1 = 2-[(2-ethylamino-ethylimino)-methyl]-6-methoxy-phenol; HL2 = 2-ethoxy-6-[(2-ethylamino-ethylimino)-methyl]-phenol) have been synthesized and structurally characterized by single crystal X-ray diffraction, UV–visible, IR, and mass spectroscopic studies. The diffraction study showed comparable structure for the two dinuclear complexes with the two metals exhibiting a distorted octahedral geometry but with a different chemical environment, built by a N4O2 set for Ni1 and N3O3 for Ni2. One ligand acts as tetradentate bridging the metals Ni1 and Ni2 with phenolate oxygen, while the other Schiff base is tridentate chelating Ni2 only. In addition, the metals are bridged by a μ1,1-azide, and Ni1 completes the coordination sphere though a terminal N azide and an aquo O atom. Complexes 1 and 2 form 1D supra-molecular network through H-bonding interactions. As complement of experimental investigations, density functional theory (DFT) calculations were performed using B3LYP method and LanL2MB basis set. The results show that complex 1 has a slightly higher HOMO-LUMO energy gap in comparison to complex 2. Calculated values of chemical potential and electronegativity are comparable for both the complexes. Complexes 1 and 2 show fluorescence emission with lifetimes of 0.23766 ns and 0.21073 ns, respectively.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123085"},"PeriodicalIF":3.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074449","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Proton conductivity in a copper(II) bipyridine glycoluril complex: The synergistic role of coordinated water and hydrogen-bonded networks. 铜（II）联吡啶乙二醇脲配合物中的质子电导率：配位水和氢键网络的协同作用。

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2026-05-01 Epub Date: 2026-01-03 DOI: 10.1016/j.ica.2026.123063

Medhavi D. Khatavkar , Rishukumar Panday , Mayank U. Singh , Sreekumar Kurungot , Avinash S. Kumbhar

A dinuclear complex of copper(II) and bipyridine glycoluril (BPG) ligand is synthesized, characterized, and structurally examined by single-crystal X-ray diffraction. The complex [Cu₂(BPG)₂(NO₃)₂(H₂O)₄](NO₃)₂ꞏ5H₂O (complex (1)) further forms a supramolecular network sustained by H-bonds between NH/C=O of BPG, coordinated/free water molecules, and nitrate anions. The complex exhibits a proton conductivity of 5.99 × 10⁻³ Sꞏcm⁻¹ at 90 °C and 95 % relative humidity (RH) with activation energy value E_a 0.35 eV, suggesting the Grötthuss proton transport mechanism. This value is consistent with those reported for proton-conducting systems in which coordinated water molecules play a critical role in facilitating efficient proton hopping across hydrogen-bonded networks.

合成了一种双核铜（II）和联吡啶乙二醇（BPG）配体配合物，并用单晶x射线衍射对其进行了表征和结构检测。配合物[Cu2(BPG)2(NO3)2(H2O)4](NO3)2ꞏ5H2O（配合物(1)）进一步形成由BPG的NH/C=O、配位/自由水分子和硝酸盐阴离子之间的氢键维持的超分子网络。在90℃和95%相对湿度（RH）条件下，该配合物的质子电导率为5.99 × 10−3 Sꞏcm−1，活化能Ea为0.35 eV，表明该配合物具有Grötthuss质子输运机制。这一数值与质子传导系统的结果一致，在这些系统中，协调的水分子在促进质子在氢键网络上的有效跳跃中起着关键作用。

引用次数: 0

Rare-earth alkyl and amide ate complexes 稀土烷基酰胺配合物

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2026-05-01 Epub Date: 2026-01-21 DOI: 10.1016/j.ica.2026.123089

Fen Wang , Yuhong Liu , Jianfeng Li, Chunming Cui

Rare-earth (RE) ate complexes, formed by the coordination of anionic ligands to neutral rare-earth complexes, have attracted increasing attention. The electronic and steric protection toward the central ions in rare-earth ate complexes significantly enhances their stability. Moreover, rare-earth alkyl and amide ate complexes have been shown to behave as promising catalysts, attributable not only to the unique electronic structures but also interatomic collaborations. This review focuses on structurally characterized rare-earth alkyl and amide ate complexes, emphasizing their synthesis, structural features, reactivity and catalytic applications.

阴离子配体与中性稀土配合物配位形成的稀土酸盐配合物越来越受到人们的关注。稀土酸盐配合物对中心离子的电子保护和空间保护显著提高了配合物的稳定性。此外，稀土烷基和酰胺酸配合物不仅具有独特的电子结构，而且具有原子间的协同作用，因此被证明是很有前途的催化剂。本文综述了稀土烷基酰胺配合物的结构特征，重点介绍了它们的合成、结构特征、反应活性和催化应用。

引用次数: 0

Luminescent spectroscopic studies of electronic excitation energy transfer between aromatic molecules and the uranyl UO22+ (VI) cation 芳族分子与铀酰UO22+ (VI)阳离子之间电子激发能转移的发光光谱研究

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2026-05-01 Epub Date: 2026-01-18 DOI: 10.1016/j.ica.2026.123079

Xiaoping Sun, Erik Ulvaeng, Kaylee Nott

The luminescence spectra of mixtures of the uranyl UO₂²⁺ (VI) ion (U) and each of the following aromatic molecules (Ar): diphenyl sulfide (Ph₂S), benzene-1,4-diol (hydroquinone, Hq), anthracene (An), 4-nitrotoluene (NT), 1-chloro-4-nitrobenzene (CNB), and 2-naphthol (NaphOH), have been studied. For each of the Ar/U pairs, Ar was found to quench the luminescence of U; and U, on the other hand, was also found to quench the luminescence of Ar. The quenching efficiency of each Ar for the U* luminescence (I_U⁰/I_U) was determined to be dependent linearly on the Ar molarity: I_U⁰/I_U = 1 + K_q(Ar)[Ar] (K_q(Ar): quenching constant of Ar for the U* luminescence). The quenching efficiency of U for the Ar* luminescence (I_Ar⁰/I_Ar) was determined to be dependent linearly on the U molarity as well: I_Ar⁰/I_Ar = 1 + K_q(U)[U] (K_q(U): quenching constant of U for the Ar* luminescence). The quenching of the Ar* luminescence (Ar = Ph₂S, Hq, and An) by U occurred via an irreversible charge-transfer from the excited state Ar* (LUMO) to the ground state U (LUMO) within an EDA complex [Ar*, U] giving an Ar radical (Ph₂S⁺^., Hq, or An^+.) and UO₂⁺ (V). The charge-transfer mechanism for luminescence quenching is supported by the UV–Vis and EPR spectroscopic studies. The luminescence spectra of the Ar/U mixtures (Ar = NT, CNB, and NaphOH) with variable Ar and U concentrations exhibited emissions of both Ar* and U*. Their spectral lines shared a common isosbestic point. This indicates reversible, quantitative electronic excitation energy transfer from Ar* (energy donor) to U (energy acceptor) leading to Ar and U*, giving rise to quenching of the Ar* luminescence by U, and the simultaneous backward transfer of electronic energy from U* to Ar (Ar* + U ⇄ Ar + U*). Kinetic analysis has been performed based on the reversible electronic energy transfer mechanism. All the results in this work can serve as the theoretical basis for development of high–efficiency UO₂²⁺–stimulated/sensitized phosphors.

研究了铀酰UO22+ (VI)离子(U)与以下芳香分子（Ar）：二苯硫醚（Ph2S）、苯-1,4-二醇（对苯二酚，Hq）、蒽（An）、4-硝基甲苯（NT）、1-氯-4-硝基苯（CNB）和2-萘酚（NaphOH）的混合物的发光光谱。对于每一对Ar/U， Ar都能猝灭U的发光；另一方面，还发现了Ar的猝灭作用。确定了各Ar对U*发光的猝灭效率（IU0/IU）与Ar的量浓度呈线性关系：IU0/IU = 1 + Kq(Ar)[Ar] （Kq(Ar): Ar对U*发光的猝灭常数）。U对Ar*发光的猝灭效率（IAr0/IAr）也与U的量浓度呈线性关系：IAr0/IAr = 1 + Kq(U)[U] （Kq(U): U对Ar*发光的猝灭常数）。在EDA配合物[Ar*， U]中，由激发态Ar* (LUMO)到基态U （LUMO）的不可逆电荷转移产生了Ar自由基（Ph2S+），从而使Ar*发光（Ar = Ph2S， Hq和An）被U猝灭。（Hq或An+）和UO2+ (V)。紫外可见光谱和EPR光谱研究支持了发光猝灭的电荷转移机制。不同Ar和U浓度的Ar/U混合物（Ar = NT， CNB和NaphOH）的发光光谱显示出Ar*和U*的双重发射。它们的光谱线有一个共同的等吸点。这表明从Ar*（能量供体）到U（能量受体）的可逆、定量的电子激发能转移导致Ar和U*，导致Ar*的发光被U猝灭，同时电子能量从U*向后转移到Ar （Ar* + U*）。基于可逆电子能量传递机理进行了动力学分析。本研究结果可为开发高效UO22+激发/敏化荧光粉提供理论依据。

{"title":"Luminescent spectroscopic studies of electronic excitation energy transfer between aromatic molecules and the uranyl UO22+ (VI) cation","authors":"Xiaoping Sun, Erik Ulvaeng, Kaylee Nott","doi":"10.1016/j.ica.2026.123079","DOIUrl":"10.1016/j.ica.2026.123079","url":null,"abstract":"<div><div>The luminescence spectra of mixtures of the uranyl UO22+ (VI) ion (U) and each of the following aromatic molecules (Ar): diphenyl sulfide (Ph2S), benzene-1,4-diol (hydroquinone, Hq), anthracene (An), 4-nitrotoluene (NT), 1-chloro-4-nitrobenzene (CNB), and 2-naphthol (NaphOH), have been studied. For each of the Ar/U pairs, Ar was found to quench the luminescence of U; and U, on the other hand, was also found to quench the luminescence of Ar. The quenching efficiency of each Ar for the U* luminescence (IU0/IU) was determined to be dependent linearly on the Ar molarity: IU0/IU = 1 + Kq(Ar)[Ar] (Kq(Ar): quenching constant of Ar for the U* luminescence). The quenching efficiency of U for the Ar* luminescence (IAr0/IAr) was determined to be dependent linearly on the U molarity as well: IAr0/IAr = 1 + Kq(U)[U] (Kq(U): quenching constant of U for the Ar* luminescence). The quenching of the Ar* luminescence (Ar = Ph2S, Hq, and An) by U occurred via an irreversible charge-transfer from the excited state Ar* (LUMO) to the ground state U (LUMO) within an EDA complex [Ar*, U] giving an Ar radical (Ph2S+., Hq, or An+.) and UO2+ (V). The charge-transfer mechanism for luminescence quenching is supported by the UV–Vis and EPR spectroscopic studies. The luminescence spectra of the Ar/U mixtures (Ar = NT, CNB, and NaphOH) with variable Ar and U concentrations exhibited emissions of both Ar* and U*. Their spectral lines shared a common isosbestic point. This indicates reversible, quantitative electronic excitation energy transfer from Ar* (energy donor) to U (energy acceptor) leading to Ar and U*, giving rise to quenching of the Ar* luminescence by U, and the simultaneous backward transfer of electronic energy from U* to Ar (Ar* + U ⇄ Ar + U*). Kinetic analysis has been performed based on the reversible electronic energy transfer mechanism. All the results in this work can serve as the theoretical basis for development of high–efficiency UO22+–stimulated/sensitized phosphors.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123079"},"PeriodicalIF":3.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035666","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Manganese MOF deposited on graphene film for effective electrochemical detection of paraquat in drinking water and fruit juice 在石墨烯薄膜上沉积锰MOF用于饮用水和果汁中百草枯的有效电化学检测

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2026-05-01 Epub Date: 2026-01-08 DOI: 10.1016/j.ica.2026.123067

Baban Dey , SK Safdar Hossain , Hayat Khan , Akbar Niaz , Arup Choudhury , Duck-Joo Yang

Paraquat (PQ) is a poisonous insecticide, even at low concentrations, but it is widely used as an agricultural weed killer. As a consequence, we are constantly exposed to PQ through our diet. Therefore, quantitative and qualitative monitoring of this insecticide in vegetables and fruits before consumption is necessary. In this work, a flexible hybrid film was synthesized by growing manganese metal organic frameworks (Mn-MOFs) on a highly conductive graphene film (GRF) using one-step solvothermal method and was explored as a sensor electrode for the electrochemical detection of PQ for the first time. The as-prepared hybrid films were characterized using different morphological and spectroscopic techniques. Different electrochemical approaches were used to assess the electrocatalytic ability of the Mn-MOF/GRF hybrid. The Mn-MOF@GRF sensor electrode displayed impressive performance in detecting PQ, with a wide linear detection range from 0.05 to 350 μM and an excellent sensitivity of 63.44 μA μM⁻¹ cm⁻². The sensor electrode further demonstrated a lower limit of detection (LOD) and quantification (LOQ) of 2.9 and 9.03 nM, respectively, with decent reproducibility, and robust anti-interference characteristics. In real-time samples analysis, the hybrid sensor electrode achieved a recovery rate in the range of 96.4–105.4% for apple juice and hand-pump drinking water samples, which is close to the recovery rate of 95.2–105.7% achieved by HPLC method for the same samples. Therefore, this flexible sensor electrode has the potential to be used to fabricate portable electrochemical biosensors for monitoring paraquat in foods.

百草枯（PQ）是一种有毒的杀虫剂，即使浓度很低，但它被广泛用作农业除草剂。因此，我们通过饮食不断接触到PQ。因此，有必要在食用前对蔬菜和水果中的该杀虫剂进行定量和定性监测。本文采用一步溶剂热法在高导电石墨烯薄膜（GRF）上生长锰金属有机骨架（Mn-MOFs），合成了一种柔性杂化膜，并首次探索了将其作为电化学检测PQ的传感器电极。用不同的形态学和光谱技术对制备的杂化膜进行了表征。采用不同的电化学方法对Mn-MOF/GRF杂化物的电催化性能进行了评价。Mn-MOF@GRF传感器电极具有良好的PQ检测性能，线性检测范围为0.05 ~ 350 μM，灵敏度为63.44 μA μM−1 cm−2。该传感器电极的检测下限（LOD）和定量下限（LOQ）分别为2.9 nM和9.03 nM，具有良好的重现性和抗干扰性。在实时样品分析中，混合传感器电极对苹果汁和手泵饮用水样品的回收率为96.4-105.4%，与HPLC法对相同样品的回收率为95.2-105.7%接近。因此，这种柔性传感电极有潜力用于制造便携式电化学生物传感器，用于监测食品中的百草枯。

{"title":"Manganese MOF deposited on graphene film for effective electrochemical detection of paraquat in drinking water and fruit juice","authors":"Baban Dey , SK Safdar Hossain , Hayat Khan , Akbar Niaz , Arup Choudhury , Duck-Joo Yang","doi":"10.1016/j.ica.2026.123067","DOIUrl":"10.1016/j.ica.2026.123067","url":null,"abstract":"<div><div>Paraquat (PQ) is a poisonous insecticide, even at low concentrations, but it is widely used as an agricultural weed killer. As a consequence, we are constantly exposed to PQ through our diet. Therefore, quantitative and qualitative monitoring of this insecticide in vegetables and fruits before consumption is necessary. In this work, a flexible hybrid film was synthesized by growing manganese metal organic frameworks (Mn-MOFs) on a highly conductive graphene film (GRF) using one-step solvothermal method and was explored as a sensor electrode for the electrochemical detection of PQ for the first time. The as-prepared hybrid films were characterized using different morphological and spectroscopic techniques. Different electrochemical approaches were used to assess the electrocatalytic ability of the Mn-MOF/GRF hybrid. The Mn-MOF@GRF sensor electrode displayed impressive performance in detecting PQ, with a wide linear detection range from 0.05 to 350 μM and an excellent sensitivity of 63.44 μA μM−1 cm−2. The sensor electrode further demonstrated a lower limit of detection (LOD) and quantification (LOQ) of 2.9 and 9.03 nM, respectively, with decent reproducibility, and robust anti-interference characteristics. In real-time samples analysis, the hybrid sensor electrode achieved a recovery rate in the range of 96.4–105.4% for apple juice and hand-pump drinking water samples, which is close to the recovery rate of 95.2–105.7% achieved by HPLC method for the same samples. Therefore, this flexible sensor electrode has the potential to be used to fabricate portable electrochemical biosensors for monitoring paraquat in foods.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123067"},"PeriodicalIF":3.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145950249","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Binding and stabilizing effects of chiral Ru(II) polypyridyl complexes Δ- and Λ-[Ru(bpy)2(bidppz)]2+ toward RNA triplex poly(U-A*U) 手性Ru（II）多吡啶基配合物Δ-和Λ-[Ru(bpy)2(bidppz)]2+对RNA三聚体（U- a *U）的结合及稳定作用

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2026-05-01 Epub Date: 2026-01-05 DOI: 10.1016/j.ica.2026.123065

Yanqin Shen , Lifeng Tan

To investigate the interaction and stabilizing effect of Ru-dppz-derived chiral ruthenium(II) polypyridyl complexes on RNA triplexes, a pair of optically pure enantiomers Δ/Λ-[Ru(bpy)₂(bidppz)]²⁺ (Δ/Λ-1; bpy = 2,2′-bipyridine, bidppz = 11-(1H-benzo[d]imidazol-2-yl)dipyrido[3,2-a:2′,3′-c]phenazine) were synthesized and characterized. The binding characteristics of the enantiomers to RNA triplex poly(U-A*U) (where “-” indicates Watson-Crick base pairing and “⁎” signifies Hoogsteen base pairing) were investigated by spectroscopic and hydrodynamic techniques. Absorption spectrophotometric measurements revealed that Λ-1 exhibited a slightly higher binding affinity to triplex poly(U-A*U) than Δ-1. This observation was further supported by emission spectroscopy and viscosity measurements, confirming that Λ-1 interacted more effectively with RNA triplex than Δ-1. Thermal melting studies revealed that Δ-1 and Λ-1 significantly stabilized the third-strand of RNA triplex, with Λ-1 exhibiting a slightly stronger stabilizing effect than Δ-1. The RNA triplex adopts a right-handed A-type helix. Consequently, the Δ-enantiomer generally exhibits higher binding affinity than the Λ-enantiomer due to superior spatial compatibility. This study highlights that not all enantiomers adhere to the Δ-preference when interacting with RNA triplex, suggesting that Ru-dppz derivatives as RNA triplex stabilizers constitutes an important step in understanding how metal complexes can be designed to target RNA structures.

为了研究Ru-dppz衍生的手性钌（II）多吡啶配合物对RNA三络合物的相互作用和稳定作用，合成了一对光学纯对映体Δ/Λ-[Ru(bpy)2(bidppz)]2+ （Δ/Λ-1; bpy = 2,2 ' -联吡啶，bidppz = 11-（1h -苯并[d]咪唑-2-基）双吡啶[3,2-a:2 ',3 ' -c]非那嗪）。对映体与RNA三聚体（U- a *U）（“-”表示Watson-Crick碱基配对，“”表示Hoogsteen碱基配对）的结合特性通过波谱和流体动力学技术进行了研究。吸收分光光度测定结果表明，Λ-1对三聚体（U- a *U）的结合亲和力略高于Δ-1。发射光谱和粘度测量进一步支持了这一观察结果，证实Λ-1与RNA三联体的相互作用比Δ-1更有效。热熔研究表明，Δ-1和Λ-1显著稳定了RNA三联体的第三链，其中Λ-1的稳定作用略强于Δ-1。RNA三联体采用右手a型螺旋结构。因此，由于优越的空间相容性，Δ-enantiomer通常比Λ-enantiomer具有更高的结合亲和力。这项研究强调，当与RNA三联体相互作用时，并非所有对映体都坚持Δ-preference，这表明Ru-dppz衍生物作为RNA三联体稳定剂是理解金属配合物如何设计靶向RNA结构的重要一步。

{"title":"Binding and stabilizing effects of chiral Ru(II) polypyridyl complexes Δ- and Λ-[Ru(bpy)2(bidppz)]2+ toward RNA triplex poly(U-A*U)","authors":"Yanqin Shen , Lifeng Tan","doi":"10.1016/j.ica.2026.123065","DOIUrl":"10.1016/j.ica.2026.123065","url":null,"abstract":"<div><div>To investigate the interaction and stabilizing effect of Ru-dppz-derived chiral ruthenium(II) polypyridyl complexes on RNA triplexes, a pair of optically pure enantiomers Δ/Λ-[Ru(bpy)2(bidppz)]2+ (Δ/Λ-1; bpy = 2,2′-bipyridine, bidppz = 11-(1H-benzo[d]imidazol-2-yl)dipyrido[3,2-a:2′,3′-c]phenazine) were synthesized and characterized. The binding characteristics of the enantiomers to RNA triplex poly(U-A*U) (where “-” indicates Watson-Crick base pairing and “⁎” signifies Hoogsteen base pairing) were investigated by spectroscopic and hydrodynamic techniques. Absorption spectrophotometric measurements revealed that Λ-1 exhibited a slightly higher binding affinity to triplex poly(U-A*U) than Δ-1. This observation was further supported by emission spectroscopy and viscosity measurements, confirming that Λ-1 interacted more effectively with RNA triplex than Δ-1. Thermal melting studies revealed that Δ-1 and Λ-1 significantly stabilized the third-strand of RNA triplex, with Λ-1 exhibiting a slightly stronger stabilizing effect than Δ-1. The RNA triplex adopts a right-handed A-type helix. Consequently, the Δ-enantiomer generally exhibits higher binding affinity than the Λ-enantiomer due to superior spatial compatibility. This study highlights that not all enantiomers adhere to the Δ-preference when interacting with RNA triplex, suggesting that Ru-dppz derivatives as RNA triplex stabilizers constitutes an important step in understanding how metal complexes can be designed to target RNA structures.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123065"},"PeriodicalIF":3.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145950250","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Generation, characterization, and reactivity of a phthalocyanine iron–oxo complex 酞菁铁氧配合物的生成、表征和反应性

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2026-05-01 Epub Date: 2026-01-16 DOI: 10.1016/j.ica.2026.123084

Candice Schlabach, Chibuzor Uwazie, Rui Zhang

Oxidation of iron(III) tetra-tert-butylphthalocyanine chloride [Fe^III(^tBu₄Pc)Cl] (1) with AgClO₃ in anaerobic CH₃CN rapidly afforded a new species (2), assigned as an iron(IV)-oxo complex, i.e., [Fe^IV(^tBu₄Pc)O]. Its formation is rationalized by thermal homolysis of the OCl bond in the chlorate ligand, leading to a one-electron oxidation of the metal center. Species 2 was characterized by UV–vis spectroscopy and ESI-MS, including an ¹⁸O-isotope exchange experiment to confirm the formation of a transient Fe(IV)=O moiety. The oxidation reactivity of the resulting iron–oxo complex was evaluated with a range of organic substrates in CH₃CN, unless otherwise specified. Overall, the second-order rate constants determined under pseudo-first-order conditions revealed that 2 exhibits moderate and substrate-dependent reactivity with pronounced solvent effects, providing the first kinetic insight into iron–oxo chemistry on a phthalocyanine framework.

铁（III）四叔丁基酞菁氯化物[FeIII(tBu₄Pc)Cl](1)与AgClO₃在厌氧CH₃CN中氧化，迅速产生了一个新的物种(2)，被指定为铁(IV)-氧配合物，即[FeIV(tBu₄Pc)O]。氯酸盐配体中OCl键的热均裂使其形成合理化，导致金属中心的单电子氧化。物种2通过紫外可见光谱和ESI-MS进行了表征，并进行了18o同位素交换实验，以确认其形成了一个瞬态的Fe(IV)=O片段。得到的铁-氧配合物的氧化反应活性在CH₃CN中用一系列有机底物进行了评估，除非另有说明。总的来说，在伪一阶条件下测定的二阶速率常数表明，2具有温和的底物依赖性反应性，具有明显的溶剂效应，为酞菁框架上的铁氧化学提供了第一个动力学见解。

{"title":"Generation, characterization, and reactivity of a phthalocyanine iron–oxo complex","authors":"Candice Schlabach, Chibuzor Uwazie, Rui Zhang","doi":"10.1016/j.ica.2026.123084","DOIUrl":"10.1016/j.ica.2026.123084","url":null,"abstract":"<div><div>Oxidation of iron(III) tetra-tert-butylphthalocyanine chloride [FeIII(tBu₄Pc)Cl] (1) with AgClO₃ in anaerobic CH₃CN rapidly afforded a new species (2), assigned as an iron(IV)-oxo complex, i.e., [FeIV(tBu₄Pc)O]. Its formation is rationalized by thermal homolysis of the O<img>Cl bond in the chlorate ligand, leading to a one-electron oxidation of the metal center. Species 2 was characterized by UV–vis spectroscopy and ESI-MS, including an 18O-isotope exchange experiment to confirm the formation of a transient Fe(IV)=O moiety. The oxidation reactivity of the resulting iron–oxo complex was evaluated with a range of organic substrates in CH₃CN, unless otherwise specified. Overall, the second-order rate constants determined under pseudo-first-order conditions revealed that 2 exhibits moderate and substrate-dependent reactivity with pronounced solvent effects, providing the first kinetic insight into iron–oxo chemistry on a phthalocyanine framework.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123084"},"PeriodicalIF":3.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035664","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Acylthiourea ligands in Ru(II)–arene chemistry: Coordination modes, structural insights, solvent and pH effects Ru(II) -芳烃化学中的酰基硫脲配体：配位模式、结构见解、溶剂和pH效应

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2026-05-01 Epub Date: 2026-01-10 DOI: 10.1016/j.ica.2026.123077

Amir Karim , Rahime Eshaghi Malekshah , Najeeb Ullah , Sodio C.N. Hsu

Acylthiourea ligands have garnered significant attention for their structural versatility and rich coordination chemistry, attributed to the presence of both hard (N,O) and soft (S) donor atoms within their frameworks. In organoruthenium(II) complexes, these ligands predominantly coordinate in a monodentate fashion via the thiocarbonyl sulfur, particularly in nonpolar or moderately polar solvents. However, under polar protic or basic conditions, bidentate coordination involving (N,S) or (O,S) donor sets becomes favorable, driven by deprotonation of the amide moiety. In Ru(II)–arene acylthiourea complexes, ligands bearing a primary thioamide functionality preferentially adopt an (N,S) bidentate coordination mode, whereas those incorporating a secondary thioamide moiety predominantly exhibit (O,S) bidentate chelation. Binuclear Ru(II)–arene complexes are obtained with specifically designed acylthiourea ligands, wherein one Ru center is coordinated through an (S,N) chelation mode while the second Ru center is bound via (O,S) chelation. This diversity in coordination modes underscores the structural adaptability of acylthiourea ligands and supports their broad applicability in the design of functional metal complexes for use in catalysis, materials development, and bioinorganic chemistry. This review provides a critical analysis of the general synthetic methodologies employed for the preparation of acylthiourea ligands and evaluates their coordination behavior and binding modes within organoruthenium complexes. This review also focuses on the effects of ligand design, solvent polarity, reaction pH, and thioamide substitution patterns on the coordination behavior of acylthiourea ligands in Ru(II) complexes.

酰基硫脲配体因其结构的多功能性和丰富的配位化学而引起了人们的极大关注，这是由于在其框架内存在硬（N，O）和软(S)给体原子。在有机钌（II）配合物中，这些配体主要通过硫羰基硫以单齿方式配位，特别是在非极性或中极性溶剂中。然而，在极性质子或碱性条件下，由于酰胺部分的去质子化，涉及（N，S）或（O，S）供体集的双齿配位变得有利。在Ru(II) -芳烃酰基硫脲配合物中，具有一级硫酰胺功能的配体优先采用（N，S）双齿配位模式，而含有二级硫酰胺部分的配体主要表现为（O，S）双齿配位模式。通过特别设计的酰基硫脲配体得到双核Ru(II) -芳烃配合物，其中一个Ru中心通过（S，N）螯合模式配位，而第二个Ru中心通过（O，S）螯合模式结合。这种配位模式的多样性强调了酰基硫脲配体的结构适应性，并支持它们在设计用于催化、材料开发和生物无机化学的功能金属配合物方面的广泛适用性。本文综述了用于制备酰基硫脲配体的一般合成方法，并评估了它们在有机钌配合物中的配位行为和结合模式。本文还综述了配体设计、溶剂极性、反应pH和硫酰胺取代模式对Ru（II）配合物中酰基硫脲配体配位行为的影响。

{"title":"Acylthiourea ligands in Ru(II)–arene chemistry: Coordination modes, structural insights, solvent and pH effects","authors":"Amir Karim , Rahime Eshaghi Malekshah , Najeeb Ullah , Sodio C.N. Hsu","doi":"10.1016/j.ica.2026.123077","DOIUrl":"10.1016/j.ica.2026.123077","url":null,"abstract":"<div><div>Acylthiourea ligands have garnered significant attention for their structural versatility and rich coordination chemistry, attributed to the presence of both hard (N,O) and soft (S) donor atoms within their frameworks. In organoruthenium(II) complexes, these ligands predominantly coordinate in a monodentate fashion via the thiocarbonyl sulfur, particularly in nonpolar or moderately polar solvents. However, under polar protic or basic conditions, bidentate coordination involving (N,S) or (O,S) donor sets becomes favorable, driven by deprotonation of the amide moiety. In Ru(II)–arene acylthiourea complexes, ligands bearing a primary thioamide functionality preferentially adopt an (N,S) bidentate coordination mode, whereas those incorporating a secondary thioamide moiety predominantly exhibit (O,S) bidentate chelation. Binuclear Ru(II)–arene complexes are obtained with specifically designed acylthiourea ligands, wherein one Ru center is coordinated through an (S,N) chelation mode while the second Ru center is bound via (O,S) chelation. This diversity in coordination modes underscores the structural adaptability of acylthiourea ligands and supports their broad applicability in the design of functional metal complexes for use in catalysis, materials development, and bioinorganic chemistry. This review provides a critical analysis of the general synthetic methodologies employed for the preparation of acylthiourea ligands and evaluates their coordination behavior and binding modes within organoruthenium complexes. This review also focuses on the effects of ligand design, solvent polarity, reaction pH, and thioamide substitution patterns on the coordination behavior of acylthiourea ligands in Ru(II) complexes.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123077"},"PeriodicalIF":3.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035754","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Computational insights into thiourea derivatives and their copper complexes as potential CDK inhibitors in HCT116 colon carcinoma cells 硫脲衍生物及其铜络合物在HCT116结肠癌细胞中作为潜在CDK抑制剂的计算见解

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2026-05-01 Epub Date: 2026-01-23 DOI: 10.1016/j.ica.2026.123087

Rahime Eshaghi Malekshah , Amir Karim , Jebiti Haribabu , Anantha Krishnan Dhanabalan , Daniel Moraga , Najeeb Ullah , Sodio C.N. Hsu

N-Acylthiourea derivatives bearing a piperazinyl group are valuable anticancer scaffolds due to their structural versatility, favorable physicochemical properties, and ability to interact with multiple cancer-related biological targets. They are considered promising leads for developing new chemotherapeutic agents. In this study, ten ligands were synthesized in our laboratory and evaluated for their cytotoxic activity against HCT116 colon carcinoma cells. Building on these findings, we designed and computationally modeled novel copper(I) complexes of the ligands as potential inhibitors of cyclin-dependent kinase 2 (CDK2), a well-established therapeutic target in colorectal cancer. A comprehensive in silico approach was employed, including molecular docking, ADMET prediction, and drug-likeness evaluation. The ligands and their copper(I) complexes were docked against the CDK2 crystal structure (PDB ID: 2VTO), and binding affinities were assessed. Before docking, all compounds were geometry optimized, and their electronic properties, such as total energy and HOMO/LUMO orbital distributions, were calculated to inform docking simulations. ProTox 3.0 predicted all compounds to be non-toxic across major endpoints, with inactivity probabilities ranging from 0.50 to 0.99. The results suggest that both the free ligands and their copper complexes exhibit favorable binding interactions with the CDK2 active site, supporting their potential as lead compounds for further development in colon cancer therapeutics. Molecular dynamics simulations using the selected OPLS-AA force field were performed to analyze RMSD, RMSF, and protein–ligand contacts for the best docking poses.

含有哌嗪基的n -酰基硫脲衍生物由于其结构通用性、良好的物理化学性质以及与多种癌症相关生物靶点相互作用的能力而成为有价值的抗癌支架。它们被认为是开发新的化疗药物的有希望的线索。在本研究中，我们在实验室合成了10种配体，并评估了它们对HCT116结肠癌细胞的细胞毒活性。基于这些发现，我们设计并计算模拟了新型铜(I)配合物作为细胞周期蛋白依赖性激酶2 （CDK2）的潜在抑制剂，CDK2是结直肠癌的一个公认的治疗靶点。采用综合的计算机方法，包括分子对接、ADMET预测和药物相似性评估。将配体及其铜(I)配合物与CDK2晶体结构（PDB ID: 2VTO）对接，并对其结合亲和力进行了评估。对接前，对所有化合物进行几何优化，并计算其电子性质，如总能量和HOMO/LUMO轨道分布，为对接模拟提供信息。ProTox 3.0预测所有化合物在主要终点都是无毒的，无活性概率在0.50到0.99之间。结果表明，游离配体及其铜络合物与CDK2活性位点表现出良好的结合相互作用，支持它们作为结肠癌治疗药物进一步开发的先导化合物的潜力。利用所选的OPLS-AA力场进行分子动力学模拟，分析最佳对接姿态的RMSD、RMSF和蛋白质-配体接触。

{"title":"Computational insights into thiourea derivatives and their copper complexes as potential CDK inhibitors in HCT116 colon carcinoma cells","authors":"Rahime Eshaghi Malekshah , Amir Karim , Jebiti Haribabu , Anantha Krishnan Dhanabalan , Daniel Moraga , Najeeb Ullah , Sodio C.N. Hsu","doi":"10.1016/j.ica.2026.123087","DOIUrl":"10.1016/j.ica.2026.123087","url":null,"abstract":"<div><div>N-Acylthiourea derivatives bearing a piperazinyl group are valuable anticancer scaffolds due to their structural versatility, favorable physicochemical properties, and ability to interact with multiple cancer-related biological targets. They are considered promising leads for developing new chemotherapeutic agents. In this study, ten ligands were synthesized in our laboratory and evaluated for their cytotoxic activity against HCT116 colon carcinoma cells. Building on these findings, we designed and computationally modeled novel copper(I) complexes of the ligands as potential inhibitors of cyclin-dependent kinase 2 (CDK2), a well-established therapeutic target in colorectal cancer. A comprehensive in silico approach was employed, including molecular docking, ADMET prediction, and drug-likeness evaluation. The ligands and their copper(I) complexes were docked against the CDK2 crystal structure (PDB ID: 2VTO<svg><path></path></svg>), and binding affinities were assessed. Before docking, all compounds were geometry optimized, and their electronic properties, such as total energy and HOMO/LUMO orbital distributions, were calculated to inform docking simulations. ProTox 3.0 predicted all compounds to be non-toxic across major endpoints, with inactivity probabilities ranging from 0.50 to 0.99. The results suggest that both the free ligands and their copper complexes exhibit favorable binding interactions with the CDK2 active site, supporting their potential as lead compounds for further development in colon cancer therapeutics. Molecular dynamics simulations using the selected OPLS-AA force field were performed to analyze RMSD, RMSF, and protein–ligand contacts for the best docking poses.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123087"},"PeriodicalIF":3.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074447","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","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 structural analysis of heteroleptic molybdenum(VI) complexes with N-alkoxy carboxamide ligands n -烷氧基羧酰胺杂电性钼配合物的合成及结构分析

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2026-04-01 Epub Date: 2026-01-06 DOI: 10.1016/j.ica.2026.123066

Sung Kwang Lee , Dongseong Park , Heenang Choi , Ji Yeon Ryu , Seung Uk Son , Bo Keun Park , Taek-Mo Chung

Bis(imido)molybdenum (VI) complexes have been studied for application as precursors in the molybdenum thin film deposition process, because of their structural stability and volatility. In this study, we introduced N-alkoxy carboxamide ligands to bis(tert-butylimido)molybdenum complex for synthesis of novel heteroleptic molybdenum(VI) complexes. Complexes, Mo(N^tBu)₂(mdpa)₂ (mdpaH = N-methoxy-2,2-dimethylpropanamide) (1), Mo(N^tBu)₂(edpa)₂ (edpaH = N-ethoxy-2,2-dimethylpropanamide) (2), Mo(N^tBu)₂(empa)₂ (empaH = N-ethoxy-2-methylpropanamide) (3), Mo(N^tBu)₂(mpa)₂ (mpaH = N-methoxypropanamide) (4), Mo(N^tBu)₂(bdpa)₂ (bdpaH = N-tert-butoxy-2,2-dimethylpropanamide) (5) and Mo(N^tBu)₂(etfa)₂ (etfaH = N-ethoxy-2,2,2-trifluoroacetamide) (6) were synthesized by double substitution reactions of Mo(N^tBu)₂Cl₂(DME) (DME = 1,2-dimethoxyethane) and sodium salt of N-alkoxy carboxamide in hexane. All new complexes were then characterized by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FT-IR) and elemental analysis (EA). To confirm the precise structure, complex 1 was analyzed by single crystal X-ray diffraction (SC-XRD). An X-ray single crystallographic study showed that complex 1 exists in a distorted octahedral molecular geometry, in which molybdenum is bound to the N- and O- atoms of the respective ligand. Thermal properties of the complexes were investigated by thermogravimetric analysis (TGA). It showed that all complexes were both vaporized and decomposed in the analysis range. The volatility of complex 4 was measured by vapor pressure measurement and it indicates that complex 4 has enough volatility (1 Torr @ 74.8 °C) for the vapor-phase deposition process.

双（亚胺）钼（VI）配合物由于其结构稳定性和易挥发性，被研究作为钼薄膜沉积过程中的前驱物。在本研究中，我们将n -烷氧基羧酰胺配体引入到双（叔丁基氨基）钼配合物上，合成了新型杂电性钼（VI）配合物。配合物Mo(NtBu)2(mdpa)2 （mdpaH = n -甲氧基-2,2-二甲基丙酰胺）(1)、Mo(NtBu)2(edpa)2 （edpaH = n -乙氧基-2,2-二甲基丙酰胺）(2)、Mo(NtBu)2(empa)2 （empaH = n -乙氧基-2-甲基丙酰胺）(3)、Mo(NtBu)2(mpa)2 （mpaH = n -甲氧基丙酰胺）(4)、以Mo(NtBu)2Cl2(DME) （DME = 1,2-二甲氧基乙烷）与n -烷氧基羧酰胺钠盐在己烷中进行双取代反应，合成Mo(NtBu)2(bdpa)2 （bdpaH = n -叔丁基-2,2-二甲基丙酰胺）(5)和Mo(NtBu)2(etfa)2 （etfaH = n -乙氧基-2,2,2-三氟乙酰胺）(6)。然后用核磁共振光谱（NMR）、傅里叶变换红外光谱（FT-IR）和元素分析（EA）对所有新配合物进行了表征。为确定配合物1的精确结构，采用单晶x射线衍射（SC-XRD）对其进行了分析。x射线单晶学研究表明，配合物1存在于扭曲的八面体分子几何结构中，其中钼与相应配体的N和O原子结合。用热重分析（TGA）研究了配合物的热性能。结果表明，在分析范围内，所有配合物均发生汽化和分解。通过蒸汽压测定了配合物4的挥发性，表明配合物4具有足够的挥发性（1 Torr @ 74.8°C），适合气相沉积过程。

{"title":"Synthesis and structural analysis of heteroleptic molybdenum(VI) complexes with N-alkoxy carboxamide ligands","authors":"Sung Kwang Lee , Dongseong Park , Heenang Choi , Ji Yeon Ryu , Seung Uk Son , Bo Keun Park , Taek-Mo Chung","doi":"10.1016/j.ica.2026.123066","DOIUrl":"10.1016/j.ica.2026.123066","url":null,"abstract":"<div><div>Bis(imido)molybdenum (VI) complexes have been studied for application as precursors in the molybdenum thin film deposition process, because of their structural stability and volatility. In this study, we introduced N-alkoxy carboxamide ligands to bis(tert-butylimido)molybdenum complex for synthesis of novel heteroleptic molybdenum(VI) complexes. Complexes, Mo(NtBu)2(mdpa)2 (mdpaH = N-methoxy-2,2-dimethylpropanamide) (1), Mo(NtBu)2(edpa)2 (edpaH = N-ethoxy-2,2-dimethylpropanamide) (2), Mo(NtBu)2(empa)2 (empaH = N-ethoxy-2-methylpropanamide) (3), Mo(NtBu)2(mpa)2 (mpaH = N-methoxypropanamide) (4), Mo(NtBu)2(bdpa)2 (bdpaH = N-tert-butoxy-2,2-dimethylpropanamide) (5) and Mo(NtBu)2(etfa)2 (etfaH = N-ethoxy-2,2,2-trifluoroacetamide) (6) were synthesized by double substitution reactions of Mo(NtBu)2Cl2(DME) (DME = 1,2-dimethoxyethane) and sodium salt of N-alkoxy carboxamide in hexane. All new complexes were then characterized by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FT-IR) and elemental analysis (EA). To confirm the precise structure, complex 1 was analyzed by single crystal X-ray diffraction (SC-XRD). An X-ray single crystallographic study showed that complex 1 exists in a distorted octahedral molecular geometry, in which molybdenum is bound to the N- and O- atoms of the respective ligand. Thermal properties of the complexes were investigated by thermogravimetric analysis (TGA). It showed that all complexes were both vaporized and decomposed in the analysis range. The volatility of complex 4 was measured by vapor pressure measurement and it indicates that complex 4 has enough volatility (1 Torr @ 74.8 °C) for the vapor-phase deposition process.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123066"},"PeriodicalIF":3.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939889","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0