Pub Date : 2025-12-18DOI: 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。
{"title":"Synthesis of gas-phase, group II metal hydride cations using preparative tandem mass spectrometry","authors":"Madeline R. Handel , Samuel J. Lenze , Lucas G. Fuller , Theodore A. Corcovilos , Michael J. van Stipdonk","doi":"10.1016/j.ica.2025.123043","DOIUrl":"10.1016/j.ica.2025.123043","url":null,"abstract":"<div><div>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 (PTMS<sup>n</sup>) 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]<sup>+</sup> (Met = Ca, Sr, Ba) and (b) allows for monitoring of intrinsic reactions with neutral species such as H<sub>2</sub>O and CH<sub>2</sub>Cl<sub>2</sub>. When exposed to H<sub>2</sub>O, the [MetH]<sup>+</sup> cations undergo a hydrolysis reaction to form the respective cationic, metal hydroxides. When allowed to react with CH<sub>2</sub>Cl<sub>2</sub>, two reaction pathways are observed, one leading to formation of [Met(CHCl<sub>2</sub>)]<sup>+</sup> (with elimination of neutral H<sub>2</sub>) and the other producing [MetCl]<sup>+</sup> (by elimination of CH<sub>3</sub>Cl). The reactions to generate the [MetH]<sup>+</sup> cations, and the ion-molecule reactions with H<sub>2</sub>O and CH<sub>2</sub>Cl<sub>2</sub>, 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.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123043"},"PeriodicalIF":3.2,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837297","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}
Pub Date : 2025-12-16DOI: 10.1016/j.ica.2025.123041
Manli Cao , Suyang Yao , Lulu Ren, Zhiyu Zhao, Shaojun Mao, Shengqiang Jiang
Octahedral chiral-at-Ir(III) complexes exhibit high structural stability and stereoselectivity in asymmetric synthesis. These properties enable them to serve as efficient chiral templates, inducing asymmetry in coordinated ligands. In our previous work, we have proved such chiral-at-Ir(III) complexes could coordinate to commercial amino acids and further oxidative dehydrogenation to imines. To further investigate this oxidative dehydrogenation process in complexes with different cyclometalating ligands, here we employed a fluoro-substituted 2-(2,4-difluorophenyl)pyridine (dfppy) as a cyclometalating ligand to synthesize the chiral Ir(III) precursor Λ-[Ir(dfppy)₂(MeCN)₂]PF₆. This complex was coordinated with D- and L-valine to yield two diastereomeric complexes, Λ-[Ir(dfppy)₂(D-val)] and Λ-[Ir(dfppy)₂(L-val)] (Val is Valine). The structure and oxidative dehydrogenation ability of these obtained diastereomers were investigated. Under visible-light irradiation, both complexes underwent dehydrogenative oxidation of the valine moiety and Λ-[Ir(dfppy)₂(D-val)] exhibited faster photooxidation kinetics than its L-valine counterpart. Their component, structural and photophysical properties were characterized by 1H NMR, mass spectrometry, single-crystal X-ray diffraction, UV–vis spectra and emission spectra.
{"title":"Synthesis, structure and photooxidative dehydrogenation of chiral Ir(III) valine complexes based on precursor [Λ-Ir(dfppy)2(MeCN)2](PF6)","authors":"Manli Cao , Suyang Yao , Lulu Ren, Zhiyu Zhao, Shaojun Mao, Shengqiang Jiang","doi":"10.1016/j.ica.2025.123041","DOIUrl":"10.1016/j.ica.2025.123041","url":null,"abstract":"<div><div>Octahedral chiral-at-Ir(III) complexes exhibit high structural stability and stereoselectivity in asymmetric synthesis. These properties enable them to serve as efficient chiral templates, inducing asymmetry in coordinated ligands. In our previous work, we have proved such chiral-at-Ir(III) complexes could coordinate to commercial amino acids and further oxidative dehydrogenation to imines. To further investigate this oxidative dehydrogenation process in complexes with different cyclometalating ligands, here we employed a fluoro-substituted 2-(2,4-difluorophenyl)pyridine (dfppy) as a cyclometalating ligand to synthesize the chiral Ir(III) precursor Λ-[Ir(dfppy)₂(MeCN)₂]PF₆. This complex was coordinated with <em>D</em>- and <em>L</em>-valine to yield two diastereomeric complexes, Λ-[Ir(dfppy)₂(<em>D</em>-val)] and Λ-[Ir(dfppy)₂(<em>L</em>-val)] (Val is Valine). The structure and oxidative dehydrogenation ability of these obtained diastereomers were investigated. Under visible-light irradiation, both complexes underwent dehydrogenative oxidation of the valine moiety and Λ-[Ir(dfppy)₂(<em>D</em>-val)] exhibited faster photooxidation kinetics than its L-valine counterpart. Their component, structural and photophysical properties were characterized by <sup>1</sup>H NMR, mass spectrometry, single-crystal X-ray diffraction, UV–vis spectra and emission spectra.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123041"},"PeriodicalIF":3.2,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882485","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}
Pub Date : 2025-12-14DOI: 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 (ɸΔ = 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.
{"title":"Synthesis, photophysicochemical and electrochemical properties of new peripheral tetra-substituted Zn(II) phthalocyanines bearing quinoline groups","authors":"Barış Seçkin Arslan , Nagihan Öztürk , Mehmet Nebioğlu , İlkay Şişman","doi":"10.1016/j.ica.2025.123040","DOIUrl":"10.1016/j.ica.2025.123040","url":null,"abstract":"<div><div>This study focuses on the synthesis of novel zinc phthalocyanines containing tetra-((6,7,8-trimethoxytetrazolo[1,5-<em>a</em>]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 (<strong>5a</strong>) and tetramethoxy (<strong>5b</strong>) quinoline moieties and their corresponding peripherally substituted zinc(II) phthalocyanine complexes (<strong>BIM8</strong> and <strong>BIM9</strong>) 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 <strong>BIM8</strong>, <strong>BIM9</strong> exhibited superior photochemical performance, including a high singlet oxygen quantum yield (ɸ<sub>Δ</sub> = 0.89), negligible aggregation tendency, sufficient fluorescence emission for imaging purposes, and notable photostability. These results demonstrate that <strong>BIM9</strong> is a promising photosensitizer candidate for PDT.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123040"},"PeriodicalIF":3.2,"publicationDate":"2025-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787879","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}
Transition metal complexes bearing redox-active ligands often exhibit multiple accessible oxidation states resulting from the electronic interplay between the metal center and the coordinated ligand framework. This study focused on the synthesis and characterization of two mononuclear copper (II) complexes incorporating redox active ligands, 3-hydroxy-4-(hydroxyimino)naphthalen-1(4H)-one(LwOx) and 3-hydroxy-4-(methoxyimino)naphthalen-1(4H)-one (LwOx-Me), the ligands differ structurally by the substitution of hydrogen atom with a methyl group in the ligand oxime backbone, this small change affects the ability of the ligand to form intramolecular hydrogen bonds within metal complexes. Remarkably, both metal complexes display multiple redox events attributed to the combined redox-active nature of quinoneoxime-based ligands and the copper(II) center. Furthermore, both complexes were evaluated as catalysts in the oxidation of alcohols. [Cu(LwOx)2] exhibited excellent catalytic activity, whereas [Cu(LwOx-Me)2] showed negligible activity; DFT studies suggest the crucial role of intramolecular hydrogen bonding in modulating the catalytic activity of Cu(II) complexes.
{"title":"Ligand design and catalytic performance of Quinone-oxime copper complexes: role of intramolecular hydrogen bonding","authors":"Vivek Mokashi , Sourav Datta , Swapan Patra , Priyabrata Banerjee , Sunita Salunke-Gawali","doi":"10.1016/j.ica.2025.123039","DOIUrl":"10.1016/j.ica.2025.123039","url":null,"abstract":"<div><div>Transition metal complexes bearing redox-active ligands often exhibit multiple accessible oxidation states resulting from the electronic interplay between the metal center and the coordinated ligand framework. This study focused on the synthesis and characterization of two mononuclear copper (II) complexes incorporating redox active ligands, 3-hydroxy-4-(hydroxyimino)naphthalen-1(4H)-one(<strong>LwOx</strong>) and 3-hydroxy-4-(methoxyimino)naphthalen-1(4H)-one (<strong>LwOx-Me</strong>), the ligands differ structurally by the substitution of hydrogen atom with a methyl group in the ligand oxime backbone, this small change affects the ability of the ligand to form intramolecular hydrogen bonds within metal complexes. Remarkably, both metal complexes display multiple redox events attributed to the combined redox-active nature of quinoneoxime-based ligands and the copper(II) center. Furthermore, both complexes were evaluated as catalysts in the oxidation of alcohols. <strong>[Cu(LwOx)</strong><sub><strong>2</strong></sub><strong>]</strong> exhibited excellent catalytic activity, whereas <strong>[Cu(LwOx-Me)</strong><sub><strong>2</strong></sub><strong>]</strong> showed negligible activity; DFT studies suggest the crucial role of intramolecular hydrogen bonding in modulating the catalytic activity of Cu(II) complexes.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123039"},"PeriodicalIF":3.2,"publicationDate":"2025-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787876","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}
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.
{"title":"Synthetic strategy, structural aspects and biological applications of multinuclear cadmium complexes using salen type N2O2 donor ligands and N2O2O2′ donor compartmental ligands: A review","authors":"Puspendu Middya , Siddhartha Majhi , Shouvik Chattopadhyay","doi":"10.1016/j.ica.2025.123029","DOIUrl":"10.1016/j.ica.2025.123029","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123029"},"PeriodicalIF":3.2,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837298","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}
Pub Date : 2025-12-11DOI: 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。
{"title":"A straightforward approach for synthesizing vanadium-doped 2D MoSe2 as cathode in high-energy lithium-ion supercapacitors","authors":"Souvik Naskar, Ishita Naskar, Karan Kumar Gupta, Chung-Hsin Lu","doi":"10.1016/j.ica.2025.123038","DOIUrl":"10.1016/j.ica.2025.123038","url":null,"abstract":"<div><div>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 V<img>Mo 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<sup>−1</sup>, 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<sup>−1</sup> and a power density of 8.7 kW kg<sup>−1</sup>, 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.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123038"},"PeriodicalIF":3.2,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837296","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}
Pub Date : 2025-12-10DOI: 10.1016/j.ica.2025.123037
Yuan Huang , Grigore A. Timco , George F.S. Whitehead , Selena J. Lockyer , Niklas Geue , Zhibo Qi , Adam Brookfield , Peter Bencok , Perdita E. Barran , Nicholas F. Chilton , Michael L. Baker , Eric J.L. McInnes , Richard E.P. Winpenny
A rare example of a seven-membered heterometallic ring [CrIII6CeIIIF7(O2CtBu)14(THF)2] (MeCN)2 (1) and five eight-membered heterometallic rings, [nPr2NH2][CrIII6LnIII2F8(O2CtBu)17Lx] (2, Ln = Ce, L = HO2CtBu, x = 2, 3, Ln = Y, L = H2O, x = 1, 4, Ln = Gd, L = HO2CtBu, x = 1; 5, Ln = Tb, L = HO2CtBu, x = 1; 6, Ln = Yb, no L) have been synthesized and structurally characterized through X-ray diffraction. The structures consist of eight metals in an octagon, with Cr…Cr and Cr…Ln edges bridged by a fluoride and two carboxylates, while the Ln…Ln edges are bridged by a fluoride and three carboxylates. The magnetisation and susceptibility of these compounds were measured using SQUID magnetometry and electron paramagnetic resonance (EPR) spectroscopy. The magnetic data were fitted with antiferromagnetic exchange interactions between chromium(III) ions, which can be fitted in the {Cr6Y2} complex 3 and these parameters were then used to fit the magnetic properties of the {Cr6Gd2} complex 4 adding in exchange interactions between the CrIII and GdIII The magnetisation and susceptibility below 80 K of 1 and 2 were fitted on the basis of CASSCF-SO calculations at the CeIII site, and showed a weak ferromagnetic interaction between CrIII and CeIII. For 5 and 6 the magnetisation data was fitted by subtracting the data for 3 and treating the residual data as a {Tb2} and {Yb2} dimer respectively. The EPR spectra are rich, and for 3 can be modelled as due to S = 1 and S = 2 states of the {Cr6} chain. The spectra of 1 and 2 are similar, consistent with very weak interactions between the CeIII and the {Cr6} chain, while the spectra of 5 and 6 are different to that of 3, suggesting that the low temperature spectroscopy is due to a spin system in which the LnIII ions interact with the {Cr6} chain.
七人的一种罕见的例子heterometallic环[CrIII6CeIIIF7 (O2CtBu) 14(四氢呋喃)2](MeCN) 2(1)和五个8人heterometallic戒指,[nPr2NH2] [CrIII6LnIII2F8 (O2CtBu) 17 lx] (2 Ln = Ce L = HO2CtBu x = 2, 3, Ln = Y L = H2O, x = 1, 4, Ln = Gd, L = HO2CtBu x = 1; 5、Ln =结核,L = HO2CtBu x = 1; 6, Ln = Yb,没有L)已经合成并通过x射线衍射结构特征。该结构由八种金属组成，其中Cr…Cr和Cr…Ln边缘由一个氟化物和两个羧酸盐桥接，而Ln…Ln边缘由一个氟化物和三个羧酸盐桥接。用SQUID磁强计和电子顺磁共振（EPR）谱法测定了这些化合物的磁化率和磁化率。磁数据配备反铁磁性的交换铬(III)离子之间的相互作用,可以安装在{Cr6Y2}复杂3和这些参数被用来适应磁性{Cr6Gd2} 4添加复杂的交流之间的交互CrIII GdIII磁化强度和磁化率低于80 K的1和2是安装的基础上CASSCF-SO CeIII网站的计算,并显示一个弱铁磁CrIII和CeIII之间的互动。对于5和6，通过减去3的数据并将剩余数据分别处理为{Tb2}和{Yb2}二聚体来拟合磁化数据。EPR谱丰富，其中3可以建模为{Cr6}链的S = 1和S = 2态。1和2的光谱相似，符合CeIII与{Cr6}链之间非常弱的相互作用，而5和6的光谱与3的光谱不同，表明低温光谱是由LnIII离子与{Cr6}链相互作用的自旋系统引起的。
{"title":"Magnetic and EPR spectroscopic studies of heterometallic rings featuring {Cr6} chains and rare-earth metal centres","authors":"Yuan Huang , Grigore A. Timco , George F.S. Whitehead , Selena J. Lockyer , Niklas Geue , Zhibo Qi , Adam Brookfield , Peter Bencok , Perdita E. Barran , Nicholas F. Chilton , Michael L. Baker , Eric J.L. McInnes , Richard E.P. Winpenny","doi":"10.1016/j.ica.2025.123037","DOIUrl":"10.1016/j.ica.2025.123037","url":null,"abstract":"<div><div>A rare example of a seven-membered heterometallic ring [Cr<sup>III</sup><sub>6</sub>Ce<sup>III</sup>F<sub>7</sub>(O<sub>2</sub>C<sup><em>t</em></sup>Bu)<sub>14</sub>(THF)<sub>2</sub>] (MeCN)<sub>2</sub> (<strong>1</strong>) and five eight-membered heterometallic rings, [<sup><em>n</em></sup>Pr<sub>2</sub>NH<sub>2</sub>][Cr<sup>III</sup><sub>6</sub>Ln<sup>III</sup><sub>2</sub>F<sub>8</sub>(O<sub>2</sub>C<sup><em>t</em></sup>Bu)<sub>17</sub>L<sub>x</sub>] (<strong>2</strong>, Ln = Ce, L = HO<sub>2</sub>C<sup><em>t</em></sup>Bu, x = 2, <strong>3</strong>, Ln = Y, L = H<sub>2</sub>O, x = 1, <strong>4</strong>, Ln = Gd, L = HO<sub>2</sub>C<sup><em>t</em></sup>Bu, x = 1; <strong>5</strong>, Ln = Tb, L = HO<sub>2</sub>C<sup><em>t</em></sup>Bu, x = 1; <strong>6</strong>, Ln = Yb, no L) have been synthesized and structurally characterized through X-ray diffraction. The structures consist of eight metals in an octagon, with Cr…Cr and Cr…Ln edges bridged by a fluoride and two carboxylates, while the Ln…Ln edges are bridged by a fluoride and three carboxylates. The magnetisation and susceptibility of these compounds were measured using SQUID magnetometry and electron paramagnetic resonance (EPR) spectroscopy. The magnetic data were fitted with antiferromagnetic exchange interactions between chromium(III) ions, which can be fitted in the {Cr<sub>6</sub>Y<sub>2</sub>} complex <strong>3</strong> and these parameters were then used to fit the magnetic properties of the {Cr<sub>6</sub>Gd<sub>2</sub>} complex <strong>4</strong> adding in exchange interactions between the Cr<sup>III</sup> and Gd<sup>III</sup> The magnetisation and susceptibility below 80 K of <strong>1</strong> and <strong>2</strong> were fitted on the basis of CASSCF-SO calculations at the Ce<sup>III</sup> site, and showed a weak ferromagnetic interaction between Cr<sup>III</sup> and Ce<sup>III.</sup> For <strong>5</strong> and <strong>6</strong> the magnetisation data was fitted by subtracting the data for <strong>3</strong> and treating the residual data as a {Tb<sub>2</sub>} and {Yb<sub>2</sub>} dimer respectively. The EPR spectra are rich, and for <strong>3</strong> can be modelled as due to <em>S</em> = 1 and <em>S</em> = 2 states of the {Cr<sub>6</sub>} chain. The spectra of <strong>1</strong> and <strong>2</strong> are similar, consistent with very weak interactions between the Ce<sup>III</sup> and the {Cr<sub>6</sub>} chain, while the spectra of <strong>5</strong> and <strong>6</strong> are different to that of <strong>3</strong>, suggesting that the low temperature spectroscopy is due to a spin system in which the Ln<sup>III</sup> ions interact with the {Cr<sub>6</sub>} chain.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123037"},"PeriodicalIF":3.2,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787882","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}
The increasing global energy demand and the environmental impacts of fossil fuel consumption have driven the exploration of sustainable energy alternatives. Hydrogen is a promising clean energy carrier, particularly when produced via renewable-powered electrolysis. However, the efficiency of conventional water electrolysis is limited by the sluggish kinetics of the oxygen evolution reaction (OER). This study explores methanol electrooxidation as a more energy-efficient anodic alternative to OER in hydrogen generation systems. We synthesized 50 wt% Pt₁Ru₁ catalysts supported on Ketjenblack carbon (PtRu/C) via two sulphite-complex-based routes: (i) sequential impregnation of Ru onto preformed Pt-sulphite complexes, and (ii) direct mixing of Pt- and Ru-sulphite precursors. The resulting catalysts were characterized using X-ray diffraction (XRD), X-ray fluorescence (XRF), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) to assess their crystallinity, phase composition, morphology, and surface properties. The electrochemical performance was evaluated through methanol electroreforming experiments conducted in a membrane–electrode assembly (MEA) configuration. Full-cell tests conducted at 90 °C revealed an initial enhancement in performance for the catalyst with Ru impregnated onto Pt-sulphite, despite the presence of some non-alloyed Ru particles. In contrast, the PtRu/C-based MEA prepared by mixing Pt- and Ru-sulphite exhibited superior durability during a 24-h chronopotentiometric test, likely due to PtRu alloy formation and the enhanced stability of Ru within the alloy. These results confirm the potential of optimized PtRu/C systems for efficient hydrogen production via methanol electroreforming and highlight the importance of synthesis strategy in tuning electrocatalyst performance and durability.
{"title":"Electroreforming of methanol employing in-house prepared PtRu/C anode catalysts for hydrogen generation at the cathode","authors":"Carmelo Lo Vecchio, Angelo Mondello, Riccardo Dollenz, Erminia Mosca, Vincenzo Baglio","doi":"10.1016/j.ica.2025.123028","DOIUrl":"10.1016/j.ica.2025.123028","url":null,"abstract":"<div><div>The increasing global energy demand and the environmental impacts of fossil fuel consumption have driven the exploration of sustainable energy alternatives. Hydrogen is a promising clean energy carrier, particularly when produced via renewable-powered electrolysis. However, the efficiency of conventional water electrolysis is limited by the sluggish kinetics of the oxygen evolution reaction (OER). This study explores methanol electrooxidation as a more energy-efficient anodic alternative to OER in hydrogen generation systems. We synthesized 50 wt% Pt₁Ru₁ catalysts supported on Ketjenblack carbon (PtRu/C) via two sulphite-complex-based routes: (i) sequential impregnation of Ru onto preformed Pt-sulphite complexes, and (ii) direct mixing of Pt- and Ru-sulphite precursors. The resulting catalysts were characterized using X-ray diffraction (XRD), X-ray fluorescence (XRF), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) to assess their crystallinity, phase composition, morphology, and surface properties. The electrochemical performance was evaluated through methanol electroreforming experiments conducted in a membrane–electrode assembly (MEA) configuration. Full-cell tests conducted at 90 °C revealed an initial enhancement in performance for the catalyst with Ru impregnated onto Pt-sulphite, despite the presence of some non-alloyed Ru particles. In contrast, the PtRu/C-based MEA prepared by mixing Pt- and Ru-sulphite exhibited superior durability during a 24-h chronopotentiometric test, likely due to Pt<img>Ru alloy formation and the enhanced stability of Ru within the alloy. These results confirm the potential of optimized PtRu/C systems for efficient hydrogen production via methanol electroreforming and highlight the importance of synthesis strategy in tuning electrocatalyst performance and durability.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123028"},"PeriodicalIF":3.2,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734156","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}
Pub Date : 2025-12-09DOI: 10.1016/j.ica.2025.123033
Ghodrat Mahmoudi , Asmet N. Azizova , Mateusz Janeta , Ömer Faruk Tutar , Ennio Zangrando , Nabajyoti Baildya , Eugeny V. Alexandrov , Subhadip Roy , Suman Adhikari
The development of efficient one-pot methodologies for the in situ construction of polydentate N-heterocyclic ligands and their integration into coordination frameworks remains a central challenge in synthetic inorganic chemistry. Herein, we report a one-pot reaction of amino-functionalized pyridine (iso)nicotinoyl hydrazones, thiocyanate, and Mn(II) salts in acetonitrile, which yields two new mixed-ligand Mn(II) coordination complexes, [Mn(HL3)2(NCS)2(H2O)2] (1) and [Mn(HL4)4(NCS)2].CH3CN.0.5(H2O) (2), where HL3 and HL4 represents two in situ formed dipyridyl-1H-1,2,4-triazole ligands. These ligands are formed through a Mn(II)-assisted cyclization of amino-functionalized pyridine (iso)nicotinoyl hydrazone precursors (HL1 and HL2 in acetonitrile). Single-crystal X-ray diffraction confirms the in situ ligand transformation and reveals that both complexes contain six-coordinate Mn(II) centers in distorted octahedral environments, extended through diverse noncovalent interactions into higher-dimensional frameworks. Furthermore, the electronic properties of both complexes 1 and 2 have been demonstrated through theoretical studies based on DFT calculations. Molecular packings of both complexes 1 and 2 show similarity for the first five levels of intermolecular interaction strength. Mechanistically, this work demonstrates the dual catalytic and template roles of Mn(II) in directing both ligand evolution and supramolecular architecture. Overall, this work presents a practical and generalizable strategy for the one-pot synthesis of adaptive coordination materials via metal-mediated heterocycle construction, contributing to ongoing advances in crystal engineering and supramolecular design.
{"title":"Mn(II)-mediated in situ cyclization of amino functionalized pyridine (iso)nicotinoyl-hydrazones into dipyridyltriazoles: One-pot route to supramolecular Mn(II)-complexes","authors":"Ghodrat Mahmoudi , Asmet N. Azizova , Mateusz Janeta , Ömer Faruk Tutar , Ennio Zangrando , Nabajyoti Baildya , Eugeny V. Alexandrov , Subhadip Roy , Suman Adhikari","doi":"10.1016/j.ica.2025.123033","DOIUrl":"10.1016/j.ica.2025.123033","url":null,"abstract":"<div><div>The development of efficient one-pot methodologies for the <em>in situ</em> construction of polydentate N-heterocyclic ligands and their integration into coordination frameworks remains a central challenge in synthetic inorganic chemistry. Herein, we report a one-pot reaction of amino-functionalized pyridine (iso)nicotinoyl hydrazones, thiocyanate, and Mn(II) salts in acetonitrile, which yields two new mixed-ligand Mn(II) coordination complexes, [Mn(HL<sup>3</sup>)<sub>2</sub>(NCS)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>] (<strong>1</strong>) and [Mn(HL<sup>4</sup>)<sub>4</sub>(NCS)<sub>2</sub>].CH<sub>3</sub>CN.0.5(H<sub>2</sub>O) (<strong>2</strong>), where HL<sup>3</sup> and HL<sup>4</sup> represents two <em>in situ</em> formed dipyridyl-1H-1,2,4-triazole ligands. These ligands are formed through a Mn(II)-assisted cyclization of amino-functionalized pyridine (iso)nicotinoyl hydrazone precursors (HL<sup>1</sup> and HL<sup>2</sup> in acetonitrile). Single-crystal X-ray diffraction confirms the <em>in situ</em> ligand transformation and reveals that both complexes contain six-coordinate Mn(II) centers in distorted octahedral environments, extended through diverse noncovalent interactions into higher-dimensional frameworks. Furthermore, the electronic properties of both complexes <strong>1</strong> and <strong>2</strong> have been demonstrated through theoretical studies based on DFT calculations. Molecular packings of both complexes <strong>1</strong> and <strong>2</strong> show similarity for the first five levels of intermolecular interaction strength. Mechanistically, this work demonstrates the dual catalytic and template roles of Mn(II) in directing both ligand evolution and supramolecular architecture. Overall, this work presents a practical and generalizable strategy for the one-pot synthesis of adaptive coordination materials <em>via</em> metal-mediated heterocycle construction, contributing to ongoing advances in crystal engineering and supramolecular design.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123033"},"PeriodicalIF":3.2,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787881","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}
Pub Date : 2025-12-08DOI: 10.1016/j.ica.2025.123032
Abigail L. Moffett , Eleanor C. Beams , Jeffrey D. Zigbuo , Colin D. McMillen , Anthony R. Chianese , Kerry-Ann Green
Dinuclear nickel(II) complexes (4a–4d) of bidentate propylene-bridged bisbenzimidazolin-2-ylidene ligands are reported. The molecular structures were confirmed by single-crystal X-ray diffraction analysis as 16-membered metallacycles. The double-bridging bidentate bis(N-heterocyclic carbenes) exhibit a trans arrangement to each other about two square planar Ni centers with trans bromide ligands. The molecular structures adopt a stretched-out or open-ring conformation with the absence of any intramolecular Ni···Ni interactions. The complexes are distinguished by the identity of the N-wingtip groups and their benzimidazole backbones. The catalytic activity of the dinuclear complexes (4a–4d) and their corresponding monochelate counterparts (3a–3d) in the Suzuki-Miyaura coupling and reductive cleavage reactions of aryl sulfamates is discussed.
{"title":"An investigation of dinuclear nickel(II) complexes featuring double-bridging bis(N-heterocyclic carbene) ligands","authors":"Abigail L. Moffett , Eleanor C. Beams , Jeffrey D. Zigbuo , Colin D. McMillen , Anthony R. Chianese , Kerry-Ann Green","doi":"10.1016/j.ica.2025.123032","DOIUrl":"10.1016/j.ica.2025.123032","url":null,"abstract":"<div><div>Dinuclear nickel(II) complexes (<strong>4a–4d</strong>) of bidentate propylene-bridged bisbenzimidazolin-2-ylidene ligands are reported. The molecular structures were confirmed by single-crystal X-ray diffraction analysis as 16-membered metallacycles. The double-bridging bidentate bis(N-heterocyclic carbenes) exhibit a <em>trans</em> arrangement to each other about two square planar Ni centers with <em>trans</em> bromide ligands. The molecular structures adopt a stretched-out or open-ring conformation with the absence of any intramolecular Ni···Ni interactions. The complexes are distinguished by the identity of the N-wingtip groups and their benzimidazole backbones. The catalytic activity of the dinuclear complexes (<strong>4a–4d</strong>) and their corresponding monochelate counterparts (<strong>3a–3d</strong>) in the Suzuki-Miyaura coupling and reductive cleavage reactions of aryl sulfamates is discussed.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123032"},"PeriodicalIF":3.2,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787877","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}
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