Inorganica Chimica Acta最新文献

{"title":"Blue-emitting iridophosphors featuring difluorophenylpyridine groups for solution-processed OLEDs","authors":"Jiangyu Zhu ,&nbsp;Lixiang Li ,&nbsp;Xianxi Liang ,&nbsp;Baohua Zhang ,&nbsp;Song Guo","doi":"10.1016/j.ica.2025.122935","DOIUrl":"10.1016/j.ica.2025.122935","url":null,"abstract":"<div><div>Two blue-emissive cationic iridophosphors (<strong>Ir1</strong> and <strong>Ir2)</strong> featuring 2-(2,4-difluorophenyl)pyridine as the cyclometalated ligand, and 2-(pyrazol-1-yl)pyridine (pzpy) and 4-(dimethylamino)-2-(pyrazol-1-yl)pyridine (dmapzpy) as the auxiliary ligands have been synthesized, and the luminescent characterization of these emitters has been investigated. Solution-phase photoluminescence spectra of <strong>Ir1/Ir2</strong> in CH₂Cl₂ exhibited blue emission peaking at 453 and 456 nm, respectively. The electroluminescence based on the two complexes suggested that the electroluminescent performance of the devices significantly improved with increasing the doping concentration. Among them, the device doped with 30 wt% <strong>Ir1</strong> demonstrated the optimal performance with the EQE_max of 4.97 %, the maximum luminance of 280 cd/m², the CE_max of 9.30 cd/A, and the PE_max of 5.31 lm/W.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122935"},"PeriodicalIF":3.2,"publicationDate":"2025-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145217456","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}

{"title":"Synthesis and structural insights into metal Bis(dithiolene) complexes featuring redox-active N-heterocyclic Carbenes","authors":"Selvakumar Jayaraman,&nbsp;Dilsha Samanali Wickramasinghe,&nbsp;Kuppuswamy Arumugam","doi":"10.1016/j.ica.2025.122921","DOIUrl":"10.1016/j.ica.2025.122921","url":null,"abstract":"<div><div>Iron and cobalt bis(dithiolene) complexes bearing redox-active N-heterocyclic carbenes (RA-NHC) of the type (RA-NHC)M(S₂C₂Ph₂)₂, (complexes <strong>3</strong>–<strong>6</strong>; M = Fe or Co; RA-NHC = 1-(ferrocenylmethyl)-3-mesitylimidazol-2-ylidene (<strong>1</strong>) or 1,3-dimesitylnaphthoquinimidazol-2-ylidene (<strong>2</strong>)) were synthesized via the reaction of NHC ligands <strong>1</strong> and <strong>2</strong> with the corresponding dithiolene dimers [M(S₂C₂Ph)₂]₂ (M = Fe or Co). The molecular structures of <strong>3</strong>–<strong>6</strong> were unambiguously assigned using single-crystal X-ray diffraction analysis. Geometrical analysis revealed <strong>3</strong> and <strong>4</strong> adopt trigonal bipyramidal geometries, while complexes <strong>5</strong> and <strong>6</strong> exhibit distorted square pyramidal configurations. Cyclic voltammetry studies indicated that all four complexes (<strong>3</strong>–<strong>6</strong>) undergo electrochemically triggered ligands dissociation of RA-NHC ligands upon reduction at approximately −1.9 V <em>vs.</em> SCE. UV–vis spectroscopic analysis showed broad absorption bands between 700 and 900 nm, which were attributed to intra-ligand charge transfer (ILCT) transitions. This report presents a comprehensive discussion of the molecular geometries, solid-state structures, and electrochemical behavior of complexes <strong>3</strong>–<strong>6</strong>.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122921"},"PeriodicalIF":3.2,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145267331","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}

{"title":"Structural robustness of crystalline sulfonated calix[4]arene complexes incorporating organic and metal cations","authors":"Irene Ling ,&nbsp;Alexandre N. Sobolev ,&nbsp;Charles S. Bond ,&nbsp;Colin L. Raston","doi":"10.1016/j.ica.2025.122933","DOIUrl":"10.1016/j.ica.2025.122933","url":null,"abstract":"<div><div>Six different sulfonated calix[4]arene-based compounds incorporating diverse metal ions (Na⁺, Y³⁺, Gd³⁺), organic guests (1-ethyl-3-methylimidazolium, EMIM⁺, tetraphenylphosphonium, PPh₄⁺), and solvents were synthesized and structurally characterized. Single-crystal X-ray analysis showed that the calixarene scaffold consistently adopts the typical cone conformation, stabilized by multiple weak intramolecular interactions. Subtle variations in metal cation coordination (e.g., mono- versus hetero-metallic assemblies) drive minor shifts in the coordination geometry, leading to previously unreported polymorphic forms and coordination motifs. In metal-only frameworks, sodium ions bridge sulfonate groups to form tightly packed bilayers devoid of guest inclusion, while heterometallic Y<img>Na networks enhance structural stability through complementary coordination and supramolecular forces. The introduction of bulky PPh₄⁺ cations expands the unit cell sixfold involving C-H···π interactions without disrupting primary metal-ligand coordination interactions. In contrast, complex with both EMIM⁺ and PPh₄⁺ exhibit mixed host-guest behaviour where EMIM⁺ is included in the calixarene cavity, while PPh₄⁺ molecules fill the interstices/voids between the bilayers. A new PPh₄⁺ inclusion polymorph displays unique mixed phenyl embraces and significantly increased hydration relative to known structures. Collectively, these findings reveal how minimal compositional adjustments govern crystal packing and host-guest inclusion, providing valuable insights for the design of customised calixarene-based materials.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122933"},"PeriodicalIF":3.2,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145217449","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}

{"title":"Synthesis, characterizations, and in vitro anticancer activity of di μ-acetato binuclear Zn(II) complexes with thiosemicarbazone ligands","authors":"Shivendra Kumar Pandey ,&nbsp;Anand Kumar Patel ,&nbsp;Seema Gupta ,&nbsp;Ray J. Butcher ,&nbsp;A. Acharya ,&nbsp;Manoj Kumar Bharty","doi":"10.1016/j.ica.2025.122926","DOIUrl":"10.1016/j.ica.2025.122926","url":null,"abstract":"<div><div>Here, we report di μ-acetato bridged Zn(II) complexes {<strong>[Zn(μ-ac)CyHCT]</strong>_{<strong>2</strong>} and <strong>[Zn(μ-ac)CyBHCT]</strong>_{<strong>2</strong>}} containing thiosemicarbazone alias hydrazine-1-carbothioamide ligands {<em>N</em>-Cyclohexyl-2-(1-(pyridin-2-yl)ethylidene)hydrazine-1-carbothioamide <strong>(HCyHCT)</strong> and <em>N</em>-Cyclohexyl-2-(phenyl(pyridin-2-yl)methylene)hydrazine-1-carbothioamide <strong>(HCyBHCT)</strong>}. The crystal structure of complexes shows that the Zn(II) centre is coordinated in a distorted trigonal bipyramidal configuration by three thiosemicarbazone atoms (two N and one S) and by an O atom from each of the two acetate groups. Further, di μ-acetato bridges in <strong>[Zn(μ-ac)CyBHCT]</strong>_{<strong>2</strong>} are showing linkage isomerism. The ligand and complexes were further studied for their anticancer activities against the HT-29 (human colon) and DL (Dalton's lymphoma cells) cancer cells. The results imply that these compounds have superior cytotoxic activity against HT-29 cells. Additionally, among all the compounds <strong>[Zn(μ-ac)CyHCT]</strong>_{<strong>2</strong>} has the most significant cytotoxic response with an IC₅₀ value close to 150 μM and 110 μM upon 24 h and 48 h incubation, respectively. Further assays DAPI staining, AO/EtBr dual staining, ROS production, and mitochondrial membrane potential measurement, were also performed to gain insights into the mechanism of cell death, and found that reduced and increased ROS production, highlighting mitochondrial-dependent apoptosis as the major mechanism for tumour cell death. In addition, the biocompatibility was further tested with HEK-293 (normal kidney) cells, which suggests the complex is biocompatible with a marginal cytotoxicity to normal cells.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122926"},"PeriodicalIF":3.2,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145217454","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}

{"title":"Mononuclear, dinuclear, and polynuclear bis(2-pyrimidylcarbonyl)amido copper(II) complexes: Synthesis, structure, thermal and magnetic properties","authors":"Burak Ay ,&nbsp;Kosei Sugai ,&nbsp;Takayuki Ishida","doi":"10.1016/j.ica.2025.122930","DOIUrl":"10.1016/j.ica.2025.122930","url":null,"abstract":"<div><div>Three copper(II) complexes, namely [Cu(<strong>bpca</strong>)(NO₃)(H₂O)] (<strong>1</strong>), [Cu₂(<strong>bpca</strong>)₂(<em>μ</em>-C₂O₄)(H₂O)₂] (<strong>2</strong>), and [Cu(<strong>bpca</strong>)(<em>μ</em>-Cl)]_n (<strong>3</strong>) (<strong>Hbpca =</strong> bis(2-pyrimidylcarbonyl)amine), have been synthesized using multidentate 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine (<strong>TPymT</strong>) and rhodizonic acid (<strong>RA</strong>) ligands. Compounds <strong>1</strong>–<strong>3</strong> have been characterized utilizing elemental analysis, FT-IR, Far-IR, ICP-OES, TGA, and single-crystal/powder X-ray diffraction analysis. Single-crystal X-ray analysis revealed that <strong>1</strong> and <strong>2</strong> crystallize in the monoclinic crystal system with space groups <em>P</em>2₁/<em>n</em> and <em>C</em>2/<em>m</em>, respectively, while <strong>3</strong> crystallizes in the orthorhombic crystal system with the <em>Fdd</em>2 space group. The thermogravimetry of the complexes supported the elemental and crystallographic results. Magnetic study clarified the presence of ferromagnetic coupling in both compounds <strong>2</strong> and <strong>3</strong>. A singlet-triplet model was applied to the susceptibility data on dinuclear <strong>2</strong>, yielding 2<em>J</em>/<em>k</em>_B = +2.04 ± 0.05 K in the <span><math><mrow><mover><mi>H</mi><mo>̂</mo></mover><mo>=</mo><mo>−</mo><mn>2</mn><mi>J</mi><msub><mover><mi>S</mi><mo>̂</mo></mover><mn>1</mn></msub><mo>.</mo><msub><mover><mi>S</mi><mo>̂</mo></mover><mn>2</mn></msub></mrow></math></span> convention. For polynuclear <strong>3</strong>, a uniform ferromagnetic chain model gave 2<em>J</em>/<em>k</em>_B = +5.57 ± 0.04 K. Density functional theory (DFT) calculations using the unrestricted B3LYP and/or M06-L functionals indicated that the magnetic couplings in <strong>2</strong> and <strong>3</strong> are ferromagnetic, consistent with the superexchange coupling mechanism.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122930"},"PeriodicalIF":3.2,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145267330","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}

{"title":"Structure and bonding in molecular and ionic complexes of iodine monochloride with pyrazine","authors":"Elena I. Davydova,&nbsp;Anna V. Pomogaeva,&nbsp;Dar'ya V. Spiridonova,&nbsp;Anna S. Lisovenko,&nbsp;Alexey Y. Timoshkin","doi":"10.1016/j.ica.2025.122927","DOIUrl":"10.1016/j.ica.2025.122927","url":null,"abstract":"<div><div>Structures of molecular and ionic compounds of ICl with pyrazine (pyz) have been established for the first time by X-ray diffraction structural analysis. In the molecular complex ICl∙pyz∙ICl (<strong>1)</strong> pyrazine serves as bidentate nonchelating ligand. The ionic complexes [Hpyz]⁺[ICl₂]⁻ (<strong>2)</strong> and [I₂∙pyz…Hpyz∙I₂]Cl (<strong>3</strong>) exhibit distinct coordination bonding patterns. The structural motif of <strong>2</strong> features infinite […pyz…H-pyz…]⁺ hydrogen bonded cationic chains and distinct [ICl₂]⁻ counterions, which interact with cationic chain not only through electrostatic anion–cation attraction but also via weak C<img>H⋯Cl hydrogen bonds.</div><div>In very peculiar structure of <strong>3</strong>, the iodine molecules act as bidentate Lewis acid, bridging the hydrogen-bonded cations [pyz…Hpyz]⁺ and the chloride anions in the infinite, almost linear chains (…I₂…pyz…Hpyz⁺…I₂…Cl⁻…I₂∙pyz…Hpyz⁺…I₂…Cl⁻…)_∞. Quantum chemical computations allowed to rationalize reactivity and establish a chemical bonding in the compounds. The dominant binding motif is governed by hydrogen bonds in [pyz…Hpyz]⁺ fragments and donor-acceptor halogen bonds Cl⁻ → I–I ← N, where iodine molecules serve as bidentate Lewis acids. Unusual linear arrangement of two Lewis acids I₂∙pyz and I₂∙Hpyz⁺ around Cl⁻ anion in <strong>3</strong> is facilitated due to packing effects forced by π-π staking between peripheral pyrazine rings.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122927"},"PeriodicalIF":3.2,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145217457","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}

{"title":"Synthesis of cobalt(III)/copper(II) complexes of N,O chelators and their DFT optimization and biological evaluation","authors":"Nitanshu Dhama,&nbsp;Mritunjay Kumar Tiwari,&nbsp;Vijay Kumar Vishvakarma,&nbsp;Rohit Yadav,&nbsp;Manish Kumar,&nbsp;Dhanraj T. Masram","doi":"10.1016/j.ica.2025.122928","DOIUrl":"10.1016/j.ica.2025.122928","url":null,"abstract":"<div><div>Three different metal complexes of formula [Co(nal)₂phen], <strong>1a</strong>, [Co(bipyam)₂] <strong>1b</strong> and [Cu(bpy)(1-Melm)(H₂O)Cl], <strong>1c</strong> (where nal = nalidixic acid, bpy = 2,2′-bipyridine, phen = 1,10-phenanhroline, bipyam = 2,2′-dipyridylamine and 1-Melm = 1-methylimidazole) have been synthesized and structurally characterized by UV/visible, FT-IR, mass spectrometry and X-ray crystallography measurements. The tetra-coordinate of complex <strong>1b</strong> adopts a square planar and hexa- and penta-coordinate complexes (<strong>1a</strong> &amp; <strong>1c)</strong> show distorted octahedral and tetrahedral geometry configurations. Density functional theory (DFT) calculations were used to optimize the molecular orbital depiction for the complexes. Utilizing a series of biophysical techniques to examine the <em>in vitro</em> binding studies of complexes (<strong>1a</strong>-<strong>1c</strong>) with BSA and DNA. The observed results were satisfied with strong binding interaction of complexes (<strong>1a</strong>-<strong>1c</strong>) in the subdomain IIIA of BSA as well as in the phosphate backbone of the DNA helix and follow the trend <strong>1a</strong> &gt; <strong>1c</strong> &gt; <strong>1c</strong>. In addition, the variation in the ability of complexes to cleave BSA and DNA has also been explored by electrophoretic mobility spectrometry, which concluded that complexes have excellent cleavage ability. The computational (MD) study of the complexes (<strong>1a</strong>-<strong>1c</strong>) was attributed to the nature of ligands bound to the metal centre that influences their <em>in vitro</em> activities. The antibacterial study concluded that the largest inhibition zone occurred in <strong>1a</strong> as compared to neomycin and other complexes. Further, these complexes have also revealed a significant antioxidant activity against DPPH radical. Cytotoxicity studies on three cancer cell lines (MCF-7, A-549 &amp; HeLa) showed that complex <strong>1a</strong> with the nal and phen ligands exhibited higher toxicity at both 24 h &amp; 48 h, respectively.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122928"},"PeriodicalIF":3.2,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145217455","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}

{"title":"Bio-inspired photocatalytic desulfurization performance of TiO2 wrapped spherical metallophthalocyanine","authors":"Jiaojiao Xu,&nbsp;Qiuxuan Ren,&nbsp;Yuqi Liu,&nbsp;Yan Yang,&nbsp;Gai Zhang","doi":"10.1016/j.ica.2025.122929","DOIUrl":"10.1016/j.ica.2025.122929","url":null,"abstract":"<div><div>The development of stable and efficient photocatalysts for the oxidative degradation of dibenzothiophene(DBT) in fuels remains a major challenge. Herein, <em>a novel</em> spherical binuclear metallophthalocyanine containing methoxy substituents Mn₂Pc₂(EP)₄ was self-assembled on TiO₂ via planar conjugated-ligand π-interaction to prepare Mn₂Pc₂(EP)₄/TiO₂ photocatalysts using a facilely “in suit” hydrothermal method. The red-shifted in the UV absorption bands of the Mn₂Pc₂(EP)₄/TiO₂ composites indicated a strong π-interaction between the composite materials. The Mn₂Pc₂(EP)₄/TiO₂ catalysts exhibited high stability and oxidative desulfurization performance towards DBT in a model oil containing n-octane. The catalytic efficiency of the Mn₂Pc₂(EP)₄/TiO₂ composite (98.85 %) was approximately 2.2 times higher than that of TiO₂ (44.97 %). The results verified that Mn₂Pc₂(EP)₄ improved the visible-light photocatalytic activity and enhanced the oxidative desulfurization activity of TiO_2. The photocatalytic efficiency of the Mn₂Pc₂(EP)₄/TiO₂ catalyst remained at 92 % for DBT after 5 reaction cycles. Thus, the samples exhibited excellent recoverability and stability compared to that of TiO₂. Mechanistic studies revealed that the ^⁎O₂-[Mn₂Pc₂(EP)₄]⁺/TiO₂(e⁻) species, which were the main active intermediate via the π-interaction self-assembling of Mn₂Pc₂(EP)₄, effectively improved the photocatalytic oxidation degradation of DBT. This study demonstrates the potential of Mn₂Pc₂(EP)₄/TiO₂ catalysts for developing environmentally friendly and efficient visible-light-driven desulfurization technology.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122929"},"PeriodicalIF":3.2,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145155908","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}

{"title":"Effect of axial ligands removal on the spin crossover in 2D iron tetracyanonickelates","authors":"Y. Avila ,&nbsp;M. González ,&nbsp;J. Rodríguez-Hernández ,&nbsp;Erick Ramírez ,&nbsp;Ilich A. Ibarra ,&nbsp;Jorge Balmaseda","doi":"10.1016/j.ica.2025.122885","DOIUrl":"10.1016/j.ica.2025.122885","url":null,"abstract":"<div><div>The effect of axial ligands removal on the spin-transition phenomenon was investigated in iron(II) tetracyanonickelate with pyridine, 3-fluoropyridine and 3-chloropyridine as intercalated species. The samples were heated at 190 °C, 210 °C, 230 °C, 250 °C and analyzed in terms of structural stability and changes in spin-crossover phenomenon using infrared spectroscopy, powder X-ray diffraction and magnetometry of superconducting quantum interference device. The results showed that the partial removal of the axial ligands caused a decrease in transition temperatures and a significant reduction in transition hysteresis loops. The spin-transition phenomenon remained even after removing more than 0.8 ligand molecules in Fe(3-fluoropyridine)₂[Ni(CN)₄] and Fe(3-chloropyridine)₂Ni(CN)₄]. The structural stability of the materials depended on <span><math><mi>π</mi></math></span>-<span><math><mi>π</mi></math></span> type interactions between the aromatic rings and dispersive type forces between the halogen groups in the inter-layer region. The findings provide deeper insight into the post-synthetic modification of spin crossover materials with a view to their application in molecular sensing.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122885"},"PeriodicalIF":3.2,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145155907","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}

{"title":"Bulky bis-guanidinate ligand-supported magnesium hydride: Synthesis, reactivity, and catalytic applications","authors":"Sayantan Mukhopadhyay,&nbsp;Anubhab Das,&nbsp;Smrutirani Padhan,&nbsp;Sharanappa Nembenna","doi":"10.1016/j.ica.2025.122924","DOIUrl":"10.1016/j.ica.2025.122924","url":null,"abstract":"<div><div>Bis-guanidinate stabilized magnesium complexes of the general formula [LMgR]₂, in which R = <em>n</em>-Bu (<strong>Mg-1</strong>), H (<strong>Mg-2</strong>), and <em>O-n</em>Bu (<strong>Mg-3</strong>), and L = {(ArHN)(ArN) − C=N − C(NAr)(NHAr); Ar = 2,6-^<em>i</em>Pr₂C₆H₃, have been synthesized and characterized by multinuclear (¹H, ¹³C{¹H}) NMR spectroscopy and single-crystal X-ray diffraction analysis. Further, the hydride derivative [LMgH]₂ (<strong>Mg-2</strong>) displayed excellent catalytic activity in the hydroboration of cyanamides and carbodiimides. <strong>Mg-2</strong> efficiently catalyzed both partial and complete hydroboration of cyanamides to yield <em>N</em>-borylimines and <em>N</em>, <em>N</em>′-bis-borylated amines, respectively. Additionally, it facilitated the selective monohydroboration of carbodiimides, affording <em>N</em>-boryl formamidines. Mechanistic investigations, supported by stoichiometric experiments, enabled the isolation and structural characterization of catalytically relevant active species: [LMgN=CH − N(Et₂)]₂ (<strong>Mg-4</strong>) for cyanamide hydroboration and [LMgN(^<em>i</em><em>Pr</em>)CHN(^<em>i</em>Pr)] (<strong>Mg-5</strong>) for carbodiimide hydroboration. These findings are summarized in the proposal of a detailed mechanistic cycle, providing fundamental insights into magnesium-mediated hydroborations.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122924"},"PeriodicalIF":3.2,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145155906","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}