Polyhedron最新文献

{"title":"Structural characterization and comparative analysis of two crystalline forms of drug cocrystal (S086) by MicroED, XPS, and XAFS","authors":"Wen-Jie Xu ,&nbsp;Jie Yan ,&nbsp;Song Li ,&nbsp;Duan-Ming Tan ,&nbsp;Sheng Hu","doi":"10.1016/j.poly.2025.117451","DOIUrl":"10.1016/j.poly.2025.117451","url":null,"abstract":"<div><div>Similar to the world’s first marketed ARNI drug sacubitril/valsartan (LCZ696), S086 is also a drug-drug cocrystal formed by neprilysin inhibitor (NEP) and angiotensin receptor blocker (ARB). ARNI drugs have played an important role in treating hypertension as a new class of antihypertensive drugs. Therefore, understanding the solid-state structure of S086 has become very meaningful. Employing advanced analytical techniques such as MicroED, XPS and XAFS, our comprehensive analysis has elucidated that the two crystalline forms, α and ξ of S086, are cocrystals derived from the synergistic combination of EXP3174, sacubitril, and calcium atoms, mediated by strong interactions. Due to the difficulty in obtaining X-ray single crystal structures, XPS and XAFS analyses, which offer unique insights into material structure, reasonably suggest that the two crystal forms of S086 possess highly similar coordination structures centered around calcium atoms with mixed ligands, but there are still subtle differences. The subtle differences in carboxylate coordination modes between α and ξ are reflected in the recently published linear and nonlinear IR spectroscopic studies of S086.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"271 ","pages":"Article 117451"},"PeriodicalIF":2.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143453876","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":"Improving the onset of oxygen redox reactions by activating surface defects with visible light on a ZnO-based electrode","authors":"C.K. Zagal Padilla ,&nbsp;Sergio A. Gamboa ,&nbsp;B. Campillo ,&nbsp;Virginia Gomez-Vidales ,&nbsp;A. Álvarez Gallegos","doi":"10.1016/j.poly.2025.117450","DOIUrl":"10.1016/j.poly.2025.117450","url":null,"abstract":"<div><div>This study investigates the influence of photoactivated oxygen vacancies (VO) on the activation of oxygen redox reactions, such as evolution (OER) and reduction (ORR) reactions. The reactions were carried out on the surface of an electrode prepared with ZnO prepared by green synthesis and supported on sterling silver. Structural and surface analyses using X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance (EPR) confirmed the presence of oxygen vacancies. Electrochemical analysis performed in an alkaline medium showed that Vo exhibited photoactivation under visible light illumination. This photoactivation process facilitated electron transfer, resulting in the formation of superoxide intermediates <span><math><mrow><msubsup><mrow><mo>(</mo><mi>O</mi></mrow><mrow><mn>2</mn></mrow><mo>-</mo></msubsup><mrow><mo>)</mo></mrow></mrow></math></span>. These intermediates contribute to the generation of singlet oxygen (¹O₂), which enhances OER activity and enables the photoexcitation of adsorbed peroxides and singlet oxygen. This process promotes the formation of triplet oxygen (³O₂), which improves the ORR kinetics. The incorporation of Mg into the Zn-O matrix may play an essential role in these processes. These results provide new insights into the design of electrocatalysts using visible-light-activated redox processes for rechargeable batteries and fuel cell applications.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"271 ","pages":"Article 117450"},"PeriodicalIF":2.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143444673","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis, crystal structure reinvestigation and chemical formula redefinition of cesium hydrogen oxalate by single crystal X-ray diffraction, IR spectroscopy, thermal and Hirshfeld surface analysis","authors":"Hamza Kherfi ,&nbsp;Malika Hamadène","doi":"10.1016/j.poly.2025.117449","DOIUrl":"10.1016/j.poly.2025.117449","url":null,"abstract":"<div><div>In attempt to prepare a bimetallic polymer oxalate with Cr and Cs atoms, colorless single crystals have been isolated and identified as CsHC₂O_4, from X-ray powder diffraction which shown the compound to be isotypic with that reported previously by Kholodkovskaya (Space Group <em>P</em>2₁/<em>c</em>). On the lack of some structural data, its structure has been reinvestigated using new and more crystallographic data. Two independent C atoms and only one H atom are present in the asymmetric unit, with one Cs atom and moreover, the symmetry center is located on the center of the two kinds of C<img>C bonds, allowing to propose the chemical formula Cs₂(C₂O₄)(H₂C₂O₄) (<strong>I</strong>).The structure consists of zigzag files of CsO₁₁ polyhedra sharing opposite faces via the C₂O₄²⁻ ions and form double layers separated by H₂C₂O₄ ligand layers, along [0<!--> <!-->0<!--> <!-->1] direction. The IR spectroscopy study, carried out by comparison with homologous compounds, is in agreement with XRD data. The thermal analysis ATG and DTA performed under different atmospheric conditions, showed different thermal decomposition process for this bidimensional (2D) compound. The Hirshfeld surface analysis and its corresponding 2D fingerprint plots revealed that the major contributors to the crystal packing are Cs⋯O contacts followed by O⋯C, O⋯O, and O⋯H contacts.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"271 ","pages":"Article 117449"},"PeriodicalIF":2.4,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143444672","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":"Novel µ-nitrido homo-/heteroleptic iron–manganese complexes as promising oxidants","authors":"Sergey A. Zdanovich ,&nbsp;Elena Yu. Tyulyaeva ,&nbsp;Vitaliy S. Sukharev ,&nbsp;Mark V. Zaitsev ,&nbsp;Svetlana V. Zaitseva","doi":"10.1016/j.poly.2025.117448","DOIUrl":"10.1016/j.poly.2025.117448","url":null,"abstract":"<div><div>Binuclear μ-bridged macrocycle dimers have been attracting considerable attention because of their catalytic ability in organic substrates oxidation. This work focuses on the preparation and properties of novel µ-nitrido iron–manganese homo-/heteroleptic complexes bearing porphyrin and phthalocyanine ligands. The compounds are identified and studied using UV, IR, EPR spectroscopy, mass spectrometry, and electrochemistry techniques. Subjecting the complexes to <em>^t</em>BuOOH in CH₂Cl₂ resulted in chemical generation of different high-valence species capable of decomposing β-carotene and peroxide at room temperature. The active reaction intermediates are rather stable to be identified using spectroscopic methods aiming at further establishing the reaction mechanism. The complexes composition is found to affect their redox properties and path of the studied substrate oxidation. The findings contribute to expanding the range of compounds with the controlled oxidizing capability to create active and durable catalysts.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"270 ","pages":"Article 117448"},"PeriodicalIF":2.4,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418947","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":"Comprehensive study of a novel cobalt(II) complex: Synthesis, X-ray crystal structure, Hirshfeld surface analysis, computational quantum investigations, and molecular docking insights","authors":"Yasmina Sabeg ,&nbsp;Rim Benali-Cherif ,&nbsp;Wahiba Falek ,&nbsp;Radhwane Takouachet ,&nbsp;Lynda Golea ,&nbsp;Muhittin Aygün ,&nbsp;Nourredine Benali-Cherif","doi":"10.1016/j.poly.2025.117445","DOIUrl":"10.1016/j.poly.2025.117445","url":null,"abstract":"<div><div>The design of metal complexes that combine structural sophistication with biological relevance has become a cornerstone of modern coordination chemistry. In this study, we present the synthesis and comprehensive characterization of a novel cobalt(II) complex, [Co(phen)₂(η²-bz)]·2bzH·NO₃ (<strong>1</strong>), featuring a distorted six-coordinate octahedral geometry, stabilized by two 1,10-phenanthroline and one benzoate ligands. The crystal structure was elucidated using single-crystal X-ray diffraction, revealing a robust supramolecular network strengthened by various non-covalent interactions, including C<img>H⋯O, O<img>H⋯O hydrogen bonds, and π–π stacking between aromatic rings. Density functional theory (DFT) calculations, employing the B3LYP/3-21G basis set, provided further insight into the optimized geometry and electronic properties, with a close match to experimental observations. Hirshfeld surface analysis quantified the intermolecular interactions, and molecular electrostatic potential (MEP) maps highlighted the reactive sites of the complex. Additionally, molecular docking studies demonstrated a strong binding affinity between the cobalt complex and Klebsiella pneumoniae receptors (PDB ID: 6RD3), suggesting potential antibacterial properties. This cobalt complex offers new insights into the structure–activity relationships of transition metal complexes and presents promising avenues for the development of novel therapeutic agents targeting multidrug-resistant bacteria. The findings from this study also pave the way for further exploration of cobalt complexes in catalytic and biomedical applications.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"271 ","pages":"Article 117445"},"PeriodicalIF":2.4,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143444674","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":"Influence of ligand donation on charge transfer properties of cyanido-bridged binuclear Fe-Ru complexes","authors":"Han Liu ,&nbsp;Xiao-Lin Liu ,&nbsp;Hao Wang ,&nbsp;Yang Liu ,&nbsp;Xin-Tao Wu ,&nbsp;Tian-Lu Sheng","doi":"10.1016/j.poly.2025.117442","DOIUrl":"10.1016/j.poly.2025.117442","url":null,"abstract":"<div><div>To investigate how the electron-donating ability of the ligand influence the metal-to-metal charge transfer (MMCT) in mixed-valence (MV) systems, a series of asymmetric binuclear cyanido-bridged complexes CpMe_x(dppe)FeCNRu(bimpy)(PPh₃)(NCCH₃), <strong>N[PF₆]₂</strong> (x = 1, 3, 4, 5; N = <strong>1</strong>, <strong>2</strong>, <strong>3</strong>, <strong>4</strong>; CpMe = methylcyclopentadiene; CpMe₃ = 1, 2, 4-trimethyl-cyclopentadiene; CpMe₄ = 1, 2, 3, 4-tetramethyl-cyclopentadienyl; CpMe₅ = 1, 2, 3, 4, 5-pentamethyl-cyclopentadienyl; dppe = 1,2-bis(diphenylphosphino)ethane; bimpy = 2, 6-Bis(benzimidazol-2-yl)pyridine; PPh₃ = triphenylphosphine), along with their one-electron oxidized products <strong>N[PF₆]₃</strong> were synthesized and well characterized. In these MV systems, significant electronic interactions between the two metal centers were revealed by electrochemistry, crystallography, FTIR, UV–vis-NIR, and supported by the DFT calculations. The results showed that the MM’CT energy from the Ru^II to the Fe^III increases as the electron-donating ability of the CpMe_X ligands was enhanced with the addition of methyl substituents. Meanwhile, all the one-electron oxidized products <strong>N[PF₆]₃</strong> belong to Class II systems.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"271 ","pages":"Article 117442"},"PeriodicalIF":2.4,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143438273","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":"Z-scheme design of hydrothermally synthesized Sm-Fe-doped LaNiO3/g-C3N4 heterostructure photo-catalyst for the efficient elimination of methylene blue & moxifloxacin pollutants","authors":"Shahid Iqbal ,&nbsp;Firdous Bibi ,&nbsp;Muhammad Jamshaid ,&nbsp;Ambreen Kalsoom ,&nbsp;Wedad A. Al-onazi ,&nbsp;Mohamed S. Elshikh ,&nbsp;Md Rezaul Karim ,&nbsp;Ismail Hossain","doi":"10.1016/j.poly.2025.117446","DOIUrl":"10.1016/j.poly.2025.117446","url":null,"abstract":"<div><div>In this current investigation, it deals with the synthesis of a highly effective Z-scheme visible light-driven Sm-Fe-doped LaNiO₃/g-C₃N₄ hetero-structure photocatalyst for the efficient elimination of toxic environmental pollutants from wastewater. Pristine LaNiO₃ nanoparticles (NP), samarium, and iron (Sm-Fe) doped LaNiO₃ NP and their nanohybrid composite Sm-Fe doped LaNiO₃/g-C₃N₄ with 15 % (g-C₃N₄) graphitic-carbon-nitride was prepared via facile glycerine-assisted hydrothermal and ultra-sonication approaches. The materials for their physico-chemical properties were characterized using SEM, TEM, P-XRD, FTIR, XPS, BET, I-V, VSM, PL, and UV–visible analysis. The morphological analysis revealed that the g-C₃N₄ sheets interact and buffer with Sm-Fe-doped LaNiO₃ NP, forming larger, elongated aggregations having highly exposed surfaces, wider particle size distributions and possessing an average particle sizes 22–34 nm. Structural investigation demonstrated the single-phase rhombohedral LaNiO₃ perovskite along with successful Sm and Fe cation doping. The Sm-Fe-doped LaNiO₃/g-C₃N₄ nanohybrid materials exhibited excellent BET surface area (96.7 m²/g), a well-porous nature with average pore sizes in the 1.5–2.6 nm range, good saturation magnetization (2.204 <span><math><mo>×</mo></math></span> 10⁻³ Ms/emu), boosted electrical conductivity (1.09 <span><math><mo>×</mo></math></span> 10² Sm⁻¹) and a narrow band gap (2.06 eV), which was credited to the Sm-Fe-doping and the combination of highly conducting g-C₃N₄ material. It was demonstrated that Sm-Fe-doped LaNiO₃ NP were uniformly dispersed on g-C₃N₄ nanohybrids, forming an intimate interface with robust interaction between LaNiO₃ and the g-C₃N₄, which promoted efficient charge mobility and separation, forming a Z-scheme photocatalytic system. The photo-degradation investigation of the newly synthesized photo-catalyst was tested against methylene blue (MB) dye and moxifloxacin (MOX) drug under solar-light irradiation. The Sm-Fe-doped LaNiO₃/g-C₃N₄ nanohybrid photocatalyst exhibited excellent removal of MB dye (97.8 %) and MOX (96.4 %) in only 55 min. This superb removal proficiency of MB dye and MOX by Sm-Fe-doped LaNiO₃/g-C₃N₄ nanohybrid was attributed to its improved magnetic, good electrical, well-porosity, and excellent optical absorption characteristics, which make the Sm-Fe-doped LaNiO₃/g-C₃N₄ nanohybrid as a novel materials for removing toxic environmental pollutants.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"270 ","pages":"Article 117446"},"PeriodicalIF":2.4,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143419057","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":"Soluble peripherally tert-butylphenoxy/tert-butylcarbazole substituted zinc phthalocyanines and their photophysical properties","authors":"E.N. Ovchenkova,&nbsp;N.G. Bichan,&nbsp;M.S. Gruzdev,&nbsp;V.A. Mozgova,&nbsp;U.V. Chervonova,&nbsp;T.N. Lomova","doi":"10.1016/j.poly.2025.117447","DOIUrl":"10.1016/j.poly.2025.117447","url":null,"abstract":"<div><div>Zinc(II) phthalocyanines containing eight <em>tert</em>-butylphenoxy and <em>tert</em>-butylcarbazole groups at the molecule periphery (ZnPc(<em>^t</em>BuPhO)₈ and ZnPc(Carb)₈, respectively) were obtained with about 20 % yield by the DBU activated phthalonitrile tetramerization in pentanol and dry quinoline, respectively. Their structure was confirmed using MALDI-TOF mass spectrometry, IR, ¹H/¹³C NMR, and electronic absorption/fluorescence spectroscopy. The ZnPc(<em>^t</em>BuPhO)₈/ZnPc(Carb)₈/H₂Pc(<em>^t</em>BuPhO)₈ photophysical parameters, including the Q-band wavelength, fluorescence/singlet oxygen quantum yields, fluorescence lifetime, and radiative/non-radiative transition constant in organic solvents, were established. The presence of ZnPc(<em>^t</em>BuPhO)₈ and ZnPc(Carb)₈ long-life excited states is confirmed by the fs-TA data. The peripheral carbazole substitution decreases slightly both the fluorescence quantum yield and fluorescence lifetime (by ∼0.6 ns) relative to that for ZnPc(<em>^t</em>BuPhO)₈, but simultaneously increases the possibility of singlet oxygen generation. The formation of the H₂Pc(<em>^t</em>BuPhO)₈ proton transfer complex in dimethylformamide leading to the increase in singlet oxygen yield more than 3 times was established. Attractive photophysical parameters, non-aggregated state in solutions, and the bathochromically located Q absorption band allow us to consider ZnPc(Carb)₈ as a promising photosensitizer.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"270 ","pages":"Article 117447"},"PeriodicalIF":2.4,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143419056","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":"Manganese(II) complexes of thiophenyl imino-ligand with synergistic behavior in biological systems, ct-DNA interactions, and catalytic oxidative performance of benzyl alcohol","authors":"Mohamed Shaker S. Adam ,&nbsp;Zakaria S. Bakhuraisa ,&nbsp;Mustafa J. Abdelmageed Abualreish ,&nbsp;Ahmed Desoky M. Mohamad ,&nbsp;Mamdouh A. Mohamed","doi":"10.1016/j.poly.2025.117441","DOIUrl":"10.1016/j.poly.2025.117441","url":null,"abstract":"<div><div>Considering a facile synthesis and high coordination ability of substituted imines, a condensation reaction between 2-aminobenzenethiol and thiophene-2-carbaldehyde produced an interesting derivative of the thiophenyl imine ligand (HLSNS). The coordination feature of HLSNS with Mn(II) ions was studied in 1 and 2: 1 M ratios, leading to the formation of two different structural complexes, MnLSNSCl and Mn(LSNS)₂, respectively. Their chemical structures were validated by several suitable techniques, covering also the micro-elemental analyses, thermogravimetric evaluation, magnetic properties, and conductivity behaviors. Biologically, the inhibitory action of HLSNS (the free ligand) and its Mn(II)-chelating reagents on the growth power of three common bacterial and fungal strains, beside three established human cancer cell lines, were evaluated in relation to the presented Mn(II) ion and the structural influences of MnLSNSCl and Mn(LSNS)₂ compared to their free ligand (HLSNS). The antimicrobial and anticancer behavior was estimated based on the measured inhibitory zone (mm) and the half-effective inhibitory concentrations (<em>IC</em>₅₀, mM). Discovering the pivotal influence of Mn(II) ions and their ratios in the two chelates on the binding strength to the calf thymus DNA (ct-DNA), which reported by the alterations in viscosity and spectrophotometric properties of DNA. The ct-DNA interaction strength was built on the values of binding constants, Gibb’s free energy, and chromism modes, confirming also the interaction modes. For the catalytic potential testing, both MnLSNSCl and Mn(LSNS)₂ were employed for the oxidative progressing of benzyl alcohol using hydrogen peroxide in a homogenous phase at 80 °C. Both catalysts exhibited superior catalytic oxidative activity. The yield percentage of selective benzaldehyde using MnLSNSCl and Mn(LSNS)₂ was 90 % after 4 h, and 84 % after 5 h, respectively. The discrepancy in the optimum activity for both catalysts pertained to the differences in their molecular structures, which helped to assume a convenient mechanism.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"270 ","pages":"Article 117441"},"PeriodicalIF":2.4,"publicationDate":"2025-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143394363","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 characterizations of a phenolato coordinate gallium(III) porphyrin: A metalloporphyrin with stabilized axial ligand bonding","authors":"Shafikul Islam ,&nbsp;Keita Fukui ,&nbsp;Md. Moshiur Rahman ,&nbsp;Kazunori Hirabayashi ,&nbsp;Toshio Shimizu ,&nbsp;Masafumi Ueda ,&nbsp;Masashi Hasegawa ,&nbsp;Hiroyasu Sato ,&nbsp;Ken-ichi Sugiura","doi":"10.1016/j.poly.2025.117439","DOIUrl":"10.1016/j.poly.2025.117439","url":null,"abstract":"<div><div>To obtain stable metal–ligand bonding in metalloporphyrins, a phenolato-coordinated gallium(III) porphyrin (Ga³⁺Por) was designed, synthesized, and characterized. The strategy behind this chemistry is that the hard acid Ga³⁺ forms a stable bond with the hard base phenolato, PhO⁻. The title complex was synthesized through a dehydration reaction between phenol and the hydroxo complex of Ga³⁺Por. The stability of the Ga-O coordination bond facilitates the detection of the parent ion signal in atmospheric pressure chemical ionization mass spectrometry, as well as in conventional experimental techniques, such as recrystallization from a hot solvent under ambient conditions. Single-crystal diffraction studies revealed that the coordination geometry of the ligand resulted in a five-coordinate Ga³⁺Por. In addition to the usual spectroscopic studies, including absorption and emission spectra, electrochemical analyses were also performed. The positively shifted oxidation potential can be explained by the incorporation of gallium, which has an insufficient shielding effect because of its filled <em>d</em>-electrons.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"271 ","pages":"Article 117439"},"PeriodicalIF":2.4,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143453875","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}