Pub Date : 2026-02-01Epub Date: 2025-11-21DOI: 10.1016/j.poly.2025.117906
M. Mohammadi, S.A. Kahani
The bimetallic CoNi (S1) and FeNi (S2) nano-alloys were synthesized by chemical co-reduction of theirs MCl2 (M = FeII, CoII and NiII) salts by aluminum nanoparticles in an acidic solid-state reaction at room temperature. The products were characterized by Fourier transform infrared spectroscopy (FTIR) spectroscopy, X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), energy-dispersive X-ray (EDX), and vibrating sample magnetometer (VSM). The X-ray diffraction patterns of products S1 and S2 revealed the presence of intermetallic, metallic, and unreacted aluminum phases. The products weight fractions were calculated using Rietveld refinement. Quantitative XRD analysis of S1 shows a weight fraction of CoNi 58.58 wt%, Co 6.04 wt%, Ni 30.14 wt% and unreacted aluminum 5.23 wt%. Whereas, calculation in S2 shows weight fraction FeNi, Fe, Ni and unreacted aluminum 22.87, 44.20, 18.16 and 14.77 wt% respectively. The weight fraction of the intermetallic CoNi phase is more than the intermetallic FeNi phase which is associated with Hum-Ruhter rules for the alloy formation, such as electronegativity, as explained in the Van Arkel-Ketelaar triangle. FESEM image of S1 and S2 show particles size distribution in the region 40–140 nm and 30–130 nm respectively. The hysteresis loop of S1 and S2 show magnetic saturation 88.374 emu/g and 61.298 emu/g respectively.
{"title":"Mechanochemical synthesis of bimetallic FeNi and CoNi nano-alloys at room temperature","authors":"M. Mohammadi, S.A. Kahani","doi":"10.1016/j.poly.2025.117906","DOIUrl":"10.1016/j.poly.2025.117906","url":null,"abstract":"<div><div>The bimetallic CoNi (S<sub>1</sub>) and FeNi (S<sub>2</sub>) nano-alloys were synthesized by chemical co-reduction of theirs MCl<sub>2</sub> (M = Fe<sup>II</sup>, Co<sup>II</sup> and Ni<sup>II</sup>) salts by aluminum nanoparticles in an acidic solid-state reaction at room temperature. The products were characterized by Fourier transform infrared spectroscopy (FTIR) spectroscopy, X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), energy-dispersive X-ray (EDX), and vibrating sample magnetometer (VSM). The X-ray diffraction patterns of products S<sub>1</sub> and S<sub>2</sub> revealed the presence of intermetallic, metallic, and unreacted aluminum phases. The products weight fractions were calculated using Rietveld refinement. Quantitative XRD analysis of S<sub>1</sub> shows a weight fraction of CoNi 58.58 wt%, Co 6.04 wt%, Ni 30.14 wt% and unreacted aluminum 5.23 wt%. Whereas, calculation in S<sub>2</sub> shows weight fraction FeNi, Fe, Ni and unreacted aluminum 22.87, 44.20, 18.16 and 14.77 wt% respectively. The weight fraction of the intermetallic CoNi phase is more than the intermetallic FeNi phase which is associated with Hum-Ruhter rules for the alloy formation, such as electronegativity, as explained in the Van Arkel-Ketelaar triangle. FESEM image of S<sub>1</sub> and S<sub>2</sub> show particles size distribution in the region 40–140 nm and 30–130 nm respectively. The hysteresis loop of S<sub>1</sub> and S<sub>2</sub> show magnetic saturation 88.374 emu/g and 61.298 emu/g respectively.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117906"},"PeriodicalIF":2.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145621421","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 : 2026-02-01Epub Date: 2025-11-19DOI: 10.1016/j.poly.2025.117900
Nitin H. Kolhe , Yasinalli Tamboli , Huda A. Bawazir , Vijay Singh Parihar
Mixed-ligand transition metal complexes have emerged as a significant area of research due to their tunable structural, electronic, and biological properties. This comprehensive review provides a detailed analysis of recent advances in the synthesis, characterization, and diverse applications of complexes formed by combining 3-formylchromone derivatives with auxiliary N, O-donor ligand 8-hydroxyquinoline. We systematically explore the coordination chemistry of chromone, a versatile pharmacophore, highlighting its role as a primary ligand. A critical examination of their biological properties, including antimicrobial, anticancer, and antioxidant activities, is presented. Furthermore, the review elucidates the key structure-activity relationships (SARs) that govern their efficacy. By compiling the current state of knowledge, this work aims to identify existing research gaps and propose future directions for the rational design of next-generation mixed-ligand complexes with tailored properties for advanced applications in medicine.
{"title":"Advances in mixed ligand transition metal complexes: Chromone derivatives and N, O donor ligands – a comprehensive review","authors":"Nitin H. Kolhe , Yasinalli Tamboli , Huda A. Bawazir , Vijay Singh Parihar","doi":"10.1016/j.poly.2025.117900","DOIUrl":"10.1016/j.poly.2025.117900","url":null,"abstract":"<div><div>Mixed-ligand transition metal complexes have emerged as a significant area of research due to their tunable structural, electronic, and biological properties. This comprehensive review provides a detailed analysis of recent advances in the synthesis, characterization, and diverse applications of complexes formed by combining 3-formylchromone derivatives with auxiliary N, O-donor ligand 8-hydroxyquinoline. We systematically explore the coordination chemistry of chromone, a versatile pharmacophore, highlighting its role as a primary ligand. A critical examination of their biological properties, including antimicrobial, anticancer, and antioxidant activities, is presented. Furthermore, the review elucidates the key structure-activity relationships (SARs) that govern their efficacy. By compiling the current state of knowledge, this work aims to identify existing research gaps and propose future directions for the rational design of next-generation mixed-ligand complexes with tailored properties for advanced applications in medicine.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117900"},"PeriodicalIF":2.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145621352","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 : 2026-02-01Epub Date: 2025-11-19DOI: 10.1016/j.poly.2025.117904
Syahrina Nur 'Ain Abdul Halim , Khomaizon Abdul Kadir Pahirul Zaman , Siti Nadiah Abdul Halim , Pei Meng Woi , Rozie Sarip
Two new gold(I) thiosemicarbazone phosphine complexes have been synthesised and characterised using various spectroscopic techniques and single-crystal X-ray diffraction. In these complexes, the gold atom is coordinated with the sulphur of thiosemicarbazone and phosphorus of triphenylphosphine, resulting in a linear structure. These complexes were also employed as precursors for the synthesis of Au monometallic clusters, resulting in very refined nanosized particles that were analysed using electrospray ionisation mass spectroscopy (ESI-MS), UV–Visible spectroscopy, X-ray photoelectron spectroscopy (XPS) and high-resolution transmission microscopy (HR-TEM). Furthermore, cyclic voltammetry (CV) analysis was conducted to evaluate the electrochemical properties of the complexes and clusters. The antibacterial properties of these nanoclusters, complexes, as well as their free thiosemicarbazone ligands, were assessed against gram-positive Staphylococcus aureus and gram-negative Escherichia coli. While the free ligands exhibited a considerable antibacterial activity, their corresponding Au(I) complexes showed diminished efficacy against both bacterial strains. In contrast, the nanoclusters demonstrated notable activity against S. aureus but proved ineffective against E. coli.
{"title":"From monomers to nanoclusters: Synthesis, characterisation and antibacterial evaluation of gold (I) complexes and their nanoclusters containing thiosemicarbazone and phosphine ligands","authors":"Syahrina Nur 'Ain Abdul Halim , Khomaizon Abdul Kadir Pahirul Zaman , Siti Nadiah Abdul Halim , Pei Meng Woi , Rozie Sarip","doi":"10.1016/j.poly.2025.117904","DOIUrl":"10.1016/j.poly.2025.117904","url":null,"abstract":"<div><div>Two new gold(I) thiosemicarbazone phosphine complexes have been synthesised and characterised using various spectroscopic techniques and single-crystal X-ray diffraction. In these complexes, the gold atom is coordinated with the sulphur of thiosemicarbazone and phosphorus of triphenylphosphine, resulting in a linear structure. These complexes were also employed as precursors for the synthesis of Au monometallic clusters, resulting in very refined nanosized particles that were analysed using electrospray ionisation mass spectroscopy (ESI-MS), UV–Visible spectroscopy, X-ray photoelectron spectroscopy (XPS) and high-resolution transmission microscopy (HR-TEM). Furthermore, cyclic voltammetry (CV) analysis was conducted to evaluate the electrochemical properties of the complexes and clusters. The antibacterial properties of these nanoclusters, complexes, as well as their free thiosemicarbazone ligands, were assessed against gram-positive <em>Staphylococcus aureus</em> and gram-negative <em>Escherichia coli</em>. While the free ligands exhibited a considerable antibacterial activity, their corresponding Au(I) complexes showed diminished efficacy against both bacterial strains. In contrast, the nanoclusters demonstrated notable activity against <em>S. aureus</em> but proved ineffective against <em>E. coli</em>.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117904"},"PeriodicalIF":2.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145621350","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 : 2026-02-01Epub Date: 2025-11-27DOI: 10.1016/j.poly.2025.117914
Mehboob Ali , Saba Sharif , Farhan Sadiq , Humaira Aslam , Zainab Altaf , Sadaf Naz , Imran Sadiq , Eman.A. Alghamdi , Muhammad Raheel , Muhammad Shahbaz , Saira Riaz , Shahzad Naseem
This study proposed the formation of rGO/Sr2Fe8O14 nanocomposite for structural, magnetic, optical and microwave absorption applications. The reduced graphene oxide (rGO) and Strontium-based T-type hexaferrite (Sr2Fe8O14) nanocomposites were prepared by ceramic method while the T-type hexaferrite was prepared by following the sol gel auto-combustion method. Respectively. The XRD analysis of all the samples confirmed the presence of both phases in the composites. The vibrating sample magnetometer (VSM) revealed that all the samples possessed a soft magnetic nature. The saturation and remanence magnetization increased while coercivity declined by enhancing T-type hexaferrite concentration in rGO. The polarization versus electric field hysteresis loops demonstrated the lossy behavior and this behavior increased with the addition of T-type hexagonal ferrites. To analyze the optical investigation, photo-luminance (PL) and UV–visible spectroscopies were employed. The PL outcomes revealed the ultraviolet and visible region emission. The UV–visible spectroscopy results showed the enhancement in absorbance of photo-energy with the addition of T-type content while optical band gap energy decreased. The pure T-type hexaferrites sample exhibited the maximum value of microwave absorption (−23.04) at 0.46 GHz frequency. These results divulge the importance of the present synthesized composites in photo-catalytic activities and microwave absorption properties.
{"title":"Exploration of structural, magnetic, electrical polarization, optical and microwave absorption properties of rGO/hexaferrites composites","authors":"Mehboob Ali , Saba Sharif , Farhan Sadiq , Humaira Aslam , Zainab Altaf , Sadaf Naz , Imran Sadiq , Eman.A. Alghamdi , Muhammad Raheel , Muhammad Shahbaz , Saira Riaz , Shahzad Naseem","doi":"10.1016/j.poly.2025.117914","DOIUrl":"10.1016/j.poly.2025.117914","url":null,"abstract":"<div><div>This study proposed the formation of rGO/Sr<sub>2</sub>Fe<sub>8</sub>O<sub>14</sub> nanocomposite for structural, magnetic, optical and microwave absorption applications. The reduced graphene oxide (rGO) and Strontium-based T-type hexaferrite (Sr<sub>2</sub>Fe<sub>8</sub>O<sub>14</sub>) nanocomposites were prepared by ceramic method while the T-type hexaferrite was prepared by following the sol gel auto-combustion method. Respectively. The XRD analysis of all the samples confirmed the presence of both phases in the composites. The vibrating sample magnetometer (VSM) revealed that all the samples possessed a soft magnetic nature. The saturation and remanence magnetization increased while coercivity declined by enhancing T-type hexaferrite concentration in rGO. The polarization versus electric field hysteresis loops demonstrated the lossy behavior and this behavior increased with the addition of T-type hexagonal ferrites. To analyze the optical investigation, photo-luminance (PL) and UV–visible spectroscopies were employed. The PL outcomes revealed the ultraviolet and visible region emission. The UV–visible spectroscopy results showed the enhancement in absorbance of photo-energy with the addition of T-type content while optical band gap energy decreased. The pure T-type hexaferrites sample exhibited the maximum value of microwave absorption (−23.04) at 0.46 GHz frequency. These results divulge the importance of the present synthesized composites in photo-catalytic activities and microwave absorption properties.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117914"},"PeriodicalIF":2.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145690657","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 : 2026-02-01Epub Date: 2025-11-24DOI: 10.1016/j.poly.2025.117910
Munmun Mondal, Ganesan Mani
The effect of an anion on the structure of the silver complex is investigated. The reaction between 2-(3,5-dimethylpyrazolylmethyl)-5-(phenylsulfonylmethyl)pyrrole LH and AgBF4 gives a discrete two-coordinate silver complex [Ag(LH)2]BF41. Conversely, the same ligand LH reacts with AgOCOCF3 to give an extended 1D polymeric network structure [Ag(μ-LH)(μ-CF3COO)]n2. With a silver ion containing the divalent sulfate ion, it forms a three-coordinate silver complex [Ag(LH)3]2SO43, which encapsulates the SO42− ion in its cavity. Yet another polymeric structure that encapsulates SO42− ion [Ag2(3,5-dimethylpyrazole)4(μ-SO4)] 4 was obtained by treating Ag2SO4 with 3,5-dimethylpyrazole. Complex 4 exhibits a dynamic behavior in solution between the sulfate-bridged complexes with the trans and cis orientations of the pyrazole NH groups, as studied by the variable temperature (VT) 1H NMR method. The important features are the argentophilic interaction, the pyrrole ring π-interaction, and the ditopic nature of ligands LH and 3,5-dimethylpyrazole, which all facilitate the formation of these structurally intriguing complexes.
{"title":"Synthesis and structural characterization of self-assembled silver(I) complexes of the pyrazole ligands: effect of anion and VT NMR study","authors":"Munmun Mondal, Ganesan Mani","doi":"10.1016/j.poly.2025.117910","DOIUrl":"10.1016/j.poly.2025.117910","url":null,"abstract":"<div><div>The effect of an anion on the structure of the silver complex is investigated. The reaction between 2-(3,5-dimethylpyrazolylmethyl)-5-(phenylsulfonylmethyl)pyrrole <strong>LH</strong> and AgBF<sub>4</sub> gives a discrete two-coordinate silver complex [Ag(<strong>LH</strong>)<sub>2</sub>]BF<sub>4</sub> <strong>1</strong>. Conversely, the same ligand <strong>LH</strong> reacts with AgOCOCF<sub>3</sub> to give an extended 1D polymeric network structure [Ag(<em>μ</em>-<strong>LH</strong>)(<em>μ</em>-CF<sub>3</sub>COO)]<sub>n</sub> <strong>2</strong>. With a silver ion containing the divalent sulfate ion, it forms a three-coordinate silver complex [Ag(<strong>LH</strong>)<sub>3</sub>]<sub>2</sub>SO<sub>4</sub> <strong>3</strong>, which encapsulates the SO<sub>4</sub><sup>2−</sup> ion in its cavity. Yet another polymeric structure that encapsulates SO<sub>4</sub><sup>2−</sup> ion [Ag<sub>2</sub>(3,5-dimethylpyrazole)<sub>4</sub>(<em>μ</em>-SO<sub>4</sub>)] <strong>4</strong> was obtained by treating Ag<sub>2</sub>SO<sub>4</sub> with 3,5-dimethylpyrazole. Complex <strong>4</strong> exhibits a dynamic behavior in solution between the sulfate-bridged complexes with the trans and cis orientations of the pyrazole NH groups, as studied by the variable temperature (VT) <sup>1</sup>H NMR method. The important features are the argentophilic interaction, the pyrrole ring π-interaction, and the ditopic nature of ligands <strong>LH</strong> and 3,5-dimethylpyrazole, which all facilitate the formation of these structurally intriguing complexes.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117910"},"PeriodicalIF":2.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145621420","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 : 2026-02-01Epub Date: 2025-10-30DOI: 10.1016/j.poly.2025.117853
Abdul Baqi , Shahbaz Sarwer , Xianhua Hou , Hadia Noor , Noreen Fatima , Haleema Riaz , Syeda Rabia Ejaz , Memona Bibi , Muhammad Imran Khan , Abdallah Shanableh , Rafael Luque
Iron-doped ZnO (Zn₁₋ₓFeₓO, x = 0.0, 0.05, 0.07, 0.10) nanoparticles were synthesized using a hydrothermal method. Various characterization techniques were employed to analyze the synthesized nanoparticles, including X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), ultraviolet-visible (UV–vis) spectroscopy, and photoluminescence (PL). XRD results showed that the crystallite size decreased with increasing iron content. SEM analysis provided insights into grain size, while EDX confirmed the successful incorporation of Fe into the ZnO lattice. Optical studies revealed a reduction in band gap energy upon Fe doping. Additionally, PL spectra exhibited shifts in peak positions with varying iron concentrations. The photocatalytic activity was evaluated through the degradation of methylene blue (MB) dye, achieving 82 % degradation after 180 min. The apparent rate constant for Fe-doped ZnO was higher than that of pure ZnO, highlighting its enhanced efficiency in wastewater remediation.
采用水热法制备了掺杂铁的ZnO纳米粒子（Zn₁￣ₓFeₓO, x = 0.0, 0.05, 0.07, 0.10）。利用x射线衍射（XRD）、扫描电子显微镜（SEM）、能量色散x射线光谱（EDX）、紫外可见光谱（UV-vis）和光致发光（PL）等表征技术对合成的纳米颗粒进行了分析。XRD结果表明，随着铁含量的增加，晶粒尺寸减小。SEM分析提供了对晶粒尺寸的见解，而EDX证实了铁成功地结合到ZnO晶格中。光学研究揭示了铁掺杂后带隙能量的降低。此外，随着铁浓度的变化，PL光谱的峰位发生了变化。通过对亚甲基蓝（MB）染料的降解来评价其光催化活性，180 min后降解率达到82%。掺铁氧化锌的表观速率常数高于纯氧化锌，表明其对废水的修复效果更好。
{"title":"Tailoring iron-doped ZnO nanoparticles for photocatalytic degradation of methylene blue","authors":"Abdul Baqi , Shahbaz Sarwer , Xianhua Hou , Hadia Noor , Noreen Fatima , Haleema Riaz , Syeda Rabia Ejaz , Memona Bibi , Muhammad Imran Khan , Abdallah Shanableh , Rafael Luque","doi":"10.1016/j.poly.2025.117853","DOIUrl":"10.1016/j.poly.2025.117853","url":null,"abstract":"<div><div>Iron-doped ZnO (Zn₁₋ₓFeₓO, x = 0.0, 0.05, 0.07, 0.10) nanoparticles were synthesized using a hydrothermal method. Various characterization techniques were employed to analyze the synthesized nanoparticles, including X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), ultraviolet-visible (UV–vis) spectroscopy, and photoluminescence (PL). XRD results showed that the crystallite size decreased with increasing iron content. SEM analysis provided insights into grain size, while EDX confirmed the successful incorporation of Fe into the ZnO lattice. Optical studies revealed a reduction in band gap energy upon Fe doping. Additionally, PL spectra exhibited shifts in peak positions with varying iron concentrations. The photocatalytic activity was evaluated through the degradation of methylene blue (MB) dye, achieving 82 % degradation after 180 min. The apparent rate constant for Fe-doped ZnO was higher than that of pure ZnO, highlighting its enhanced efficiency in wastewater remediation.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117853"},"PeriodicalIF":2.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145479276","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 : 2026-02-01Epub Date: 2025-11-04DOI: 10.1016/j.poly.2025.117860
Svetlana A. Belova , Alexander S. Belov , Ekaterina G. Lebed , Anastasia A. Danshina , Pavel V. Dorovatovskii , Artem S. Bogomyakov , Alexey I. Dmitriev , Mikhail V. Zhidkov , Denis V. Korchagin , Yan Z. Voloshin
Template condensation of 4-acetylthiazoloxime as a chelating ligand synthon and phenylboronic acid as a Lewis-acidic cross-linking agent on the nickel(II) ion using its perchlorate salt gave the ionic associate of phenylboron-monocapped nickel(II)-centered tris-thiazoloximate cation with ClO4− counter-anion. That with metal(II) chlorides (M2+ = Fe2+, Co2+, Ni2+, Mn2+ and Zn2+) as the sources of M2+ ions afforded the corresponding chloride-H-bonded pseudomacrobicyclic intracomplexes. As follows from the single-crystal X-ray diffraction data, their pseudomacrobicyclic structures are formed by CH…Cl− contacts with three N,S-heterocyclic groups of thiazoloximate synthons. Fe(II), Co(II) and Zn(II) ions are located in the centers of their trigonal-prismatic MN6-coordination polyhedra, while geometry of NiN6-polyhedra is intermediate between a trigonal prism and trigonal antiprism. All the prepared metal(II) pseudoclathrochelates were also characterized using elemental analysis, PXRD, MALDI-TOF MS, UV–vis and NMR methods. According to the magnetometry and X-ray diffraction data, their metal(II) ions are in high-spin states. The ac and dc magnetic studies, supported by the SA-CASSCF/NEVPT2 quantum chemical calculations, revealed that a given cobalt(II) pseudoclathrochelate exhibits the strong uniaxial magnetic anisotropy due to the unquenched angular orbital momentum. It also demonstrates a zero-field single-molecule magnet behavior with quantum tunneling of the magnetization as the only one magnetically sensitive relaxation mechanism.
{"title":"Synthesis, structure and magnetic properties of the monocapped 3d-metal(II) tris-N,S-heterocyclooximates: the design of cobalt pseudoclathrochelate with a single-ion magnet behavior","authors":"Svetlana A. Belova , Alexander S. Belov , Ekaterina G. Lebed , Anastasia A. Danshina , Pavel V. Dorovatovskii , Artem S. Bogomyakov , Alexey I. Dmitriev , Mikhail V. Zhidkov , Denis V. Korchagin , Yan Z. Voloshin","doi":"10.1016/j.poly.2025.117860","DOIUrl":"10.1016/j.poly.2025.117860","url":null,"abstract":"<div><div>Template condensation of 4-acetylthiazoloxime as a chelating ligand synthon and phenylboronic acid as a Lewis-acidic cross-linking agent on the nickel(II) ion using its perchlorate salt gave the ionic associate of phenylboron-monocapped nickel(II)-centered tris-thiazoloximate cation with ClO<sub>4</sub><sup>−</sup> counter-anion. That with metal(II) chlorides (M<sup>2+</sup> = Fe<sup>2+</sup>, Co<sup>2+</sup>, Ni<sup>2+</sup>, Mn<sup>2+</sup> and Zn<sup>2+</sup>) as the sources of M<sup>2+</sup> ions afforded the corresponding chloride-H-bonded pseudomacrobicyclic intracomplexes. As follows from the single-crystal X-ray diffraction data, their pseudomacrobicyclic structures are formed by C<img>H…Cl<sup>−</sup> contacts with three <em>N,S</em>-heterocyclic groups of thiazoloximate synthons. Fe(II), Co(II) and Zn(II) ions are located in the centers of their trigonal-prismatic <em>MN</em><sub><em>6</em></sub>-coordination polyhedra, while geometry of <em>NiN</em><sub><em>6</em></sub>-polyhedra is intermediate between a trigonal prism and trigonal antiprism. All the prepared metal(II) pseudoclathrochelates were also characterized using elemental analysis, PXRD, MALDI-TOF MS, UV–vis and NMR methods. According to the magnetometry and X-ray diffraction data, their metal(II) ions are in high-spin states. The <em>ac</em> and <em>dc</em> magnetic studies, supported by the SA-CASSCF/NEVPT2 quantum chemical calculations, revealed that a given cobalt(II) pseudoclathrochelate exhibits the strong uniaxial magnetic anisotropy due to the unquenched angular orbital momentum. It also demonstrates a zero-field single-molecule magnet behavior with quantum tunneling of the magnetization as the only one magnetically sensitive relaxation mechanism.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117860"},"PeriodicalIF":2.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145479277","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 : 2026-02-01Epub Date: 2025-10-25DOI: 10.1016/j.poly.2025.117850
Isaac de los Rios Hierro , Franco Scalambra , Vicente Jara-Pérez , Antonio Romerosa
The Ruthenium(II) phenylvinylidene complex [RuCp(=C=CHPh)(mPTA)(PPh3)](CF3SO3)2 (2) has been synthesized and characterized by NMR, IR and elemental analysis and its structure by single crystal X-ray diffraction (mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane). The chemical reactivity of this complex against water, acid medium, O2, CO, isopropylamine, cyclohexylamine, 2-aminopyridine, ethanethiol and ethanol was studied. As a result, new amino and thio-carbenes were obtained and characterized. Additionally, complex 2 was evaluated as catalyst for the isomerisation of linear allylic alcohols with different tail lengths.
合成了钌（II）苯基偏乙烯配合物[RuCp(=C=CHPh)(mPTA)(PPh3)](CF3SO3)2(2)，并通过核磁共振、红外光谱和元素分析对其进行了表征，通过单晶x射线衍射对其结构进行了表征（mPTA = n -甲基-1,3,5-三氮杂-7-磷adamantane）。研究了该配合物对水、酸性介质、O2、CO、异丙胺、环己胺、2-氨基吡啶、乙醇和乙醇的化学反应性。结果得到了新的氨基和硫代碳烯，并对其进行了表征。此外，络合物2作为不同尾长线性烯丙醇异构化的催化剂进行了评价。
{"title":"Synthesis of the new water soluble vinyl ruthenium complex [RuCp(=C=CPh)(PPh3)(mPTA2](CF3SO3) (mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane): chemical reactivity and catalytic properties for redox isomerization of allylic alcohols","authors":"Isaac de los Rios Hierro , Franco Scalambra , Vicente Jara-Pérez , Antonio Romerosa","doi":"10.1016/j.poly.2025.117850","DOIUrl":"10.1016/j.poly.2025.117850","url":null,"abstract":"<div><div>The Ruthenium(II) phenylvinylidene complex [RuCp(=C=CHPh)(mPTA)(PPh<sub>3</sub>)](CF<sub>3</sub>SO<sub>3</sub>)<sub>2</sub> (<strong>2</strong>) has been synthesized and characterized by NMR, IR and elemental analysis and its structure by single crystal X-ray diffraction (mPTA = <em>N-</em>methyl-1,3,5-triaza-7-phosphaadamantane). The chemical reactivity of this complex against water, acid medium, O<sub>2</sub>, CO, isopropylamine, cyclohexylamine, 2-aminopyridine, ethanethiol and ethanol was studied. As a result, new amino and thio-carbenes were obtained and characterized. Additionally, complex <strong>2</strong> was evaluated as catalyst for the isomerisation of linear allylic alcohols with different tail lengths.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117850"},"PeriodicalIF":2.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145479278","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 : 2026-02-01Epub Date: 2025-11-05DOI: 10.1016/j.poly.2025.117871
Bipul Chandra Biswas , Asadul Islam Shimul , Mohd Shkir , Farhat S. Khan , Mohamed Benghanem , R. Marnadu , Md. Azizur Rahman
Ca3BiBr3 is a promising candidate for solar cell applications due to its exceptional optical and electrical properties. Its absorptive properties have the capability to improve efficiency and minimize production costs in solar energy systems. To examine the optoelectronic characteristics and determine the most effective structure for improved performance, this investigation implements extensive simulations utilizing SCAPS-1D and DFT tools. DFT computations reveal that Ca3BiBr3 has a direct bandgap of 1.491 eV, accompanied by excellent absorption coefficients and exceptional structural stability, underscoring its promise as an effective material for solar applications. The device structure that has been evaluated using SCAPS-1D is composed of Ag/FTO/ETL/Ca3BiBr3/HTL/Ni, which includes a single electron transport layer (ETL) and multiple hole transport layers (HTLs). The device's efficacy was enhanced by optimizing critical parameters, such as thickness, temperature, doping concentration, defect density, and series-shunt resistances. The configuration of Ag/FTO/ZnO/Ca3BiBr3/CBTS/ Ni displayed the highest power conversion efficiency (PCE) of 28.57 %, an open-circuit voltage (VOC) of 1.154 V, a short-circuit current density (JSC) of 27.964 mA/cm2, and a fill factor (FF) of 88.52 %. This optimized design outperformed devices with alternative HTLs, including CuO, CFTS, Spiro-OMeTAD, CuI, and CBTS. The significance of precise material and structural optimization in enhancing the efficacy of perovskite solar cells (PSCs) is underscored by this study. To improve interpretability, machine learning-based Random Forest algorithms were adopted to analyze the influence of critical factors on device performance. The results highlight that the characteristics of the resistance and absorber layers are crucial in influencing total efficiency. The integration of machine learning with conventional simulation methods establishes a strong foundation for the advancement of scalable, efficient PV technologies.
{"title":"A computational and machine learning-driven investigation of Ca3BiBr3 perovskite solar cells: Fine-tuning the hole transport layer for enhanced performance","authors":"Bipul Chandra Biswas , Asadul Islam Shimul , Mohd Shkir , Farhat S. Khan , Mohamed Benghanem , R. Marnadu , Md. Azizur Rahman","doi":"10.1016/j.poly.2025.117871","DOIUrl":"10.1016/j.poly.2025.117871","url":null,"abstract":"<div><div>Ca<sub>3</sub>BiBr<sub>3</sub> is a promising candidate for solar cell applications due to its exceptional optical and electrical properties. Its absorptive properties have the capability to improve efficiency and minimize production costs in solar energy systems. To examine the optoelectronic characteristics and determine the most effective structure for improved performance, this investigation implements extensive simulations utilizing SCAPS-1D and DFT tools. DFT computations reveal that Ca<sub>3</sub>BiBr<sub>3</sub> has a direct bandgap of 1.491 eV, accompanied by excellent absorption coefficients and exceptional structural stability, underscoring its promise as an effective material for solar applications. The device structure that has been evaluated using SCAPS-1D is composed of Ag/FTO/ETL/Ca<sub>3</sub>BiBr<sub>3</sub>/HTL/Ni, which includes a single electron transport layer (ETL) and multiple hole transport layers (HTLs). The device's efficacy was enhanced by optimizing critical parameters, such as thickness, temperature, doping concentration, defect density, and series-shunt resistances. The configuration of Ag/FTO/ZnO/Ca<sub>3</sub>BiBr<sub>3</sub>/CBTS/ Ni displayed the highest power conversion efficiency (PCE) of 28.57 %, an open-circuit voltage (V<sub>OC</sub>) of 1.154 V, a short-circuit current density (J<sub>SC</sub>) of 27.964 mA/cm<sup>2</sup>, and a fill factor (FF) of 88.52 %. This optimized design outperformed devices with alternative HTLs, including CuO, CFTS, Spiro-OMeTAD, CuI, and CBTS. The significance of precise material and structural optimization in enhancing the efficacy of perovskite solar cells (PSCs) is underscored by this study. To improve interpretability, machine learning-based Random Forest algorithms were adopted to analyze the influence of critical factors on device performance. The results highlight that the characteristics of the resistance and absorber layers are crucial in influencing total efficiency. The integration of machine learning with conventional simulation methods establishes a strong foundation for the advancement of scalable, efficient PV technologies.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117871"},"PeriodicalIF":2.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145528104","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 : 2026-02-01Epub Date: 2025-11-03DOI: 10.1016/j.poly.2025.117863
Md Gishan , Mridul Karmakar , Rosa M. Gomila , Antonio Frontera , Shouvik Chattopadhyay
We report the synthesis and structural characterization of three zinc(II) tetrazolate complexes [Zn(PTZ)2(H2O)2] (1), [Zn(HL1)(PTZ)]2 (2), and [Zn(HL2)(PTZ)]2 (3) obtained via in situ [3 + 2] cycloaddition of azide with 2-cyanopyridine under mild conditions [HPTZ = 5(2-pyridyl)tetrazole, H2L1 = 4-chloro-2-(((2-((2-hydroxyethyl)amino)ethyl)imino)methyl)phenol, H2L2 = 4-bromo-2-(((2-((2-hydroxyethyl)amino)ethyl)imino)methyl)phenol]. X-ray diffraction analysis reveals that complex 1 forms discrete mononuclear units that self-assemble into 2D hydrogen-bonded sheets, driven by directional OH⋯N interactions between the coordinated water molecules and the tetrazolate moieties, reinforced by π–π stacking. In contrast, the dinuclear complexes 2 and 3 exhibit bridging μ-NN-tetrazolate ligands and distorted octahedral coordination geometries. Surprisingly, their solid-state structures are stabilized by unconventional halogen⋯π interactions between the negatively charged Cl (in 2) or Br (in 3) atoms and the electron-rich π-system of Zn-bound phenolate rings. These counterintuitive contacts are supported by Hirshfeld surface analysis and will be rationalized through molecular electrostatic potential (MEP) surface analysis, energetically evaluated via DFT calculations, and further characterized using the Non-Covalent Interaction (NCIplot) and Quantum Theory of Atoms in Molecules (QTAIM) approaches. This combined experimental and theoretical investigation provides new insights into the nature and strength of hydrogen bonding and halogen⋯π interactions in tetrazolate-based supramolecular assemblies.
{"title":"Tandem synthesis of zinc tetrazolate complexes via [3 + 2] cyclo-addition at ambient condition and exploration of noncovalent interactions in their solid state structures","authors":"Md Gishan , Mridul Karmakar , Rosa M. Gomila , Antonio Frontera , Shouvik Chattopadhyay","doi":"10.1016/j.poly.2025.117863","DOIUrl":"10.1016/j.poly.2025.117863","url":null,"abstract":"<div><div>We report the synthesis and structural characterization of three zinc(II) tetrazolate complexes [Zn(PTZ)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>] (<strong>1</strong>), [Zn(HL<sup>1</sup>)(PTZ)]<sub>2</sub> (<strong>2</strong>), and [Zn(HL<sup>2</sup>)(PTZ)]<sub>2</sub> (<strong>3</strong>) obtained via in situ [3 + 2] cycloaddition of azide with 2-cyanopyridine under mild conditions [HPTZ = 5(2-pyridyl)tetrazole, H<sub>2</sub>L<sup>1</sup> = 4-chloro-2-(((2-((2-hydroxyethyl)amino)ethyl)imino)methyl)phenol, H<sub>2</sub>L<sup>2</sup> = 4-bromo-2-(((2-((2-hydroxyethyl)amino)ethyl)imino)methyl)phenol]. X-ray diffraction analysis reveals that complex <strong>1</strong> forms discrete mononuclear units that self-assemble into 2D hydrogen-bonded sheets, driven by directional O<img>H⋯N interactions between the coordinated water molecules and the tetrazolate moieties, reinforced by π–π stacking. In contrast, the dinuclear complexes <strong>2</strong> and <strong>3</strong> exhibit bridging μ-NN-tetrazolate ligands and distorted octahedral coordination geometries. Surprisingly, their solid-state structures are stabilized by unconventional halogen⋯π interactions between the negatively charged Cl (in <strong>2</strong>) or Br (in 3) atoms and the electron-rich π-system of Zn-bound phenolate rings. These counterintuitive contacts are supported by Hirshfeld surface analysis and will be rationalized through molecular electrostatic potential (MEP) surface analysis, energetically evaluated via DFT calculations, and further characterized using the Non-Covalent Interaction (NCIplot) and Quantum Theory of Atoms in Molecules (QTAIM) approaches. This combined experimental and theoretical investigation provides new insights into the nature and strength of hydrogen bonding and halogen⋯π interactions in tetrazolate-based supramolecular assemblies.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117863"},"PeriodicalIF":2.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145528100","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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