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}
Pub Date : 2026-02-01Epub Date: 2025-12-15DOI: 10.1016/j.poly.2025.117935
Gabriella S. Godinho, Kevin K. Lee, Qien Feng, Guang Wu, Justin J. Wilson, Trevor W. Hayton
The complexation of the uranyl ion (UO22+) by macrocyclic ligands is hindered by the rigidly enforced trans orientation of its oxo ligands. To further investigate this coordination chemistry challenge, here we investigate the reactivity of UO22+ with two different 18-membered aza-crown macrocycles, diaza-dibenzo-18-crown-6 (DADBC) and 7,16-bis(N-methylacetamide)diaza-18-crown-6 (BAM). The reaction of uranyl triflate, [UO2(OTf)2(THF)3], with DADBC in toluene afforded [UO2(DADBC)][OTf]2, in which the UO22+ ion is fully encapsulated by the macrocycle. This conclusion was supported by NMR, UV–Vis, IR, and Raman spectroscopies, as well as single-crystal X-ray crystallography. Attempts to form the in-macrocycle complex of BAM, however, were unsuccessful. The reaction of BAM with [UO2(OTf)2(THF)3] in THF/CH2Cl2 unexpectedly afforded crystals of [H2BAM][OTf]2, where the protons are derived from solvate water in the BAM crystal lattice. In contrast, reaction of BAM with UO2(NO3)2·6H2O resulted in formation of the coordination polymer, [UO2(κ2-NO3)2(μ-BAM)]∞. The crystal structure of this compound revealed that the BAM ligand is coordinated to UO22+ via its pendent carboxamide donors, while the donor atoms within the macrocyclic cavity remained unbound. The X-ray crystal structure of the free BAM ligand was also obtained, which showed that it exists in an identical conformation to that seen in the structure of [UO2(κ2-NO3)2(μ-BAM)]∞, where the pendent carboxamide donors are engaged in an intramolecular hydrogen-bonding interaction with the donor atoms within the macrocycle. These results suggest that the enthalpic penalty of breaking these intramolecular hydrogen bonds prevents UO22+ from “threading the needle.” In contrast, DADBC, which lacks such intramolecular hydrogen-bonding interactions, can readily accommodate UO22+. This comparison demonstrates how subtle modifications to the macrocycle, such as cavity size, rigidity, and pendant donor groups, can affect its affinity for UO22+, and provide insights into macrocycle chelator design for this ion for applications in separations, medicine, and energy.
{"title":"To thread or not to thread: Reaction of uranyl (UO22+) with two Aza-crown macrocycles1","authors":"Gabriella S. Godinho, Kevin K. Lee, Qien Feng, Guang Wu, Justin J. Wilson, Trevor W. Hayton","doi":"10.1016/j.poly.2025.117935","DOIUrl":"10.1016/j.poly.2025.117935","url":null,"abstract":"<div><div>The complexation of the uranyl ion (UO<sub>2</sub><sup>2+</sup>) by macrocyclic ligands is hindered by the rigidly enforced <em>trans</em> orientation of its oxo ligands. To further investigate this coordination chemistry challenge, here we investigate the reactivity of UO<sub>2</sub><sup>2+</sup> with two different 18-membered aza-crown macrocycles, diaza-dibenzo-18-crown-6 (<strong>DADBC</strong>) and 7,16-bis(<em>N</em>-methylacetamide)diaza-18-crown-6 (<strong>BAM</strong>). The reaction of uranyl triflate, [UO<sub>2</sub>(OTf)<sub>2</sub>(THF)<sub>3</sub>], with <strong>DADBC</strong> in toluene afforded [UO<sub>2</sub>(<strong>DADBC</strong>)][OTf]<sub>2</sub>, in which the UO<sub>2</sub><sup>2+</sup> ion is fully encapsulated by the macrocycle. This conclusion was supported by NMR, UV–Vis, IR, and Raman spectroscopies, as well as single-crystal X-ray crystallography. Attempts to form the in-macrocycle complex of <strong>BAM</strong>, however, were unsuccessful. The reaction of <strong>BAM</strong> with [UO<sub>2</sub>(OTf)<sub>2</sub>(THF)<sub>3</sub>] in THF/CH<sub>2</sub>Cl<sub>2</sub> unexpectedly afforded crystals of [H<sub>2</sub><strong>BAM</strong>][OTf]<sub>2</sub>, where the protons are derived from solvate water in the <strong>BAM</strong> crystal lattice. In contrast, reaction of <strong>BAM</strong> with UO<sub>2</sub>(NO<sub>3</sub>)<sub>2</sub>·6H<sub>2</sub>O resulted in formation of the coordination polymer, [UO<sub>2</sub>(κ<sup>2</sup>-NO<sub>3</sub>)<sub>2</sub>(μ-<strong>BAM</strong>)]<sub>∞</sub>. The crystal structure of this compound revealed that the <strong>BAM</strong> ligand is coordinated to UO<sub>2</sub><sup>2+</sup> via its pendent carboxamide donors, while the donor atoms within the macrocyclic cavity remained unbound. The X-ray crystal structure of the free <strong>BAM</strong> ligand was also obtained, which showed that it exists in an identical conformation to that seen in the structure of [UO<sub>2</sub>(κ<sup>2</sup>-NO<sub>3</sub>)<sub>2</sub>(μ-<strong>BAM</strong>)]<sub>∞</sub>, where the pendent carboxamide donors are engaged in an intramolecular hydrogen-bonding interaction with the donor atoms within the macrocycle. These results suggest that the enthalpic penalty of breaking these intramolecular hydrogen bonds prevents UO<sub>2</sub><sup>2+</sup> from “threading the needle.” In contrast, <strong>DADBC</strong>, which lacks such intramolecular hydrogen-bonding interactions, can readily accommodate UO<sub>2</sub><sup>2+</sup>. This comparison demonstrates how subtle modifications to the macrocycle, such as cavity size, rigidity, and pendant donor groups, can affect its affinity for UO<sub>2</sub><sup>2+</sup>, and provide insights into macrocycle chelator design for this ion for applications in separations, medicine, and energy.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"285 ","pages":"Article 117935"},"PeriodicalIF":2.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145798005","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: 2025-11-17DOI: 10.1016/j.poly.2025.117895
Jun Yuan , Yong Wang , Lizhen Chen , Jianlong Wang
Bis(2,4-dinitro-1H-imidazol-1-yl)ethane (BDNIE) was synthesized in a single step from dibromoethane and 2,4-dinitroimidazole. The compound was fully characterized by X-ray single-crystal diffraction, nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, high-resolution mass spectrometry (HRMS), elemental analysis, and thermogravimetry-differential scanning calorimetry (TG-DSC). Theoretical detonation pressure (P) and velocity (vD) were calculated using Gaussian 09 and the K-J equation. Crystal structure analysis, combined with non-covalent interaction (NCI), energy framework, and Hirshfeld surface analyses, revealed an extensive network of hydrogen bonds and π-π interactions within the BDNIE crystal. These interactions contribute to its favorable density (1.77 g cm−3), excellent thermal stability (Td = 323.98 °C), acceptable detonation performance (vD = 7816 m s−1, P = 26.7 GPa), and low mechanical sensitivity (IS = 35 J, FS = 360 N). These advantages highlight the potential of BDNIE as an insensitive heat-resistant explosive.
{"title":"Synergistic non-covalent interactions for enhanced thermal stability in high-performance energetic materials: Bis(2,4-dinitro-1H-imidazolyl)ethane","authors":"Jun Yuan , Yong Wang , Lizhen Chen , Jianlong Wang","doi":"10.1016/j.poly.2025.117895","DOIUrl":"10.1016/j.poly.2025.117895","url":null,"abstract":"<div><div>Bis(2,4-dinitro-1H-imidazol-1-yl)ethane (BDNIE) was synthesized in a single step from dibromoethane and 2,4-dinitroimidazole. The compound was fully characterized by X-ray single-crystal diffraction, nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, high-resolution mass spectrometry (HRMS), elemental analysis, and thermogravimetry-differential scanning calorimetry (TG-DSC). Theoretical detonation pressure (P) and velocity (v<sub>D</sub>) were calculated using Gaussian 09 and the K-J equation. Crystal structure analysis, combined with non-covalent interaction (NCI), energy framework, and Hirshfeld surface analyses, revealed an extensive network of hydrogen bonds and <em>π</em>-<em>π</em> interactions within the BDNIE crystal. These interactions contribute to its favorable density (1.77 g cm<sup>−3</sup>), excellent thermal stability (T<sub>d</sub> = 323.98 °C), acceptable detonation performance (v<sub>D</sub> = 7816 m s<sup>−1</sup>, <em>P</em> = 26.7 GPa), and low mechanical sensitivity (IS = 35 J, FS = 360 N). These advantages highlight the potential of BDNIE as an insensitive heat-resistant explosive.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117895"},"PeriodicalIF":2.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145577695","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: 2025-11-16DOI: 10.1016/j.poly.2025.117896
Tara Karampour , Morteza Rouhani , Marjan Jebeli Javan
Aromaticity in boron-containing heterocycles exhibits notable sensitivity to electronic excitation. In this study, we present a comprehensive analysis of the aromatic and antiaromatic behavior of 1H-borole and 1H-borirene in both their ground singlet (S₀) and first excited triplet (T₁) states using structural, magnetic, and energetic criteria. Bond length alternation (ΔBL), harmonic oscillator model of aromaticity (HOMA), nucleus-independent chemical shifts (NICS), localized orbital locator (LOL-π) maps, and isomerization stabilization energy (ISE) were all employed to assess the π-electron delocalization in these systems. The results consistently indicate an inversion of aromatic character upon excitation: 1H-borole transitions from antiaromatic to aromatic, while 1H-borirene behaves oppositely. These insights expand our understanding of excited-state aromaticity in electron-deficient heterocycles and underscore the utility of a multi-criteria approach to aromaticity evaluation.
{"title":"Aromatic and Antiaromatic switching in 1H-Borole and 1H-Borirene: Insights from ground and triplet states","authors":"Tara Karampour , Morteza Rouhani , Marjan Jebeli Javan","doi":"10.1016/j.poly.2025.117896","DOIUrl":"10.1016/j.poly.2025.117896","url":null,"abstract":"<div><div>Aromaticity in boron-containing heterocycles exhibits notable sensitivity to electronic excitation. In this study, we present a comprehensive analysis of the aromatic and antiaromatic behavior of 1<em>H</em>-borole and 1<em>H</em>-borirene in both their ground singlet (<em>S₀</em>) and first excited triplet (<em>T₁</em>) states using structural, magnetic, and energetic criteria. Bond length alternation (ΔBL), harmonic oscillator model of aromaticity (HOMA), nucleus-independent chemical shifts (NICS), localized orbital locator (LOL-π) maps, and isomerization stabilization energy (ISE) were all employed to assess the π-electron delocalization in these systems. The results consistently indicate an inversion of aromatic character upon excitation: 1<em>H</em>-borole transitions from antiaromatic to aromatic, while 1<em>H</em>-borirene behaves oppositely. These insights expand our understanding of excited-state aromaticity in electron-deficient heterocycles and underscore the utility of a multi-criteria approach to aromaticity evaluation.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117896"},"PeriodicalIF":2.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145577698","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: 2025-12-01DOI: 10.1016/j.poly.2025.117917
Metin Yıldırım , Burcu Somtürk Yilmaz , Mehmet Çimentepe , Adem Necip , Özden Dellal
In recent years, various nanostructures, including nanoflowers, have attracted attention due to their effective biomedical properties. In this study, M@hNFs were synthesized using morin as the organic component and Cu2+ ions as the inorganic component. The prepared nanoflowers were characterized by SEM, EDX, FTIR, and XRD analyses, and their biological activities were subsequently investigated, including anticancer effects against MCF-7 breast cancer cells, acetylcholinesterase (AChE) inhibitory activity, antioxidant capacity, antibacterial activity against Staphylococcus aureus, Enterococcus faecalis (E. faecalis), Pseudomonas aeruginosa, Escherichia coli, methicillin-resistant Staphylococcus aureus (MRSA), and multidrug-resistant Escherichia coli (MDR E. coli) using the broth microdilution method, as well as antibiofilm activity against MRSA and MDR E. coli. SEM analysis revealed that the synthesized M@hNFs exhibited a diameter of 24.69 μm. Antioxidant assays demonstrated IC₅₀ values of 131.3 μg/mL (DPPH) and 51.3 μg/mL (ABTS). The AChE inhibitory activity was confirmed with an IC₅₀ value of 72.2 ± 2.1 μg/mL. Furthermore, M@hNFs reduced the viability of MCF-7 cells to 56 % at 500 μg/mL. In antibacterial assays, the synthesized hNFs exhibited stronger activity compared with morin alone, showing the most potent effect against E. faecalis with a MIC value of 32 μg/mL. Importantly, the hNFs also demonstrated activity against resistant strains, inhibiting MRSA and MDR E. coli at 256 μg/mL. At 1024 μg/mL, M@Cu-hNFs inhibited biofilm formation by MRSA and MDR E. coli by 69.7 % and 66.3 %, respectively. Taken together, these findings indicate that the prepared M@hNFs possess multiple biomedical properties and hold significant potential for further studies and future biomedical applications.
近年来，包括纳米花在内的各种纳米结构因其有效的生物医学特性而备受关注。本研究以桑里素为有机组分，Cu2+离子为无机组分合成了M@hNFs。采用SEM、EDX、FTIR和XRD对制备的纳米花进行了表征，并对其生物活性进行了研究，包括对MCF-7乳腺癌细胞的抗癌作用、对乙酰胆碱酯酶（AChE）的抑制活性、抗氧化能力、对金黄色葡萄球菌、粪肠球菌（E. faecalis）、铜绿假单胞菌、大肠杆菌、耐甲氧西林金黄色葡萄球菌（MRSA）的抑菌活性。利用肉汤微量稀释法检测耐多药大肠杆菌（MDR E. coli），以及抗MRSA和MDR E. coli的抗菌膜活性。SEM分析表明，合成的M@hNFs的直径为24.69 μm。抗氧化试验显示IC₅₀值为131.3 μg/mL （DPPH）和51.3 μg/mL （ABTS）。证实了AChE的抑制活性，IC₅₀值为72.2±2.1 μg/mL。此外，M@hNFs在500 μg/mL时将MCF-7细胞的存活率降低至56%。在抗菌实验中，合成的hNFs比单独的桑苷具有更强的抑菌活性，对粪肠杆菌的抑制作用最强，MIC值为32 μg/mL。重要的是，hnf也显示出对耐药菌株的活性，在256 μg/mL的浓度下抑制MRSA和MDR大肠杆菌。在1024 μg/mL浓度下，M@Cu-hNFs对MRSA和MDR大肠杆菌形成生物膜的抑制作用分别为69.7%和66.3%。综上所述，这些发现表明制备的M@hNFs具有多种生物医学特性，具有进一步研究和未来生物医学应用的巨大潜力。
{"title":"Antioxidant, anti-acetylcholinesterase, antimicrobial, and anticancer activities of Morin–Cu(II) hybrid Nanoflowers","authors":"Metin Yıldırım , Burcu Somtürk Yilmaz , Mehmet Çimentepe , Adem Necip , Özden Dellal","doi":"10.1016/j.poly.2025.117917","DOIUrl":"10.1016/j.poly.2025.117917","url":null,"abstract":"<div><div>In recent years, various nanostructures, including nanoflowers, have attracted attention due to their effective biomedical properties. In this study, M@hNFs were synthesized using morin as the organic component and Cu<sup>2+</sup> ions as the inorganic component. The prepared nanoflowers were characterized by SEM, EDX, FTIR, and XRD analyses, and their biological activities were subsequently investigated, including anticancer effects against MCF-7 breast cancer cells, acetylcholinesterase (AChE) inhibitory activity, antioxidant capacity, antibacterial activity against <em>Staphylococcus aureus</em>, <em>Enterococcus faecalis</em> (<em>E. faecalis</em>), <em>Pseudomonas aeruginosa</em>, <em>Escherichia coli</em>, methicillin-resistant <em>Staphylococcus aureus</em> (MRSA), and multidrug-resistant <em>Escherichia coli</em> (MDR <em>E. coli</em>) using the broth microdilution method, as well as antibiofilm activity against MRSA and MDR <em>E. coli</em>. SEM analysis revealed that the synthesized M@hNFs exhibited a diameter of 24.69 μm. Antioxidant assays demonstrated IC₅₀ values of 131.3 μg/mL (DPPH) and 51.3 μg/mL (ABTS). The AChE inhibitory activity was confirmed with an IC₅₀ value of 72.2 ± 2.1 μg/mL. Furthermore, M@hNFs reduced the viability of MCF-7 cells to 56 % at 500 μg/mL. In antibacterial assays, the synthesized hNFs exhibited stronger activity compared with morin alone, showing the most potent effect against <em>E. faecalis</em> with a MIC value of 32 μg/mL. Importantly, the hNFs also demonstrated activity against resistant strains, inhibiting MRSA and MDR <em>E. coli</em> at 256 μg/mL. At 1024 μg/mL, M@Cu-hNFs inhibited biofilm formation by MRSA and MDR <em>E. coli</em> by 69.7 % and 66.3 %, respectively. Taken together, these findings indicate that the prepared M@hNFs possess multiple biomedical properties and hold significant potential for further studies and future biomedical applications.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"285 ","pages":"Article 117917"},"PeriodicalIF":2.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145693468","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: 2025-12-01DOI: 10.1016/j.poly.2025.117913
Mostafa Riahi Farsani
A novel heterogeneous catalyst based on a Keplerate-type polyoxometalate and ionic liquid, W₇₂Fe₃₀-IL, was synthesized via anion exchange between the giant {W₇₂Fe₃₀} cluster and [3-aminoethyl-1-methylimidazolium]Br. The structure of this catalyst was confirmed by FT-IR, Raman, XRD, CHNS, XRF, ICP and thermogravimetric analyses. The resulting hybrid exhibited excellent catalytic performance in the oxidative desulfurization (ODS) of model sulfur-containing compounds, including dibenzothiophene (DBT), benzothiophene (BT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT), using hydrogen peroxide as a green oxidant under mild conditions. Various reaction parameters—oxidant-to-substrate ratio, catalyst loading, temperature, acid promoter, and substrate type—were systematically studied. W₇₂Fe₃₀-IL achieved 99.5 % sulfur removal from DBT at 40 °C within 90 min with an optimal H₂O₂/DBT molar ratio of 4:1. The catalytic activity followed the order DBT > 4,6-DMDBT > BT, correlating with electronic density and steric hindrance around the sulfur atom. Moreover, the catalyst showed excellent reusability over five cycles with minimal activity loss. High structural stability was confirmed by XRD and FTIR, with the hot filtration test and ICP analyse indicating no leaching. This study highlights the potential of Keplerate-type POM-ILs as efficient, recyclable, and environmentally friendly catalysts for deep fuel desulfurization, offering a promising alternative to conventional hydrodesulfurization, which operates under harsher conditions.
{"title":"A Keplerate type polyoxometalate-based ionic liquids as heterogeneous hybrid catalysts for efficient oxidation desulfurization using hydrogen peroxide under mild reaction conditions","authors":"Mostafa Riahi Farsani","doi":"10.1016/j.poly.2025.117913","DOIUrl":"10.1016/j.poly.2025.117913","url":null,"abstract":"<div><div>A novel heterogeneous catalyst based on a Keplerate-type polyoxometalate and ionic liquid, W₇₂Fe₃₀-IL, was synthesized via anion exchange between the giant {W₇₂Fe₃₀} cluster and [3-aminoethyl-1-methylimidazolium]Br. The structure of this catalyst was confirmed by FT-IR, Raman, XRD, CHNS, XRF, ICP and thermogravimetric analyses. The resulting hybrid exhibited excellent catalytic performance in the oxidative desulfurization (ODS) of model sulfur-containing compounds, including dibenzothiophene (DBT), benzothiophene (BT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT), using hydrogen peroxide as a green oxidant under mild conditions. Various reaction parameters—oxidant-to-substrate ratio, catalyst loading, temperature, acid promoter, and substrate type—were systematically studied. W₇₂Fe₃₀-IL achieved 99.5 % sulfur removal from DBT at 40 °C within 90 min with an optimal H₂O₂/DBT molar ratio of 4:1. The catalytic activity followed the order DBT > 4,6-DMDBT > BT, correlating with electronic density and steric hindrance around the sulfur atom. Moreover, the catalyst showed excellent reusability over five cycles with minimal activity loss. High structural stability was confirmed by XRD and FTIR, with the hot filtration test and ICP analyse indicating no leaching. This study highlights the potential of Keplerate-type POM-ILs as efficient, recyclable, and environmentally friendly catalysts for deep fuel desulfurization, offering a promising alternative to conventional hydrodesulfurization, which operates under harsher conditions.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"285 ","pages":"Article 117913"},"PeriodicalIF":2.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145693470","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.2025.117908
Stefano Elli, Antonino Famulari, Javier Martí-Rujas
The self-assembly of tris-pyridyl-benzene ligand with ZnI2 in the presence of benzaldehyde yields a poly-[n]-catenane formed of large M12L8 metal organic cages (MOCs) which is used to study guest exchange of small non-aromatic molecules like nitromethane. X-ray crystallographic analysis revealed that guest exchange reaction takes place via gas-solid single-crystal-to-single-crystal (SCSC) process. The single crystal X-ray diffraction (SC-XRD) data allowed to determine the ordered guest content within the M12L8 nanocages. Density Functional Theory (DFT) calculations specific for solid state crystalline systems have been carried out to estimate the energy interactions among host and guest molecules (Ehost-guest) and to compute the maps of electrostatic potential (MEPs) for each guest. The outcomes of the DFT results helped to rationalize the guest exchange reaction considering both ordered and disordered molecules in the system were the Ehost-guest differs only in ∼4 kcal/mol. The role of the interlocking among M12L8 cages in the host dynamic behavior and the overall catenane structural stability is emphasised. The observed nitromethane guest uptake is important in the field of gas-solid molecular inclusion for instance in applications for the absorption of gases like CO2, CH4, SO2 or NOx compounds.
{"title":"Nitromethane gas absorption in interlocked icosahedral M12L8 nanocages","authors":"Stefano Elli, Antonino Famulari, Javier Martí-Rujas","doi":"10.1016/j.poly.2025.117908","DOIUrl":"10.1016/j.poly.2025.117908","url":null,"abstract":"<div><div>The self-assembly of tris-pyridyl-benzene ligand with ZnI<sub>2</sub> in the presence of benzaldehyde yields a poly-[n]-catenane formed of large M<sub>12</sub>L<sub>8</sub> metal organic cages (MOCs) which is used to study guest exchange of small non-aromatic molecules like nitromethane. X-ray crystallographic analysis revealed that guest exchange reaction takes place via gas-solid single-crystal-to-single-crystal (SCSC) process. The single crystal X-ray diffraction (SC-XRD) data allowed to determine the ordered guest content within the M<sub>12</sub>L<sub>8</sub> nanocages. Density Functional Theory (DFT) calculations specific for solid state crystalline systems have been carried out to estimate the energy interactions among host and guest molecules (<em>E</em><sub>host-guest</sub>) and to compute the maps of electrostatic potential (MEPs) for each guest. The outcomes of the DFT results helped to rationalize the guest exchange reaction considering both ordered and disordered molecules in the system were the <em>E</em><sub>host-guest</sub> differs only in ∼4 kcal/mol. The role of the interlocking among M<sub>12</sub>L<sub>8</sub> cages in the host dynamic behavior and the overall catenane structural stability is emphasised. The observed nitromethane guest uptake is important in the field of gas-solid molecular inclusion for instance in applications for the absorption of gases like CO<sub>2</sub>, CH<sub>4</sub>, SO<sub>2</sub> or NOx compounds.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117908"},"PeriodicalIF":2.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145621351","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: 2025-12-08DOI: 10.1016/j.poly.2025.117919
Tiantian Luo , Junyi Wang , Ruiyan Wang , Jiale Wang , Hao Yan , Bei Zhang , Qi Zhou
In this study, a one-dimensional core–shell photocatalyst composed of hydrogenated TiO2 (H-TiO2) coated with an amorphous metal–organic framework (MOF) was synthesized via a simple hydrothermal method and applied as an efficient peroxymonosulfate (PMS) activator for Rhodamine B (RhB) degradation. Under simulated sunlight irradiation for 20 min, the optimized H-TiO2/BPDC*2 catalyst achieved 99.40 % RhB removal at an initial concentration of 100 mg/L. Its apparent kinetic rate constant was 4.28 and 1.06 times higher than those of H-TiO2 and H-TiO2/BPDC, respectively. The enhanced performance is attributed to the core–shell heterojunction structure, which improves light absorption and charge separation, as evidenced by increased photocurrent, reduced photoluminescence intensity, and shorter time-resolved photoluminescence (TRPL) decay. Furthermore, the catalyst exhibited excellent stability over multiple cycles, demonstrating strong potential for practical wastewater treatment applications. Mechanistic studies revealed that ·O2- and 1O2 were the dominant reactive species involved in the degradation process.
{"title":"Efficient photocatalytic degradation of rhodamine B by amorphous MOF-coated hydrogenated titanium dioxide core-shell photocatalyst coupled with peroxymonosulfate activation","authors":"Tiantian Luo , Junyi Wang , Ruiyan Wang , Jiale Wang , Hao Yan , Bei Zhang , Qi Zhou","doi":"10.1016/j.poly.2025.117919","DOIUrl":"10.1016/j.poly.2025.117919","url":null,"abstract":"<div><div>In this study, a one-dimensional core–shell photocatalyst composed of hydrogenated TiO<sub>2</sub> (H-TiO<sub>2</sub>) coated with an amorphous metal–organic framework (MOF) was synthesized via a simple hydrothermal method and applied as an efficient peroxymonosulfate (PMS) activator for Rhodamine B (RhB) degradation. Under simulated sunlight irradiation for 20 min, the optimized H-TiO<sub>2</sub>/BPDC*2 catalyst achieved 99.40 % RhB removal at an initial concentration of 100 mg/L. Its apparent kinetic rate constant was 4.28 and 1.06 times higher than those of H-TiO<sub>2</sub> and H-TiO<sub>2</sub>/BPDC, respectively. The enhanced performance is attributed to the core–shell heterojunction structure, which improves light absorption and charge separation, as evidenced by increased photocurrent, reduced photoluminescence intensity, and shorter time-resolved photoluminescence (TRPL) decay. Furthermore, the catalyst exhibited excellent stability over multiple cycles, demonstrating strong potential for practical wastewater treatment applications. Mechanistic studies revealed that ·O<sub>2</sub><sup>-</sup> and <sup>1</sup>O<sub>2</sub> were the dominant reactive species involved in the degradation process.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"285 ","pages":"Article 117919"},"PeriodicalIF":2.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748526","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.2025.117915
Xunfei Ma , Bo Sun , Xiaochen Liu , Han Yu , Na Sun , Zhe Gong , Mingdong Zhou , Yaguang Sun
The electrochemical performance of aqueous zinc-ion batteries (ZIBs) is significantly hindered by dendritic growth of the zinc anode, which shortens the cycling life. To address these challenges, a two-dimensional (2D) zinc-based metal-organic framework (MOF), namely a Zn(II) coordination polymer (ZHPCA) [1], was synthesized via a solvothermal method. The ZCu-modified zinc electrode (ZCu@Zn) was fabricated by integrating ZHPCA with copper powder as an interfacial modification layer (ZCu), using carboxymethyl cellulose (CMC) as a binder. The ZCu layer effectively mitigated both the hydrogen evolution reaction (HER) and surface corrosion of the zinc anode. During the zinc deposition/stripping process, ZCu provided an effective substrate for zinc-ion nucleation, enabling uniform deposition and structural homogenization, thereby effectively suppressing dendrite growth. As a result, the assembled ZCu@Zn||ZCu@Zn symmetric battery demonstrated a low over potential of 40 mV and an extended cycle life of 900 h. In addition, activated carbon (AC) was employed as the cathode to assemble ZCu@Zn||AC hybrid capacitors, which exhibited a significantly enhanced capacitive performance. In conclusion, employing ZCu@Zn as a modified zinc anode offers a promising strategy for improving the stability and reversibility of aqueous zinc-ion batteries.
{"title":"Functional MOFs anode protection layer design for high-performance aqueous zinc ion batteries","authors":"Xunfei Ma , Bo Sun , Xiaochen Liu , Han Yu , Na Sun , Zhe Gong , Mingdong Zhou , Yaguang Sun","doi":"10.1016/j.poly.2025.117915","DOIUrl":"10.1016/j.poly.2025.117915","url":null,"abstract":"<div><div>The electrochemical performance of aqueous zinc-ion batteries (ZIBs) is significantly hindered by dendritic growth of the zinc anode, which shortens the cycling life. To address these challenges, a two-dimensional (2D) zinc-based metal-organic framework (MOF), namely a Zn(II) coordination polymer (ZHPCA) [<span><span>1</span></span>], was synthesized via a solvothermal method. The ZCu-modified zinc electrode (ZCu@Zn) was fabricated by integrating ZHPCA with copper powder as an interfacial modification layer (ZCu), using carboxymethyl cellulose (CMC) as a binder. The ZCu layer effectively mitigated both the hydrogen evolution reaction (HER) and surface corrosion of the zinc anode. During the zinc deposition/stripping process, ZCu provided an effective substrate for zinc-ion nucleation, enabling uniform deposition and structural homogenization, thereby effectively suppressing dendrite growth. As a result, the assembled ZCu@Zn||ZCu@Zn symmetric battery demonstrated a low over potential of 40 mV and an extended cycle life of 900 h. In addition, activated carbon (AC) was employed as the cathode to assemble ZCu@Zn||AC hybrid capacitors, which exhibited a significantly enhanced capacitive performance. In conclusion, employing ZCu@Zn as a modified zinc anode offers a promising strategy for improving the stability and reversibility of aqueous zinc-ion batteries.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"285 ","pages":"Article 117915"},"PeriodicalIF":2.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145693374","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.2025.117899
A. Tesmar , A. Sikorski , P. Niedziałkowski , B. Matusiewicz , I. Inkielewicz-Stępniak , D. Wyrzykowski
The nature of the counterions is a key factor in designing nitrilotriacetate (nta) oxidovanadium(IV) salts. Selecting the appropriate counterion affects the formation of complexes with either mono- or hetero-ligands in the coordination sphere, as well as mono- or heteronuclear entities. N-heterocyclic compounds can serve dual roles: they can act as counterions and simultaneously chelate the vanadium(IV) cation, or they can function solely as counterions without directly coordinating with the metal centre. Consequently, it enables the design of new coordination compounds with desirable physicochemical and biological properties. In this article, we present the crystal structure of a novel heteroligand nitrilotriacetate (nta) oxidovanadium(IV) complex salt of a general formula, [(2-NH2–3-OH)pyH)][VO(nta)(2-NH2–3-O-pyH)]∙H2O, where 2-amino-3-hydroxypyridine acts as both a zwitterionic ligand (2-NH2–3-O-pyH)± and a counterion [(2-NH2–3-OH)pyH]+. The physicochemical properties of the newly synthesized complex salt were thoroughly investigated and analyzed, including its ABTS•+ radical scavenging activity and reactivity towards hydrogen peroxide (H2O2). These studies aimed to explore potential structural features of the oxidovanadium(IV) species that may influence their antioxidant activity. Finally, the potential of 2-amino-3-hydroxypyridine and [(2-NH2–3-OH)pyH)][VO(nta)(2-NH2–3-O-pyH)]∙H2O as cytoprotective agents against oxidative damage induced by H2O2 was assessed using the HT22 hippocampal neuronal cell line.
{"title":"A novel heteroligand nitrilotriacetate oxidovanadium(IV) complex salt with 2-amino-3-hydroxypyridine as a zwitterionic ligand and counterion: Structural characterisation, antioxidant activity and cytoprotective potential","authors":"A. Tesmar , A. Sikorski , P. Niedziałkowski , B. Matusiewicz , I. Inkielewicz-Stępniak , D. Wyrzykowski","doi":"10.1016/j.poly.2025.117899","DOIUrl":"10.1016/j.poly.2025.117899","url":null,"abstract":"<div><div>The nature of the counterions is a key factor in designing nitrilotriacetate (nta) oxidovanadium(IV) salts. Selecting the appropriate counterion affects the formation of complexes with either mono- or hetero-ligands in the coordination sphere, as well as mono- or heteronuclear entities. N-heterocyclic compounds can serve dual roles: they can act as counterions and simultaneously chelate the vanadium(IV) cation, or they can function solely as counterions without directly coordinating with the metal centre. Consequently, it enables the design of new coordination compounds with desirable physicochemical and biological properties. In this article, we present the crystal structure of a novel heteroligand nitrilotriacetate (nta) oxidovanadium(IV) complex salt of a general formula, [(2-NH<sub>2</sub>–3-OH)pyH)][VO(nta)(2-NH<sub>2</sub>–3-O-pyH)]∙H<sub>2</sub>O, where 2-amino-3-hydroxypyridine acts as both a zwitterionic ligand (2-NH<sub>2</sub>–3-O-pyH)<sup>±</sup> and a counterion [(2-NH<sub>2</sub>–3-OH)pyH]<sup>+</sup>. The physicochemical properties of the newly synthesized complex salt were thoroughly investigated and analyzed, including its ABTS<sup>•+</sup> radical scavenging activity and reactivity towards hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>). These studies aimed to explore potential structural features of the oxidovanadium(IV) species that may influence their antioxidant activity. Finally, the potential of 2-amino-3-hydroxypyridine and [(2-NH<sub>2</sub>–3-OH)pyH)][VO(nta)(2-NH<sub>2</sub>–3-O-pyH)]∙H<sub>2</sub>O as cytoprotective agents against oxidative damage induced by H<sub>2</sub>O<sub>2</sub> was assessed using the HT22 hippocampal neuronal cell line.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117899"},"PeriodicalIF":2.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145621348","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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