Complexes of diethyl (5-ethyl-2-hydroxy-3-nitrophenyl)phosphonate with uranyl and neptunyl nitrates [UO2(HL1)2(NO3)2] and [NpO2(HL1)2(NO3)2] were synthesized and characterized for the first time. A procedure was developed for the preparation of diethyl (5-ethyl-2-hydroxy-3-nitrophenyl)phosphonate by nitration of diethyl (5-ethyl-2-hydroxyphenyl)phosphonate with a solution of uranyl nitrate in acetonitrile, in the form of the complex [UO2(HL1)2(NO3)2]. Using HCl, uranyl could be separated from the complex and, thus, the uncoordinated ligand HL1 could be isolated and identified, which was subsequently used to prepare the complex [NpO2(HL1)2(NO3)2] and in solvent extraction experiments. The extraction of U(VI) and Pu(VI) by HL1 in 1,2-dichloroethane and meta-trifluoromethylnitrobenzene from nitric acid solutions was investigated.
{"title":"Synthesis of diethyl (5-ethyl-2-hydroxy-3-nitrophenyl)phosphonate and its complexation properties towards hexavalent actinides: crystal structure and solvent extraction studies","authors":"Alina Sivolap , Vladimir Baulin , Yuliana Rogacheva , Dmitriy Baulin , Alexander Fedoseev , Mikhail Grigoriev , Vladislav Sharov , Galina Kostikova","doi":"10.1016/j.poly.2025.117868","DOIUrl":"10.1016/j.poly.2025.117868","url":null,"abstract":"<div><div>Complexes of diethyl (5-ethyl-2-hydroxy-3-nitrophenyl)phosphonate with uranyl and neptunyl nitrates [UO<sub>2</sub>(HL<sup>1</sup>)<sub>2</sub>(NO<sub>3</sub>)<sub>2</sub>] and [NpO<sub>2</sub>(HL<sup>1</sup>)<sub>2</sub>(NO<sub>3</sub>)<sub>2</sub>] were synthesized and characterized for the first time. A procedure was developed for the preparation of diethyl (5-ethyl-2-hydroxy-3-nitrophenyl)phosphonate by nitration of diethyl (5-ethyl-2-hydroxyphenyl)phosphonate with a solution of uranyl nitrate in acetonitrile, in the form of the complex [UO<sub>2</sub>(HL<sup>1</sup>)<sub>2</sub>(NO<sub>3</sub>)<sub>2</sub>]. Using HCl, uranyl could be separated from the complex and, thus, the uncoordinated ligand HL<sup>1</sup> could be isolated and identified, which was subsequently used to prepare the complex [NpO<sub>2</sub>(HL<sup>1</sup>)<sub>2</sub>(NO<sub>3</sub>)<sub>2</sub>] and in solvent extraction experiments. The extraction of U(VI) and Pu(VI) by HL<sup>1</sup> in 1,2-dichloroethane and meta-trifluoromethylnitrobenzene from nitric acid solutions was investigated.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117868"},"PeriodicalIF":2.6,"publicationDate":"2025-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145528099","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-03DOI: 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":"2025-11-03","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 : 2025-11-01DOI: 10.1016/j.poly.2025.117865
Shuanglong Liu , Adam V. Bruce , Dmitry Skachkov , James N. Fry , Hai-Ping Cheng
In this work, we examine low-energy adsorption configurations of four dodecanuclear manganese single-molecule magnets (Mn12), where the ligand R being H, CH3, CHCl2 or C6H5, on a molybdenum disulfide (MoS2) monolayer using force field and density functional theory calculations. The van der Waals interaction is shown to be crucial for determining the adsorption energy. Some electrons transfer from the substrate to the molecules upon surface adsorption, resulting in a reduction of the magnetic anisotropy energy of Mn12. Since the lowest unoccupied molecular orbital of Mn12 is close to the valence band of MoS2, a negative electric field is more effective in modulating charge transfer and energy band alignment, and thus altering the magnetic anisotropy energy, compared with a positive electric field. A significant increase in the magnetic anisotropy energy of Mn12 with the ligand or under a sufficiently high electric field has been predicted. Our calculations show that the molecules remain intact on the surface both before and after the electric field is applied. Finally, a two-level system formed by different adsorption configurations is evaluated, and the tunability of its energy barrier under an electric field is demonstrated. Our study sheds light on tuning the properties of single-molecule magnets using an electric field, when the molecules are supported on a surface.
{"title":"Tuning the magnetic anisotropy energy of MoS2-supported Mn12 complexes by electric field: A first-principles study","authors":"Shuanglong Liu , Adam V. Bruce , Dmitry Skachkov , James N. Fry , Hai-Ping Cheng","doi":"10.1016/j.poly.2025.117865","DOIUrl":"10.1016/j.poly.2025.117865","url":null,"abstract":"<div><div>In this work, we examine low-energy adsorption configurations of four dodecanuclear manganese single-molecule magnets <figure><img></figure> (Mn<sub>12</sub>), where the ligand R being H, CH<sub>3</sub>, CHCl<sub>2</sub> or C<sub>6</sub>H<sub>5</sub>, on a molybdenum disulfide (MoS<sub>2</sub>) monolayer using force field and density functional theory calculations. The van der Waals interaction is shown to be crucial for determining the adsorption energy. Some electrons transfer from the substrate to the molecules upon surface adsorption, resulting in a reduction of the magnetic anisotropy energy of Mn<sub>12</sub>. Since the lowest unoccupied molecular orbital of Mn<sub>12</sub> is close to the valence band of MoS<sub>2</sub>, a negative electric field is more effective in modulating charge transfer and energy band alignment, and thus altering the magnetic anisotropy energy, compared with a positive electric field. A significant increase in the magnetic anisotropy energy of Mn<sub>12</sub> with the ligand <figure><img></figure> or <figure><img></figure> under a sufficiently high electric field has been predicted. Our calculations show that the molecules remain intact on the surface both before and after the electric field is applied. Finally, a two-level system formed by different adsorption configurations is evaluated, and the tunability of its energy barrier under an electric field is demonstrated. Our study sheds light on tuning the properties of single-molecule magnets using an electric field, when the molecules are supported on a surface.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"283 ","pages":"Article 117865"},"PeriodicalIF":2.6,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145467000","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-31DOI: 10.1016/j.poly.2025.117856
Naveen K. Yadav , Rajesh K. Yadav , Shaifali Mishra , Rehana Shahin , Kanchan Sharma , Vinay K. Mishra , Surendra K. Jaiswal , Ghadah Shukri Albakri , Maha Awjan Alreshidi , Krishna Kumar Yadav , Jin Ook Baeg
Solar-powered photocatalytic pathway introduces molecular oxygen into the sulfides. The pharmaceutical ingredient (sulfoxidation product) was transformed by harnessing sunlight to generate the necessary energy for the catalytic-oxidative reactions. The mechanistic pathway involves oxidants, which are green and sustainable reagents, i.e., oxygen/air, thereby maintaining aerobic oxidative and mild conditions. Herein, we develop an eco-friendly, reusable Gr@TBA photocatalyst via one-pot condensation of glucose-derived graphene (Gr) and 2,4,6-tribromoaniline (TBA). The Gr@TBA photocatalyst shows its excellent opto-electronic properties and charge separation capabilities by creating electron channels and also targets the chemo-selective (95 % sulfoxide selectivity at 90 % conversion) transformation to sulfoxide from sulfide.
{"title":"Harnessing photocatalytic activity of graphene covalently coupled TBA catalyst for oxygenation of sulfides using solar spectrum: Mechanistic studies and synthetic uses","authors":"Naveen K. Yadav , Rajesh K. Yadav , Shaifali Mishra , Rehana Shahin , Kanchan Sharma , Vinay K. Mishra , Surendra K. Jaiswal , Ghadah Shukri Albakri , Maha Awjan Alreshidi , Krishna Kumar Yadav , Jin Ook Baeg","doi":"10.1016/j.poly.2025.117856","DOIUrl":"10.1016/j.poly.2025.117856","url":null,"abstract":"<div><div>Solar-powered photocatalytic pathway introduces molecular oxygen into the sulfides. The pharmaceutical ingredient (sulfoxidation product) was transformed by harnessing sunlight to generate the necessary energy for the catalytic-oxidative reactions. The mechanistic pathway involves oxidants, which are green and sustainable reagents, i.e., oxygen/air, thereby maintaining aerobic oxidative and mild conditions. Herein, we develop an eco-friendly, reusable Gr@TBA photocatalyst via one-pot condensation of glucose-derived graphene (Gr) and 2,4,6-tribromoaniline (TBA). The Gr@TBA photocatalyst shows its excellent opto-electronic properties and charge separation capabilities by creating electron channels and also targets the chemo-selective (95 % sulfoxide selectivity at 90 % conversion) transformation to sulfoxide from sulfide.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"283 ","pages":"Article 117856"},"PeriodicalIF":2.6,"publicationDate":"2025-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145467045","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-30DOI: 10.1016/j.poly.2025.117867
Nan Xu , Emily Suchta , Michael J. Shaw , Gadden Lych , Navamoney Arulsamy , Sela Cameron , Joshua Bueno
Nitrosonaphthols belong to the class of C-nitroso compounds, having an additional hydroxyl group on the naphthalene ring. Their coordination chemistry is rich due to the presence of both nitroso and hydroxyl groups. Despite the various binding modes of nitrosonaphthols in metal complexes, their interactions with heme model complexes remain unexplored. In this work, we report the synthesis and characterization of a six-coordinate ruthenium nitrosyl porphyrin complex, (OEP)Ru(NO)(η1-ONC10H6O) from the reaction of excess 2-nitroso-1-naphthol with the nitrosyl ruthenium alkoxide precursor, (OEP)Ru(NO)(O-i-C5H11) (OEP = 2,3,7,8,12,13,17,18-octaethylporphinato dianion). The complex was characterized by various methods, including 1D and 2D NMR spectroscopy (COSY, HSQC, HMBC, and 1D-NOE), IR spectroscopy, and single-crystal X-ray crystallography. The molecular structure of (OEP)Ru(NO)(η1-ONC10H6O) reveals monodentate O-binding to the metal through the nitroso oxygen atom of the oxo-oxime tautomer. The intermolecular interactions within the crystalline packing of the complex were investigated using Hirshfeld surface analysis. In addition, the redox behavior of (OEP)Ru(NO)(η1-ONC10H6O) was studied through cyclic voltammetry in CH2Cl2. As far as we know, the structure of (OEP)Ru(NO)(η1-ONC10H6O) represents the first member of the class of monodentate 1,2-nitrosonaphthol metal complexes.
{"title":"Synthesis, solid state molecular structure, and cyclic voltammetry of a ruthenium nitrosyl porphyrin with a nitrosonaphthol ligand","authors":"Nan Xu , Emily Suchta , Michael J. Shaw , Gadden Lych , Navamoney Arulsamy , Sela Cameron , Joshua Bueno","doi":"10.1016/j.poly.2025.117867","DOIUrl":"10.1016/j.poly.2025.117867","url":null,"abstract":"<div><div>Nitrosonaphthols belong to the class of <em>C</em>-nitroso compounds, having an additional hydroxyl group on the naphthalene ring. Their coordination chemistry is rich due to the presence of both nitroso and hydroxyl groups. Despite the various binding modes of nitrosonaphthols in metal complexes, their interactions with heme model complexes remain unexplored. In this work, we report the synthesis and characterization of a six-coordinate ruthenium nitrosyl porphyrin complex, (OEP)Ru(NO)(<em>η</em><sup>1</sup>-ONC<sub>10</sub>H<sub>6</sub>O) from the reaction of excess 2-nitroso-1-naphthol with the nitrosyl ruthenium alkoxide precursor, (OEP)Ru(NO)(O-<em>i</em>-C<sub>5</sub>H<sub>11</sub>) (OEP = 2,3,7,8,12,13,17,18-octaethylporphinato dianion). The complex was characterized by various methods, including 1D and 2D NMR spectroscopy (COSY, HSQC, HMBC, and 1D-NOE), IR spectroscopy, and single-crystal X-ray crystallography. The molecular structure of (OEP)Ru(NO)(<em>η</em><sup>1</sup>-ONC<sub>10</sub>H<sub>6</sub>O) reveals monodentate <em>O</em>-binding to the metal through the nitroso oxygen atom of the oxo-oxime tautomer. The intermolecular interactions within the crystalline packing of the complex were investigated using Hirshfeld surface analysis. In addition, the redox behavior of (OEP)Ru(NO)(<em>η</em><sup>1</sup>-ONC<sub>10</sub>H<sub>6</sub>O) was studied through cyclic voltammetry in CH<sub>2</sub>Cl<sub>2</sub>. As far as we know, the structure of (OEP)Ru(NO)(<em>η</em><sup>1</sup>-ONC<sub>10</sub>H<sub>6</sub>O) represents the first member of the class of monodentate 1,2-nitrosonaphthol metal complexes.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"283 ","pages":"Article 117867"},"PeriodicalIF":2.6,"publicationDate":"2025-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145467044","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-30DOI: 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":"2025-10-30","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 : 2025-10-29DOI: 10.1016/j.poly.2025.117855
Sifanele Phundulu, Zipho Samuel, Isaac Mulaudzi, Nnamdi Nwahara, John Mack, Tebello Nyokong
The development of highly efficient materials to replace expensive silicon-based solar cells remains a significant challenge in photovoltaic technology. In this study, we report on the use of 4-(10,15,20-tris(4-methoxyphenyl)porphyrin-5-yl)benzoic acid (compound 1), 4-(10,15,20-tris(4-phenoxyphenyl)porphyrin-5-yl)benzoic acid (compound 2), copper(II) 4-(10,15,20-tris(4-methoxyphenyl)porphyrin)benzoic acid (compound 3), and copper(II) 4-(10,15,20-tris(4-phenoxyphenyl)porphyrin) (compound 4) as dyes in dye-sensitized solar cells (DSSC) using reduced graphene oxide as cathode materials. The effect of methoxy and phenoxy meso substituents on the efficiency of the DSSCs was investigated. Notably, compound 3 demonstrated an improved efficiency of 0.81 %, outperforming compounds 1, 2, and 4, which exhibited efficiencies of 0.49 %, 0.46 %, and 0.53 %, respectively.
{"title":"The use of methoxy and phenoxy meso-substituted porphyrin dyes and reduced graphene oxide for dye-sensitized solar cells","authors":"Sifanele Phundulu, Zipho Samuel, Isaac Mulaudzi, Nnamdi Nwahara, John Mack, Tebello Nyokong","doi":"10.1016/j.poly.2025.117855","DOIUrl":"10.1016/j.poly.2025.117855","url":null,"abstract":"<div><div>The development of highly efficient materials to replace expensive silicon-based solar cells remains a significant challenge in photovoltaic technology. In this study, we report on the use of 4-(10,15,20-tris(4-methoxyphenyl)porphyrin-5-yl)benzoic acid (compound <strong>1</strong>), 4-(10,15,20-tris(4-phenoxyphenyl)porphyrin-5-yl)benzoic acid (compound <strong>2</strong>), copper(II) 4-(10,15,20-tris(4-methoxyphenyl)porphyrin)benzoic acid (compound <strong>3</strong>), and copper(II) 4-(10,15,20-tris(4-phenoxyphenyl)porphyrin) (compound <strong>4)</strong> as dyes in dye-sensitized solar cells (DSSC) using reduced graphene oxide as cathode materials. The effect of methoxy and phenoxy <em>meso</em> substituents on the efficiency of the DSSCs was investigated. Notably, compound <strong>3</strong> demonstrated an improved efficiency of 0.81 %, outperforming compounds <strong>1</strong>, <strong>2</strong>, and <strong>4</strong>, which exhibited efficiencies of 0.49 %, 0.46 %, and 0.53 %, respectively.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"283 ","pages":"Article 117855"},"PeriodicalIF":2.6,"publicationDate":"2025-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145467043","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-29DOI: 10.1016/j.poly.2025.117866
David A. Wink , Leandro L. Coutinho , Robert Y.S. Cheng , Lisa A. Ridnour , Jon Fukuto
The recognition of nitric oxide and nitrogen oxides as key elements in human biology has driven the development of one of the most extensive areas of research in recent decades, consistently uncovering new insights into therapy and disease. These molecules are central to redox biology, with their inorganic chemistry playing a significant role in many biological systems. This review explores how fundamental chemical properties, kinetics, and thermodynamics influence important biological outcomes, including cancer, covering both normal physiology and disease states. The distinct chemical traits of these compounds allow for precise regulation of biological processes. Emerging concepts in cancer and other diseases will be discussed to highlight innovative treatments for advanced-stage conditions.
{"title":"Fundamental inorganic chemistry and cancer and inflammatory mechanism of NO. kinetic approach to revealing insights into Cancer and other diseases","authors":"David A. Wink , Leandro L. Coutinho , Robert Y.S. Cheng , Lisa A. Ridnour , Jon Fukuto","doi":"10.1016/j.poly.2025.117866","DOIUrl":"10.1016/j.poly.2025.117866","url":null,"abstract":"<div><div>The recognition of nitric oxide and nitrogen oxides as key elements in human biology has driven the development of one of the most extensive areas of research in recent decades, consistently uncovering new insights into therapy and disease. These molecules are central to redox biology, with their inorganic chemistry playing a significant role in many biological systems. This review explores how fundamental chemical properties, kinetics, and thermodynamics influence important biological outcomes, including cancer, covering both normal physiology and disease states. The distinct chemical traits of these compounds allow for precise regulation of biological processes. Emerging concepts in cancer and other diseases will be discussed to highlight innovative treatments for advanced-stage conditions.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"284 ","pages":"Article 117866"},"PeriodicalIF":2.6,"publicationDate":"2025-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145577750","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-27DOI: 10.1016/j.poly.2025.117862
Harshita Srivastava, Ambrish Kumar Srivastava
We present a computational study on oxygen-centered superalkali clusters, OnLi2n+1+ (n = 1–5), constructed by sequential addition of OLi2 units. Optimized geometries and electronic analyses confirm stable configurations with distinct symmetries and pronounced superalkali behavior. The VEA values confirm a strong electron-trapping ability, with OLi3+ exhibiting the highest value (3.459 eV), while larger clusters show structural sensitivity through non-monotonic variations. The Egap decreases systematically from 10.53 eV (OLi3+) to 8.93 eV (O5Li11+), indicating enhanced frontier orbital delocalization and increasing chemical reactivity with cluster size, while maintaining reasonable electronic stability. QTAIM analysis reveals that OLi bonds are mainly ionic, supported by moderate electron density (ρ ≈ 0.04 a.u.) and positive Laplacian, with a slight covalent character in specific cases. These features strengthen the structural robustness and unusual electronic properties of the clusters. Overall, the OnLi2n+1+ series represents a new class of oxygen-centered superalkalis with potential implications for molecular activation, redox chemistry, and hydrogen storage applications.
我们提出了一个氧中心超碱簇OnLi2n+1+ (n = 1 - 5)的计算研究，它是由OLi2单元的顺序加法构造的。优化的几何形状和电子分析证实了具有独特对称性和明显超碱行为的稳定结构。VEA值证实了其较强的电子捕获能力，其中OLi3+表现出最高的值（3.459 eV），而较大的团簇通过非单调变化表现出结构敏感性。Egap从10.53 eV （OLi3+）下降到8.93 eV (O5Li11+)，表明边界轨道离域增强，化学反应性随簇大小而增加，同时保持了合理的电子稳定性。QTAIM分析表明，OLi键主要是离子键，由中等电子密度（ρ≈0.04 a.u.）和正拉普拉斯键支撑，在特定情况下具有轻微的共价特征。这些特点加强了结构的坚固性和不寻常的电子性质的集群。总的来说，OnLi2n+1+系列代表了一类新的以氧为中心的超碱，在分子活化、氧化还原化学和储氢应用方面具有潜在的意义。
{"title":"Computational exploitation of OnLi2n+1+ (n = 1–5): A new oxygen-centred series of superalkali clusters","authors":"Harshita Srivastava, Ambrish Kumar Srivastava","doi":"10.1016/j.poly.2025.117862","DOIUrl":"10.1016/j.poly.2025.117862","url":null,"abstract":"<div><div>We present a computational study on oxygen-centered superalkali clusters, O<sub><em>n</em></sub>Li<sub>2<em>n</em>+1</sub><sup>+</sup> (<em>n</em> = 1–5), constructed by sequential addition of OLi<sub>2</sub> units. Optimized geometries and electronic analyses confirm stable configurations with distinct symmetries and pronounced superalkali behavior. The VEA values confirm a strong electron-trapping ability, with OLi<sub>3</sub><sup>+</sup> exhibiting the highest value (3.459 eV), while larger clusters show structural sensitivity through non-monotonic variations. The <em>E</em><sub>gap</sub> decreases systematically from 10.53 eV (OLi<sub>3</sub><sup>+</sup>) to 8.93 eV (O<sub>5</sub>Li<sub>11</sub><sup>+</sup>), indicating enhanced frontier orbital delocalization and increasing chemical reactivity with cluster size, while maintaining reasonable electronic stability. QTAIM analysis reveals that O<img>Li bonds are mainly ionic, supported by moderate electron density (<em>ρ</em> ≈ 0.04 a.u.) and positive Laplacian, with a slight covalent character in specific cases. These features strengthen the structural robustness and unusual electronic properties of the clusters. Overall, the O<sub><em>n</em></sub>Li<sub>2<em>n</em>+1</sub><sup>+</sup> series represents a new class of oxygen-centered superalkalis with potential implications for molecular activation, redox chemistry, and hydrogen storage applications.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"283 ","pages":"Article 117862"},"PeriodicalIF":2.6,"publicationDate":"2025-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145417770","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-27DOI: 10.1016/j.poly.2025.117864
Abhilash Pandey , Devanand Sahu , Rajat Kumar Roy , Srishti Dutta , Dishen Kumar , Vanshika Sharma , Uttam Kumar Das , Aalokita Verma , Goutam Kumar Patra
Herein, a novel benzil mono-hydrazone derivative, (2E,2E)-2-(2-(4-(pyridin-4-yl)benzylidene) hydrazono)-1,2-diphenylethanone (L) has been reported. This benzil mono-hydrazone derivative incorporates an asymmetric benzil core that enables enhanced π–π conjugation and dual donor sites (CO and C=N–N) that facilitate selective coordination with Ni2+. Unlike conventional Schiff-base or symmetric hydrazone sensors, this design allows a distinct colorimetric response visible to the naked eye and a strong fluorescence quenching effect due to metal–ligand charge transfer (MLCT). This combination of asymmetric framework and multifunctional binding sites confers superior selectivity and sensitivity towards Ni2+ over other competing metal ions. FTIR, NMR, ESI-MS, chemical analyses, X-ray single crystal analysis, and DFT studies have been used to characterise L. In a 1:1 methanol-water (v/v) mixture, the receptor L recognised Ni2+ with variations in UV–Vis absorption, and fluorescence quenching. The response mechanisms of fluorescent colorimetric sensing have been investigated using FTIR, ESI-MS, UV–Vis and fluorescence titrations. The colorimetric and fluorometric sensitivities are of 2.64 × 10−6 M and 2.40 × 10−6 M respectively for Ni2+ ions and both the values are adequate below the WHO allowable limits in aqueous solution. A 1:1 stoichiometric complexation between L and Ni2+ has been determined based on the Job's plot experiment, ESI-MS spectra and DFT studies. Receptor L may be effectively used for the detection and measurement of Ni2+ ions in environmental samples. L can also be utilised to construct INHIBIT-type of molecular logic gate and as an antibacterial agent.
{"title":"A new monohydrazone-based fluorescent colorimetric optical chemosensor for selective and sensitive detection of Ni2+ in aqueous medium: Biological, environmental and logic gate application","authors":"Abhilash Pandey , Devanand Sahu , Rajat Kumar Roy , Srishti Dutta , Dishen Kumar , Vanshika Sharma , Uttam Kumar Das , Aalokita Verma , Goutam Kumar Patra","doi":"10.1016/j.poly.2025.117864","DOIUrl":"10.1016/j.poly.2025.117864","url":null,"abstract":"<div><div>Herein, a novel benzil mono-hydrazone derivative, (2E,2E)-2-(2-(4-(pyridin-4-yl)benzylidene) hydrazono)-1,2-diphenylethanone (<strong>L</strong>) has been reported. This benzil mono-hydrazone derivative incorporates an asymmetric benzil core that enables enhanced π–π conjugation and dual donor sites (C<img>O and C=N–N) that facilitate selective coordination with Ni<sup>2+</sup>. Unlike conventional Schiff-base or symmetric hydrazone sensors, this design allows a distinct colorimetric response visible to the naked eye and a strong fluorescence quenching effect due to metal–ligand charge transfer (MLCT). This combination of asymmetric framework and multifunctional binding sites confers superior selectivity and sensitivity towards Ni<sup>2+</sup> over other competing metal ions. FTIR, NMR, ESI-MS, chemical analyses, X-ray single crystal analysis, and DFT studies have been used to characterise L. In a 1:1 methanol-water (<em>v</em>/v) mixture, the receptor <strong>L</strong> recognised Ni<sup>2+</sup> with variations in UV–Vis absorption, and fluorescence quenching. The response mechanisms of fluorescent colorimetric sensing have been investigated using FTIR, ESI-MS, UV–Vis and fluorescence titrations. The colorimetric and fluorometric sensitivities are of 2.64 × 10<sup>−6</sup> M and 2.40 × 10<sup>−6</sup> M respectively for Ni<sup>2+</sup> ions and both the values are adequate below the WHO allowable limits in aqueous solution. A 1:1 stoichiometric complexation between <strong>L</strong> and Ni<sup>2+</sup> has been determined based on the Job's plot experiment, ESI-MS spectra and DFT studies. Receptor <strong>L</strong> may be effectively used for the detection and measurement of Ni<sup>2+</sup> ions in environmental samples. <strong>L</strong> can also be utilised to construct INHIBIT-type of molecular logic gate and as an antibacterial agent.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"283 ","pages":"Article 117864"},"PeriodicalIF":2.6,"publicationDate":"2025-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145467042","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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