Pub Date : 2026-01-24DOI: 10.1016/j.poly.2026.117983
Robinur Rahman , Subas Rajbangshi , Hikari Kawashima , Masashi Hasegawa , Reo Ohno , Daisuke Hayauchi , Miki Hasegawa , Vladimir N. Nesterov , German E. Pieslinger , Shishir Ghosh
Two rhenium tricarbonyl diimine complexes namely fac-[Re(CO)3(κ2-phen){κ1-(N)-sac}] (1) (phen = 1,10-phenanthroline) and fac-[Re(CO)3(κ2-bpy){κ1-(N)-sac}] (2) (bpy = 2,2′-bipyridine) have been prepared from the reactions of [Re(CO)4(NCMe){κ1-(N)-sac}] (sacH = saccharin) with corresponding diimine. Both complexes are photoluminescent upon UV irradiation, and display phosphorescence (ΦPL = 0.5–2.7%, τ = 0.14–0.05 μs) in solution at room temperature as expected. DFT/TD-DFT calculations, carried out to interrogate their exited-state character, reveal that both absorption and emission are MLCT in nature for both complexes in accordant with the experimental observations. Both complexes have also been found to dissolve in all common organic solvents.
{"title":"Photoluminescent rhenium tricarbonyl diimine complexes bearing a saccharinate ligand","authors":"Robinur Rahman , Subas Rajbangshi , Hikari Kawashima , Masashi Hasegawa , Reo Ohno , Daisuke Hayauchi , Miki Hasegawa , Vladimir N. Nesterov , German E. Pieslinger , Shishir Ghosh","doi":"10.1016/j.poly.2026.117983","DOIUrl":"10.1016/j.poly.2026.117983","url":null,"abstract":"<div><div>Two rhenium tricarbonyl diimine complexes namely <em>fac</em>-[Re(CO)<sub>3</sub>(κ<sup>2</sup>-phen){κ<sup>1</sup>-(N)-sac}] (<strong>1</strong>) (phen = 1,10-phenanthroline) and <em>fac</em>-[Re(CO)<sub>3</sub>(κ<sup>2</sup>-bpy){κ<sup>1</sup>-(<em>N</em>)-sac}] (<strong>2</strong>) (bpy = 2,2′-bipyridine) have been prepared from the reactions of [Re(CO)<sub>4</sub>(NCMe){κ<sup>1</sup>-(<em>N</em>)-sac}] (sacH = saccharin) with corresponding diimine. Both complexes are photoluminescent upon UV irradiation, and display phosphorescence (<em>Φ</em><sub>PL</sub> = 0.5–2.7%, <em>τ</em> = 0.14–0.05 μs) in solution at room temperature as expected. DFT/TD-DFT calculations, carried out to interrogate their exited-state character, reveal that both absorption and emission are MLCT in nature for both complexes in accordant with the experimental observations. Both complexes have also been found to dissolve in all common organic solvents.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"288 ","pages":"Article 117983"},"PeriodicalIF":2.6,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146081187","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 : 2026-01-24DOI: 10.1016/j.poly.2026.117981
Abrar Nazir , Ali B.M. Ali , Ejaz Ahmad Khera , Muhammad Faizan , Awatif Alshamari , Dalia H. Elkamchouchi , Ramesh Sharma
In present work, we assessed the structural, electronic, optical, and charge transport features of novel GaSiX3 (where X = Cl, I) perovskites using density functional theory, with a focus on their probable applications in optoelectronics and solar cells. We employed the formation energy, binding energy, tolerance factor, and the Murnaghan equation of state to confirm the structural and thermodynamic stability of the studied composites. The band structure and total density of states (TDOS) results indicate that the band gaps of 2.85 eV for GaSiCl3 and 1.02 eV for GaSiI3 have been observed, respectively. The partial density of states indicates that the contributions to the formation of the valence and conduction bands arise from the Ga-4p, Si-3p, Cl-3s, and I-5p energy states. Regarding optical behavior, GaSiI3 is a good choice for optoelectronic and solar cell applications since it exhibits the greatest conductivity and absorption of electromagnetic radiation (156–553 nm) in the visible and ultraviolet regions. Using the BoltzTraP code, the thermoelectric properties of the perovskites under study have been computed. These findings regarding the thermoelectric parameters reveal that these composites are suitable for thermoelectric devices due to their higher electrical conductivity, power factor, and figure of merit values. The results of the composites being studied offer a new avenue for researchers to explore possible applications in solar cells and thermoelectric applications.
{"title":"Unraveling the multifunctional prospects of novel GaSiX3 (X = Cl, I) ternary perovskites for solar cells applications and green energy: A density functional theory approach","authors":"Abrar Nazir , Ali B.M. Ali , Ejaz Ahmad Khera , Muhammad Faizan , Awatif Alshamari , Dalia H. Elkamchouchi , Ramesh Sharma","doi":"10.1016/j.poly.2026.117981","DOIUrl":"10.1016/j.poly.2026.117981","url":null,"abstract":"<div><div>In present work, we assessed the structural, electronic, optical, and charge transport features of novel GaSiX<sub>3</sub> (where X = Cl, I) perovskites using density functional theory, with a focus on their probable applications in optoelectronics and solar cells. We employed the formation energy, binding energy, tolerance factor, and the Murnaghan equation of state to confirm the structural and thermodynamic stability of the studied composites. The band structure and total density of states (TDOS) results indicate that the band gaps of 2.85 eV for GaSiCl<sub>3</sub> and 1.02 eV for GaSiI<sub>3</sub> have been observed, respectively. The partial density of states indicates that the contributions to the formation of the valence and conduction bands arise from the Ga-<em>4p</em>, Si-<em>3p</em>, Cl-<em>3s</em>, and I-<em>5p</em> energy states. Regarding optical behavior, GaSiI<sub>3</sub> is a good choice for optoelectronic and solar cell applications since it exhibits the greatest conductivity and absorption of electromagnetic radiation (156–553 nm) in the visible and ultraviolet regions. Using the BoltzTraP code, the thermoelectric properties of the perovskites under study have been computed. These findings regarding the thermoelectric parameters reveal that these composites are suitable for thermoelectric devices due to their higher electrical conductivity, power factor, and figure of merit values. The results of the composites being studied offer a new avenue for researchers to explore possible applications in solar cells and thermoelectric applications.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"288 ","pages":"Article 117981"},"PeriodicalIF":2.6,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146081190","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 : 2026-01-22DOI: 10.1016/j.poly.2026.117975
Jacob P. Brannon , Joseph M. Sperling , Thomas E. Albrecht
By utilizing tri-(3,5-dimethoxyphenyl)phosphine oxide (OP(Ph3,5OMe)3) as a bulky ligand for complexing f-block elements, a series of pseudo-octahedral complexes of the form mer-LnBr3(OP(Ph3,5OMe)3)3 (Ln3+ = La3+–Lu3+ excluding Pm3+) were synthesized and characterized. This synthetic procedure was then applied to U(IV) and U(VI) where the trans-UX4(OP(Ph3,5OMe)3)2 and trans-UVIO2X2(OP(Ph3,5OMe)3)2 (X− = Cl−, Br−, I−) complexes were obtained. The pseudo-octahedral local geometry about the metal centers was retained in all 20 compounds. These complexes were characterized by sc-XRD, p-XRD, solid-state Raman spectroscopy, solution and solid-state UV–vis-NIR spectroscopy, and 1H, 13C, and 31P NMR spectroscopies. UV–vis-NIR spectra show only a few, weak 4f → 4f transitions for the lanthanide complexes as well as a reduction in the number and intensity of 5f → 5f transitions for U4+. This is ascribed to the pseudo-centrosymmetric, local coordination environment enforcing Laporte's selection rules. Bond metrics were used in conjunction with Natural Bonding Orbital (NBO) calculations to obtain the Natural Localized Molecular Orbitals (NLMOs) for investigation of the covalent contributions to bonding as it relates to the Inverse Trans Influence. There is a mild polarization of the Ln–L bonds that causes slightly heightened orbital mixing, but these effects are small in comparison with the U(IV) and U(VI) complexes. The observed orbital mixing is weak, but stronger than expected for a hard donor ligand with the Ln(III) cations. In contrast, the U(IV) and U(VI) complexes yield results similar to what would be expected in the lanthanide complexes based on Fajan's rules.
{"title":"Comprehensive analysis of pseudo-octahedral lanthanide(III) and uranium(IV and VI) tri-(3,5-dimethoxyphenyl)phosphine oxide complexes","authors":"Jacob P. Brannon , Joseph M. Sperling , Thomas E. Albrecht","doi":"10.1016/j.poly.2026.117975","DOIUrl":"10.1016/j.poly.2026.117975","url":null,"abstract":"<div><div>By utilizing tri-(3,5-dimethoxyphenyl)phosphine oxide (OP(Ph<sup>3,5OMe</sup>)<sub>3</sub>) as a bulky ligand for complexing <em>f</em>-block elements, a series of pseudo-octahedral complexes of the form <em>mer</em>-LnBr<sub>3</sub>(OP(Ph<sup>3,5OMe</sup>)<sub>3</sub>)<sub>3</sub> (Ln<sup>3+</sup> = La<sup>3+</sup>–Lu<sup>3+</sup> excluding Pm<sup>3+</sup>) were synthesized and characterized. This synthetic procedure was then applied to U(IV) and U(VI) where the <em>trans</em>-UX<sub>4</sub>(OP(Ph<sup>3,5OMe</sup>)<sub>3</sub>)<sub>2</sub> and <em>trans</em>-U<sup>VI</sup>O<sub>2</sub>X<sub>2</sub>(OP(Ph<sup>3,5OMe</sup>)<sub>3</sub>)<sub>2</sub> (X<sup>−</sup> = Cl<sup>−</sup>, Br<sup>−</sup>, I<sup>−</sup>) complexes were obtained. The pseudo-octahedral local geometry about the metal centers was retained in all 20 compounds. These complexes were characterized by sc-XRD, p-XRD, solid-state Raman spectroscopy, solution and solid-state UV–vis-NIR spectroscopy, and <sup>1</sup>H, <sup>13</sup>C, and <sup>31</sup>P NMR spectroscopies. UV–vis-NIR spectra show only a few, weak 4<em>f</em> → 4<em>f</em> transitions for the lanthanide complexes as well as a reduction in the number and intensity of 5<em>f</em> → 5<em>f</em> transitions for U<sup>4+</sup>. This is ascribed to the pseudo-centrosymmetric, local coordination environment enforcing Laporte's selection rules. Bond metrics were used in conjunction with Natural Bonding Orbital (NBO) calculations to obtain the Natural Localized Molecular Orbitals (NLMOs) for investigation of the covalent contributions to bonding as it relates to the Inverse Trans Influence. There is a mild polarization of the Ln–L bonds that causes slightly heightened orbital mixing, but these effects are small in comparison with the U(IV) and U(VI) complexes. The observed orbital mixing is weak, but stronger than expected for a hard donor ligand with the Ln(III) cations. In contrast, the U(IV) and U(VI) complexes yield results similar to what would be expected in the lanthanide complexes based on Fajan's rules.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"288 ","pages":"Article 117975"},"PeriodicalIF":2.6,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146081123","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 : 2026-01-20DOI: 10.1016/j.poly.2026.117979
Fatima S. Jalli, Tariq J. Alwan
This study reports the development of a high-performance gas sensor for detecting CO2 gas. The sensor is fabricated using a polypyrrole/tin dioxide (Ppy/SnO₂) nanocomposite with varying SnO₂ loadings (0–4 wt%). The sensing mechanism is attributed to the formation of p-n heterojunctions at the Ppy/SnO₂ interface, which significantly enhances the response. The optimal composite, containing 4 wt% SnO₂, demonstrated outstanding performance, achieving a remarkable sensitivity of up to 91% toward 5 ppm CO₂. Operating the sensor at a relatively low working temperature of 70 °C was found to be ideal, offering an excellent balance between high sensitivity and significantly improved response and recovery times. These findings establish the Ppy/SnO₂ nanocomposite as a promising material for fabricating efficient, low-power sensors for practical CO₂ leak detection applications.
{"title":"Fabrication and characterization of a Ppy/SnO2 nanocomposite gas sensor for low-concentration CO2 detection","authors":"Fatima S. Jalli, Tariq J. Alwan","doi":"10.1016/j.poly.2026.117979","DOIUrl":"10.1016/j.poly.2026.117979","url":null,"abstract":"<div><div>This study reports the development of a high-performance gas sensor for detecting CO<sub>2</sub> gas. The sensor is fabricated using a polypyrrole/tin dioxide (Ppy/SnO₂) nanocomposite with varying SnO₂ loadings (0–4 wt%). The sensing mechanism is attributed to the formation of p-n heterojunctions at the Ppy/SnO₂ interface, which significantly enhances the response. The optimal composite, containing 4 wt% SnO₂, demonstrated outstanding performance, achieving a remarkable sensitivity of up to 91% toward 5 ppm CO₂. Operating the sensor at a relatively low working temperature of 70 °C was found to be ideal, offering an excellent balance between high sensitivity and significantly improved response and recovery times. These findings establish the Ppy/SnO₂ nanocomposite as a promising material for fabricating efficient, low-power sensors for practical CO₂ leak detection applications.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"288 ","pages":"Article 117979"},"PeriodicalIF":2.6,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146081183","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 : 2026-01-19DOI: 10.1016/j.poly.2026.117976
Fisayo Rachael Jegede , Saira Nayab , Minyoung Yoon , Gaeun Lee , Hyosun Lee , Sang-Ho Lee
A series of Co(II) and Cu(II) complexes supported by N,N′-bidentate ligands derived from aminomethylpyridine and aminomethylquinoline were synthesized and characterized. The ligands 2-(piperidin-1-ylmethyl)pyridine (LA), 4-(pyridin-2-yl)methyl)morpholine (LB), 2-(piperidin-1-ylmethyl)quinoline (LC), and 4-(quinolin-2-yl)methyl)morpholine (LD) reacted with [CoCl2·6H2O] or [CuCl2·2H2O] in a 1:1 M ratio to yield the corresponding dichloro complexes, formulated as [LnMX2] (where Ln = LA–LD; M = Co, Cu). X-ray diffraction analysis revealed that all [LnCoCl2] complexes (Ln = LA–LC) adopt distorted tetrahedral geometries. In contrast, the copper complexes displayed ligand-dependent geometries: [LCCuCl2] is distorted square-planar, while LB afforded dimeric [{CuCl(LB)}2(μ-Cl)2] species with distorted square-pyramidal copper centers. The ring-opening polymerization of rac-lactide was efficiently catalyzed by the in-situ-generated [LnM(OiPr)2] species (Ln = LA–LD; M = Co, Cu) upon treatment with LiOiPr. Catalytic activity was observed at both 0 °C and 25 °C, producing poly(lactide) (PLA) with pronounced heterotacticity. High monomer conversions were achieved; however, the resulting polymers exhibited moderately broad dispersities (PDIs = 1.22–1.38) and relatively low molecular weights, indicative of a moderate degree of polymerization control.
以氨基甲基吡啶和氨基甲基喹啉为原料合成了一系列以N，N '双齿配体负载的Co（II）和Cu（II）配合物，并对其进行了表征。配体2-（哌啶-1-基甲基）吡啶（LA）、4-（吡啶-2-基甲基）啉（LB）、2-（哌啶-1-基甲基）喹啉（LC）和4-（哌啶-1-基甲基）啉（LD）与[CoCl2·6H2O]或[CuCl2·2H2O]以1:1的M比反应生成相应的二氯配合物[LnMX2] （Ln = LA - LD; M = Co, Cu）。x射线衍射分析表明，所有[LnCoCl2]配合物（Ln = LA-LC）均为畸变四面体。相反，铜配合物表现出与配体相关的几何形状：[LCCuCl2]是扭曲的方形平面，而LB是具有扭曲的方形锥体铜中心的二聚体[{CuCl(LB)}2(μ-Cl)2]。在LiOiPr处理下，原位生成的[LnM(OiPr)2]物质（Ln = LA-LD; M = Co, Cu）有效地催化了racc -丙交酯的开环聚合。在0℃和25℃下均观察到催化活性，生成具有明显杂性的聚丙交酯（PLA）。单体转化率高；然而，所得到的聚合物具有中等宽的分散度（pdi = 1.22-1.38）和相对较低的分子量，表明聚合控制程度适中。
{"title":"Structural diversity of cobalt(II) and copper(II) complexes with aminomethylpyridine/quinoline derivatives: application in rac-lactide polymerization","authors":"Fisayo Rachael Jegede , Saira Nayab , Minyoung Yoon , Gaeun Lee , Hyosun Lee , Sang-Ho Lee","doi":"10.1016/j.poly.2026.117976","DOIUrl":"10.1016/j.poly.2026.117976","url":null,"abstract":"<div><div>A series of Co(II) and Cu(II) complexes supported by <em>N</em>,<em>N</em>′-bidentate ligands derived from aminomethylpyridine and aminomethylquinoline were synthesized and characterized. The ligands 2-(piperidin-1-ylmethyl)pyridine (<strong>L</strong><sub><strong>A</strong></sub>), 4-(pyridin-2-yl)methyl)morpholine (<strong>L</strong><sub><strong>B</strong></sub>), 2-(piperidin-1-ylmethyl)quinoline (<strong>L</strong><sub><strong>C</strong></sub>), and 4-(quinolin-2-yl)methyl)morpholine (<strong>L</strong><sub><strong>D</strong></sub>) reacted with [CoCl<sub>2</sub>·6H<sub>2</sub>O] or [CuCl<sub>2</sub>·2H<sub>2</sub>O] in a 1:1 M ratio to yield the corresponding dichloro complexes, formulated as <strong>[L</strong><sub><strong>n</strong></sub><strong>MX</strong><sub><strong>2</strong></sub><strong>]</strong> (where L<sub>n</sub> = <strong>L</strong><sub><strong>A</strong></sub><strong>–L</strong><sub><strong>D</strong></sub>; M = Co, Cu). X-ray diffraction analysis revealed that all <strong>[L</strong><sub><strong>n</strong></sub><strong>CoCl</strong><sub><strong>2</strong></sub><strong>]</strong> complexes (L<sub>n</sub> = L<sub>A</sub>–L<sub>C</sub>) adopt distorted tetrahedral geometries. In contrast, the copper complexes displayed ligand-dependent geometries: <strong>[L</strong><sub><strong>C</strong></sub><strong>CuCl</strong><sub><strong>2</strong></sub><strong>]</strong> is distorted square-planar, while L<sub>B</sub> afforded dimeric <strong>[{CuCl(L</strong><sub><strong>B</strong></sub><strong>)}</strong><sub><strong>2</strong></sub><strong>(μ-Cl)</strong><sub><strong>2</strong></sub><strong>]</strong> species with distorted square-pyramidal copper centers. The ring-opening polymerization of <em>rac</em>-lactide was efficiently catalyzed by the <em>in-situ</em>-generated <strong>[L</strong><sub><strong>n</strong></sub><strong>M(O</strong><sup><strong><em>i</em></strong></sup><strong>Pr)</strong><sub><strong>2</strong></sub><strong>]</strong> species (L<sub>n</sub> = L<sub>A</sub>–L<sub>D</sub>; M = Co, Cu) upon treatment with LiO<sup><em>i</em></sup>Pr. Catalytic activity was observed at both 0 °C and 25 °C, producing poly(lactide) (PLA) with pronounced heterotacticity. High monomer conversions were achieved; however, the resulting polymers exhibited moderately broad dispersities (PDIs = 1.22–1.38) and relatively low molecular weights, indicative of a moderate degree of polymerization control.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"288 ","pages":"Article 117976"},"PeriodicalIF":2.6,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146081189","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 : 2026-01-19DOI: 10.1016/j.poly.2026.117966
Jing Wei , Zi-Rui Liu , Jian Zhu , Xi-Xi Wang , Zhi-Ying Wang , Xiao-Wei Fan , Yu-Hui Tan , Chao Shi , Yun-Zhi Tang
In recent years, organic-inorganic hybrid lead-free materials have become a promising platform for preparing various stimuli-responsive materials with excellent optoelectronic properties. Here, we synthetise a zero-dimensional zinc-based hybrid, [3,3-difluorocyclobutylammonium]2ZnCl4 ([DFCBA]2ZnCl4, 1), and thoroughly discuss its various-temperature single-crystal structures, switchable dielectric constant behavior, and optical properties. 1 undergoes reversible structural phase transitions with dielectric switching property characteristics at around 354 K upon heating-cooling cycles. Interestingly, both the crystalline phases exhibit monoclinic structure. At room temperature, the organic cations display partial disordered configurations, while at high temperatures, they become highly ordered. This asymmetric symmetry breaking originates from the reverse temperature transition between disordered and ordered states of the [DFCBA]+ cation, which modulates the material's dielectric response. Optical characterization reveals that [DFCBA]2ZnCl4 possesses a direct band gap of 4.68 eV, with its photoluminescence (PL) spectrum showing a maximum emission peak at 481 nm and a fluorescence lifetime of 7.923 μs. Combining its outstanding dielectric switching properties with unique optical characteristics, this zero-dimensional zinc-based hybrid material demonstrates significant potential for applications in ultraviolet-responsive devices, high-insulation optical coatings, and novel optoelectronic devices.
{"title":"A zero-dimensional zinc-based hybrid showing switchable dielectric constant, inverse symmetry breaking and fluorescence property","authors":"Jing Wei , Zi-Rui Liu , Jian Zhu , Xi-Xi Wang , Zhi-Ying Wang , Xiao-Wei Fan , Yu-Hui Tan , Chao Shi , Yun-Zhi Tang","doi":"10.1016/j.poly.2026.117966","DOIUrl":"10.1016/j.poly.2026.117966","url":null,"abstract":"<div><div>In recent years, organic-inorganic hybrid lead-free materials have become a promising platform for preparing various stimuli-responsive materials with excellent optoelectronic properties. Here, we synthetise a zero-dimensional zinc-based hybrid, [3,3-difluorocyclobutylammonium]<sub>2</sub>ZnCl<sub>4</sub> ([DFCBA]<sub>2</sub>ZnCl<sub>4</sub>, <strong>1</strong>), and thoroughly discuss its various-temperature single-crystal structures, switchable dielectric constant behavior, and optical properties. <strong>1</strong> undergoes reversible structural phase transitions with dielectric switching property characteristics at around 354 K upon heating-cooling cycles. Interestingly, both the crystalline phases exhibit monoclinic structure. At room temperature, the organic cations display partial disordered configurations, while at high temperatures, they become highly ordered. This asymmetric symmetry breaking originates from the reverse temperature transition between disordered and ordered states of the [DFCBA]<sup>+</sup> cation, which modulates the material's dielectric response. Optical characterization reveals that [DFCBA]<sub>2</sub>ZnCl<sub>4</sub> possesses a direct band gap of 4.68 eV, with its photoluminescence (PL) spectrum showing a maximum emission peak at 481 nm and a fluorescence lifetime of 7.923 μs. Combining its outstanding dielectric switching properties with unique optical characteristics, this zero-dimensional zinc-based hybrid material demonstrates significant potential for applications in ultraviolet-responsive devices, high-insulation optical coatings, and novel optoelectronic devices.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"288 ","pages":"Article 117966"},"PeriodicalIF":2.6,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146081192","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 : 2026-01-19DOI: 10.1016/j.poly.2026.117977
İskender Muz , Niyazi Bulut
The detection of chloroquine (CQ), a widely used antimalarial drug with emerging therapeutic roles but potential cardiotoxicity, necessitate the development of sensitive and selective biosensors. This study employs density functional theory (DFT) to systematically screen the adsorption performance and sensing potential of chloroquine on Cr-, Fe-, Mg-, Ni-, Si- and Ti-doped (ZnO)20 nanoclusters. Among all investigated dopants, the Mg-doped (ZnO)20 nanocluster exhibits the most favorable characteristics for CQ detection. It shows the highest adsorption energy (−58.11 kcal/mol), the shortest binding distance (2.10 Å) between the drug's N atom and the nanocluster's Zn site, and a significant change in dipole moment after CQ adsorption. Electronic structure analysis reveals that Mg-doping induces the most pronounced reduction in the HOMO-LUMO energy gap after CQ interaction (∼13% change), indicating enhanced charge transfer and a strong electrical signal response. The RDG and NCI analyses confirm that the adsorption is primarily governed by weak van der Waals forces (physical adsorption), the distinct electronic perturbation caused by CQ on the Mg-doped surface is notable. The results demonstrate that Mg-doped (ZnO)20 nanocluster is the most promising candidate for the development of efficient CQ biosensor.
{"title":"Enhanced chloroquine sensing on Cr, Fe, Mg, Ni, Si, and Ti-doped zinc oxide nanoclusters: A DFT study","authors":"İskender Muz , Niyazi Bulut","doi":"10.1016/j.poly.2026.117977","DOIUrl":"10.1016/j.poly.2026.117977","url":null,"abstract":"<div><div>The detection of chloroquine (CQ), a widely used antimalarial drug with emerging therapeutic roles but potential cardiotoxicity, necessitate the development of sensitive and selective biosensors. This study employs density functional theory (DFT) to systematically screen the adsorption performance and sensing potential of chloroquine on Cr-, Fe-, Mg-, Ni-, Si- and Ti-doped (ZnO)<sub>20</sub> nanoclusters. Among all investigated dopants, the Mg-doped (ZnO)<sub>20</sub> nanocluster exhibits the most favorable characteristics for CQ detection. It shows the highest adsorption energy (−58.11 kcal/mol), the shortest binding distance (2.10 Å) between the drug's N atom and the nanocluster's Zn site, and a significant change in dipole moment after CQ adsorption. Electronic structure analysis reveals that Mg-doping induces the most pronounced reduction in the HOMO-LUMO energy gap after CQ interaction (∼13% change), indicating enhanced charge transfer and a strong electrical signal response. The RDG and NCI analyses confirm that the adsorption is primarily governed by weak van der Waals forces (physical adsorption), the distinct electronic perturbation caused by CQ on the Mg-doped surface is notable. The results demonstrate that Mg-doped (ZnO)<sub>20</sub> nanocluster is the most promising candidate for the development of efficient CQ biosensor.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"287 ","pages":"Article 117977"},"PeriodicalIF":2.6,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146038651","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 : 2026-01-19DOI: 10.1016/j.poly.2026.117978
Louchachha Isam , Faris Abdelmajid , Khaldoune Khadija , Rafya Meriem , Edder Youssef , Boualy Brahim , Rachid Hsissou , Ait Ali Mustapha , Karim Abdallah
Functionalized sesquiterpenes are a highly sought-after compounds for their olfactive as well as therapeutic properties. Herein, we report the oxidation of γ-dehydro-arylhimachalene, an olefin obtained via the aromatization of himachalene mixture, the major components of cadar oil, using ruthenium- and vanadium-based catalysts. While ruthenium catalyzed oxidation leads to the formation of a ketone and an aldehyde with poor selectivity, vanadium-catalyzed oxidation of the same substrate using hydrogen peroxide as an oxidant leads to the selective formation of the ketone. Finally, γ-dehydro-arylhimachalene, the ketone and the aldehyde were explored as antibacterial agents against two gram positive (Staphylococcus Aureus and Enterococcus faecalis) and two gram negative (Escherechia Coli and Pseudomonas aeruginosa) bacteria. The ketone showed the best activity against E.coli and P. aeruginosa with MIC equal to 0.78 mg/mL and 0.1 mg/mL respectively, while γ-dehydro-arylhimachalene displayed the best activity, with MIC equal to 1.56 and 0.2 mg/mL against S.aureus and E. faecalis respectively.
{"title":"Catalytic oxidation of γ-dehydro-arylhimachalene: synthesis and antibacterial study of novel oxygenated derivatives of himachalanes","authors":"Louchachha Isam , Faris Abdelmajid , Khaldoune Khadija , Rafya Meriem , Edder Youssef , Boualy Brahim , Rachid Hsissou , Ait Ali Mustapha , Karim Abdallah","doi":"10.1016/j.poly.2026.117978","DOIUrl":"10.1016/j.poly.2026.117978","url":null,"abstract":"<div><div>Functionalized sesquiterpenes are a highly sought-after compounds for their olfactive as well as therapeutic properties. Herein, we report the oxidation of γ-dehydro-arylhimachalene, an olefin obtained via the aromatization of himachalene mixture, the major components of cadar oil, using ruthenium- and vanadium-based catalysts. While ruthenium catalyzed oxidation leads to the formation of a ketone and an aldehyde with poor selectivity, vanadium-catalyzed oxidation of the same substrate using hydrogen peroxide as an oxidant leads to the selective formation of the ketone. Finally, γ-dehydro-arylhimachalene, the ketone and the aldehyde were explored as antibacterial agents against two gram positive (<em>Staphylococcus Aureus</em> and <em>Enterococcus faecalis)</em> and two gram negative (<em>Escherechia Coli</em> and <em>Pseudomonas aeruginosa)</em> bacteria<em>.</em> The ketone showed the best activity against <em>E.coli</em> and <em>P. aeruginosa</em> with MIC equal to 0.78 mg/mL and 0.1 mg/mL respectively, while γ-dehydro-arylhimachalene displayed the best activity, with MIC equal to 1.56 and 0.2 mg/mL against S.aureus and <em>E. faecalis</em> respectively.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"287 ","pages":"Article 117978"},"PeriodicalIF":2.6,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146038652","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 : 2026-01-17DOI: 10.1016/j.poly.2026.117962
Jan Janczak
The new arsenic (III) phthalocyanine complex [(AsIIIPc)2(I)2(As6I6) - (1) was obtained in a crystalline form by direct reaction of phthalonitrile with arsenic powder in an oxidation atmosphere of iodine vapor. This complex is a unique example of arsenic phthalocyanine complex in which in both parts of the complex the arsenic is in different oxidation state: As3+ in (AsPc)+ unit and As1+ in a neutral molecule As6I6. In the crystal the arsenic phthalocyanine (AsPc)+ unit is non-planar, the arsenic(III) protrudes out of the cavity by 0.7699(12) Å, forming a saucer shape of Pc unit. The neutral, unique As6I6 molecule is centrosymmetric in which there are six As1+ joined together to form a six-membered ring As6I6 in the chair conformation that is rendered dianionic As6I82− by the μ3-iodide anions that cap both faces of the ring. The interaction between the building units of the crystal was analyzed using the Hirshfeld surface and the analysis of the 2D fingerprint plots. UV–Vis absorption spectra of 1 were taken in CH2Cl2 and toluene solutions in the concentration range from 8 × 10−5 to 10−6 mol/l. No significant changes related to aggregation in solutions were observed. The Q-band in toluene solution is red shifted by ∼10 nm in comparison to that in CH2Cl2 solution. Oxidation of [(AsIIIPc)I]2(As6I6) yields AsVPc derivative. Both AsIII and AsV phthalocyanine derivatives absorb near infrared light (600–900 nm) which should be intriguing with the point of view of potential use as photosensitizers for PDT and as an infrared cut filter for plasma display and silicon photodiodes as well as materials showing strong electron donors/acceptors properties.
{"title":"Synthesis, structure and UV–vis characterization of arsenic(III) phthalocyanine obtained in iodine vapor: [(AsIIIPc)]2(I)2(As6I6)","authors":"Jan Janczak","doi":"10.1016/j.poly.2026.117962","DOIUrl":"10.1016/j.poly.2026.117962","url":null,"abstract":"<div><div>The new arsenic (III) phthalocyanine complex [(As<sup>III</sup>Pc)<sub>2</sub>(I)<sub>2</sub>(As<sub>6</sub>I<sub>6</sub>) - (<strong>1</strong>) was obtained in a crystalline form by direct reaction of phthalonitrile with arsenic powder in an oxidation atmosphere of iodine vapor. This complex is a unique example of arsenic phthalocyanine complex in which in both parts of the complex the arsenic is in different oxidation state: As<sup>3+</sup> in (AsPc)<sup>+</sup> unit and As<sup>1+</sup> in a neutral molecule As<sub>6</sub>I<sub>6</sub>. In the crystal the arsenic phthalocyanine (AsPc)<sup>+</sup> unit is non-planar, the arsenic(III) protrudes out of the cavity by 0.7699(12) Å, forming a saucer shape of Pc unit. The neutral, unique As<sub>6</sub>I<sub>6</sub> molecule is centrosymmetric in which there are six As<sup>1+</sup> joined together to form a six-membered ring As<sub>6</sub>I<sub>6</sub> in the chair conformation that is rendered dianionic As<sub>6</sub>I<sub>8</sub><sup>2−</sup> by the μ<sub>3</sub>-iodide anions that cap both faces of the ring. The interaction between the building units of the crystal was analyzed using the Hirshfeld surface and the analysis of the 2D fingerprint plots. UV–Vis absorption spectra of <strong>1</strong> were taken in CH<sub>2</sub>Cl<sub>2</sub> and toluene solutions in the concentration range from 8 × 10<sup>−5</sup> to 10<sup>−6</sup> mol/l. No significant changes related to aggregation in solutions were observed. The Q-band in toluene solution is red shifted by ∼10 nm in comparison to that in CH<sub>2</sub>Cl<sub>2</sub> solution. Oxidation of [(As<sup>III</sup>Pc)I]<sub>2</sub>(As<sub>6</sub>I<sub>6</sub>) yields As<sup>V</sup>Pc derivative. Both As<sup>III</sup> and As<sup>V</sup> phthalocyanine derivatives absorb near infrared light (600–900 nm) which should be intriguing with the point of view of potential use as photosensitizers for PDT and as an infrared cut filter for plasma display and silicon photodiodes as well as materials showing strong electron donors/acceptors properties.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"288 ","pages":"Article 117962"},"PeriodicalIF":2.6,"publicationDate":"2026-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146039935","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}
The effective remediation of high-viscosity crude oil remains a pressing challenge due to the limited molecular mobility and inefficient diffusion under ambient conditions. Herein, we report a hierarchically engineered two-dimensional (2-D) heterostructure composed of vertically aligned mesoporous polydopamine-derived carbon (mPDA) layers integrated with Ti3C2Tx MXene nanosheets, constructed via a single-micelle-directed interfacial assembly strategy. This “sandwich-like” configuration not only suppresses MXene restacking and oxidation but also establishes continuous mesoporous nanochannels, enabling efficient light-to-heat conversion and accelerated oil diffusion. Embedded within a compressible cellulose aerogel scaffold, the resultant 2-D mPDA@MXene/COA composite achieves superior photothermal-assisted crude oil remediation, exhibiting an enhanced separation efficiency of 87.2% under sunlight-1.36 times higher than in the dark. The aerogel also delivers an exceptional organic solvent uptake capacity of up to 79.5 g/g (for carbon tetrachloride), strong chemical tolerance in acidic, basic, and saline media, and excellent reusability with >85% retention after 10 cycles. This work provides a scalable and generalizable platform for designing functional mesoporous carbon–MXene heterostructures, offering a promising route toward solar-driven environmental remediation under extreme operating conditions.
{"title":"Engineered 2-D mesoporous carbon/MXene heterostructures for enhanced photothermal crude oil remediation","authors":"Yihan Gao, Chaochao Yang, Kerun Zhu, Yan Ai, Tong Wang, Wei Zhang, Wei Li, Dongyuan Zhao","doi":"10.1016/j.poly.2026.117974","DOIUrl":"10.1016/j.poly.2026.117974","url":null,"abstract":"<div><div>The effective remediation of high-viscosity crude oil remains a pressing challenge due to the limited molecular mobility and inefficient diffusion under ambient conditions. Herein, we report a hierarchically engineered two-dimensional (2-D) heterostructure composed of vertically aligned mesoporous polydopamine-derived carbon (mPDA) layers integrated with Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> MXene nanosheets, constructed <em>via</em> a single-micelle-directed interfacial assembly strategy. This “sandwich-like” configuration not only suppresses MXene restacking and oxidation but also establishes continuous mesoporous nanochannels, enabling efficient light-to-heat conversion and accelerated oil diffusion. Embedded within a compressible cellulose aerogel scaffold, the resultant 2-D mPDA@MXene/COA composite achieves superior photothermal-assisted crude oil remediation, exhibiting an enhanced separation efficiency of 87.2% under sunlight-1.36 times higher than in the dark. The aerogel also delivers an exceptional organic solvent uptake capacity of up to 79.5 g/g (for carbon tetrachloride), strong chemical tolerance in acidic, basic, and saline media, and excellent reusability with >85% retention after 10 cycles. This work provides a scalable and generalizable platform for designing functional mesoporous carbon–MXene heterostructures, offering a promising route toward solar-driven environmental remediation under extreme operating conditions.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"288 ","pages":"Article 117974"},"PeriodicalIF":2.6,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146081185","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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