Pub Date : 2026-01-30DOI: 10.1016/j.molstruc.2026.145514
Dandan Li , Yingkun Liu , Lin Wang , Juan Lin , Junfeng Li , Aoxiang Feng , Fan Yang , Bo Zhang , Zhihong Xu , Jian-Yong Wang
Lipid droplets (LDs) are central to the pathogenesis of diverse metabolic disorders. Tumor cells frequently accumulate elevated levels of these neutral-lipid reservoirs as an energy supply. To visualize this hallmark, a fluorine-boron complexed dipyrromethene (BODIPY) derivative fluorescent probe, HBTOMe-BF2, was designed and developed. The probe combines excellent photostability and a high fluorescence quantum yield with a large, strictly linear spectral response to solvent polarity (R2>0.95), enabling accurate reporting of micro-environmental changes in living cells. Moreover, HBTOMe-BF2 selectively targets lipid droplets; we successfully employed it for imaging neutral lipids in cells and for visualizing lipid reservoirs in plant tissues. This work provides a robust tool for real-time tracking of lipid-droplet dynamics and offers new opportunities for deciphering lipid-related cellular processes.
{"title":"Borondifluoride engineered polarity-sensitive fluorescent probe for monitoring lipid droplet in cells and plants","authors":"Dandan Li , Yingkun Liu , Lin Wang , Juan Lin , Junfeng Li , Aoxiang Feng , Fan Yang , Bo Zhang , Zhihong Xu , Jian-Yong Wang","doi":"10.1016/j.molstruc.2026.145514","DOIUrl":"10.1016/j.molstruc.2026.145514","url":null,"abstract":"<div><div>Lipid droplets (LDs) are central to the pathogenesis of diverse metabolic disorders. Tumor cells frequently accumulate elevated levels of these neutral-lipid reservoirs as an energy supply. To visualize this hallmark, a fluorine-boron complexed dipyrromethene (BODIPY) derivative fluorescent probe, <strong>HBTOMe-BF<sub>2</sub></strong>, was designed and developed. The probe combines excellent photostability and a high fluorescence quantum yield with a large, strictly linear spectral response to solvent polarity (R<sup>2</sup>>0.95), enabling accurate reporting of micro-environmental changes in living cells. Moreover, <strong>HBTOMe-BF<sub>2</sub></strong> selectively targets lipid droplets; we successfully employed it for imaging neutral lipids in cells and for visualizing lipid reservoirs in plant tissues. This work provides a robust tool for real-time tracking of lipid-droplet dynamics and offers new opportunities for deciphering lipid-related cellular processes.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1360 ","pages":"Article 145514"},"PeriodicalIF":4.7,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146192489","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-30DOI: 10.1016/j.molstruc.2026.145529
C. Raksha , Jayasree G. Elambalassery , Akhil Sivan
The present work reports the design and synthesis of two benzimidazole-thiazolidine fused spiroheterocycles, STCH and STCP, developed through a combined computational and experimental approach. Density Functional Theory (DFT) calculations, including geometry optimisation and frequency analysis, confirmed their stability, while Natural Bond Orbital (NBO) analysis provided insights into their electronic characteristics. The compounds were synthesised via a multicomponent reaction and purified using column chromatography, with structures fully characterised by FT-IR, NMR, HRMS, and single-crystal X-ray diffraction (XRD). Topological analyses, including Electron Localisation Function (ELF), Localised Orbital Locator (LOL), Reduced Density Gradient (RDG), and Quantum Theory of Atoms in Molecules (QTAIM), revealed bonding and non-bonding interactions, intramolecular hydrogen bonding, and weak stabilising forces, further supported by Hirshfeld surface analysis. Drug-likeness and safety evaluations, based on ADME and toxicity predictions, suggested favourable pharmacokinetic properties. Molecular docking studies against α-glucosidase and α-amylase inhibitors highlighted strong binding affinities of both compounds, underscoring their potential as antidiabetic agents. Collectively, these integrative computational and experimental findings establish STCH and STCP as promising molecular scaffolds for further therapeutic development.
{"title":"Integrated spectroscopic, DFT, and topological analysis of benzimidazole-thiazolidine spiro heterocycles with promising antidiabetic potential","authors":"C. Raksha , Jayasree G. Elambalassery , Akhil Sivan","doi":"10.1016/j.molstruc.2026.145529","DOIUrl":"10.1016/j.molstruc.2026.145529","url":null,"abstract":"<div><div>The present work reports the design and synthesis of two benzimidazole-thiazolidine fused spiroheterocycles, <strong>STCH</strong> and <strong>STCP</strong>, developed through a combined computational and experimental approach. Density Functional Theory (DFT) calculations, including geometry optimisation and frequency analysis, confirmed their stability, while Natural Bond Orbital (NBO) analysis provided insights into their electronic characteristics. The compounds were synthesised <em>via</em> a multicomponent reaction and purified using column chromatography, with structures fully characterised by FT-IR, NMR, HRMS, and single-crystal X-ray diffraction (XRD). Topological analyses, including Electron Localisation Function (ELF), Localised Orbital Locator (LOL), Reduced Density Gradient (RDG), and Quantum Theory of Atoms in Molecules (QTAIM), revealed bonding and non-bonding interactions, intramolecular hydrogen bonding, and weak stabilising forces, further supported by Hirshfeld surface analysis. Drug-likeness and safety evaluations, based on ADME and toxicity predictions, suggested favourable pharmacokinetic properties. Molecular docking studies against α-glucosidase and α-amylase inhibitors highlighted strong binding affinities of both compounds, underscoring their potential as antidiabetic agents. Collectively, these integrative computational and experimental findings establish <strong>STCH</strong> and <strong>STCP</strong> as promising molecular scaffolds for further therapeutic development.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1359 ","pages":"Article 145529"},"PeriodicalIF":4.7,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146171085","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-30DOI: 10.1016/j.molstruc.2026.145518
Chen Li, Guo Xu, Yang Zhao, Jing Liang, Xiao-Peng Zhang
Herein, several neutral difluoro-substituted cyclometalated Pt(II) complexes incorporating halide/isocyanide ligands, [Pt(κ2-N^C)(CNXyl)X] (N^C = (−)-3-(4-fluoro-3-(3-fluoropyridin-2-yl)phenyl)-7,7-dimethyl-5,6,7,8-tetrahydro-6,8-methanoisoquinoline; CNXyl = 2,6-dimethylphenyl isocyanide; X = Cl (−)-1, Br (−)-2, or I (−)-3), were isolated from the reaction between [Pt(κ3-N^C^N′)(CNXyl)]OTf and n-Bu4NX. The preparation and photoluminescence properties of ionic [Pt(κ3-N^C^N′)(CNXyl)]OTf precursor and (−)-1 have been previously reported, and new complexes in this report are the -Br ((−)-2) and -I ((−)-3) derivatives. Single-crystal X-ray diffraction on (−)-2 and (−)-3 revealed a slightly distorted square-planar geometry in a trans-NC^N,CNR configuration. All κ2-N^C-coordinated Pt(II) complexes were weakly emissive in CH2Cl2 or THF but emitted bright luminescence with emission quantum yields of up to 77% in rigid media (solid state and PMMA films). A distinct aggregation-induced emission behavior was observed in mixed THF/H2O solution. Crystallites of the [Pt(κ2-N^C)(CNXyl)X] complexes demonstrated irreversible luminescence thermochromism with a luminescence change from green to red.
{"title":"Thermochromism and luminescent properties of κ2-N^C-coordinated cyclometalated Pt(II) complexes incorporating halide/isocyanide","authors":"Chen Li, Guo Xu, Yang Zhao, Jing Liang, Xiao-Peng Zhang","doi":"10.1016/j.molstruc.2026.145518","DOIUrl":"10.1016/j.molstruc.2026.145518","url":null,"abstract":"<div><div>Herein, several neutral difluoro-substituted cyclometalated Pt(II) complexes incorporating halide/isocyanide ligands, [Pt(<em>κ</em><sup>2</sup>-N^C)(CNXyl)X] (N^<em>C</em> = (−)-3-(4-fluoro-3-(3-fluoropyridin-2-yl)phenyl)-7,7-dimethyl-5,6,7,8-tetrahydro-6,8-methanoisoquinoline; CNXyl = 2,6-dimethylphenyl isocyanide; <em>X</em> = Cl (−)-<strong>1</strong>, Br (−)-<strong>2</strong>, or I (−)-<strong>3</strong>), were isolated from the reaction between [Pt(<em>κ</em><sup>3</sup>-N^C^N′)(CNXyl)]OTf and <em>n</em>-Bu<sub>4</sub>NX. The preparation and photoluminescence properties of ionic [Pt(<em>κ</em><sup>3</sup>-N^C^N′)(CNXyl)]OTf precursor and (−)-<strong>1</strong> have been previously reported, and new complexes in this report are the -Br ((−)-<strong>2</strong>) and -I ((−)-<strong>3</strong>) derivatives. Single-crystal X-ray diffraction on (−)-<strong>2</strong> and (−)-<strong>3</strong> revealed a slightly distorted square-planar geometry in a <strong><em>trans-N<sub>C^N</sub>,CNR</em></strong> configuration. All <em>κ</em><sup>2</sup><em>-</em>N^C-coordinated Pt(II) complexes were weakly emissive in CH<sub>2</sub>Cl<sub>2</sub> or THF but emitted bright luminescence with emission quantum yields of up to 77% in rigid media (solid state and PMMA films). A distinct aggregation-induced emission behavior was observed in mixed THF/H<sub>2</sub>O solution. Crystallites of the [Pt(<em>κ<sup>2</sup>-</em>N^C)(CNXyl)X] complexes demonstrated irreversible luminescence thermochromism with a luminescence change from green to red.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1359 ","pages":"Article 145518"},"PeriodicalIF":4.7,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146171086","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The organic–inorganic hybrid species A(2-AMP), formed through salt formation of an Anderson-type polyoxometalate (POM) with 2-amino-4-methylpyridine (2-AMP), was synthesized and characterized, and its structural features, physicochemical behavior, and biological activity were established. Single-crystal X-ray diffraction confirmed the hybrid structure, revealing two half-POM units associated with three 2-AMP cations through hydrogen bonding and electrostatic interactions. FTIR, UV–Vis, and MALDI-TOF spectroscopies verified the integrity of the hybrid framework. Thermal analysis (TGA/DTA) demonstrated multi-step decomposition with stability up to 290 °C. Cyclic voltammetry showed multiple quasi-reversible redox processes (–1.5 to +1.5 V), indicating that the POM-centered electron-transfer behavior is modulated by the organic ligand. A(2-AMP) exhibited moderate cytotoxicity against H2452 mesothelioma cells, with an IC₅₀ of 71.62 µg/mL (≈51.4 µM), and DNA cleavage assays showed no genotoxicity, suggesting cytotoxic effects via non-DNA-targeted mechanisms. These findings establish A(2-AMP) as a structurally well-defined, redox-active hybrid with moderate cytotoxic potential and highlight its applicability as a tunable platform for metallotherapeutic development.
{"title":"Pyridine-based Anderson-type polyoxometalate hybrid: Synthesis, structural elucidation, and electrochemical and biological properties","authors":"Eyüp Akgün , Nihal Deligönül , Sabahattin Comertpay , Jülide Nacaroğlu Ballı , Mehmet Tümer","doi":"10.1016/j.molstruc.2026.145522","DOIUrl":"10.1016/j.molstruc.2026.145522","url":null,"abstract":"<div><div>The organic–inorganic hybrid species A(2-AMP), formed through salt formation of an Anderson-type polyoxometalate (POM) with 2-amino-4-methylpyridine (2-AMP), was synthesized and characterized, and its structural features, physicochemical behavior, and biological activity were established. Single-crystal X-ray diffraction confirmed the hybrid structure, revealing two half-POM units associated with three 2-AMP cations through hydrogen bonding and electrostatic interactions. FTIR, UV–Vis, and MALDI-TOF spectroscopies verified the integrity of the hybrid framework. Thermal analysis (TGA/DTA) demonstrated multi-step decomposition with stability up to 290 °C. Cyclic voltammetry showed multiple quasi-reversible redox processes (–1.5 to +1.5 V), indicating that the POM-centered electron-transfer behavior is modulated by the organic ligand. A(2-AMP) exhibited moderate cytotoxicity against H2452 mesothelioma cells, with an IC₅₀ of 71.62 µg/mL (≈51.4 µM), and DNA cleavage assays showed no genotoxicity, suggesting cytotoxic effects via non-DNA-targeted mechanisms. These findings establish A(2-AMP) as a structurally well-defined, redox-active hybrid with moderate cytotoxic potential and highlight its applicability as a tunable platform for metallotherapeutic development.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1360 ","pages":"Article 145522"},"PeriodicalIF":4.7,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146191432","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-30DOI: 10.1016/j.molstruc.2026.145517
Jia-Yu Gu , Xin-Ran Chen , Fei Li , Wen-Ya Ding , Jia Cao , Wei-Wei Ge , Kai Chen
Three new coordination polymers based on cucurbit[5]uril (Q[5]) have been successfully synthesized. Their chemical formulas are {[Ni(H2O)2(Q[5])]·(1,5-NDS)}·14H2O (1), {[Co(H2O)2(Q[5])]·(1,5-NDS)}·15H2O (2), and {[Zn(H2O)2(Q[5])]·(1,5-NDS)}·10H2O (3). These polymers were obtained through the self-assembly of Q[5] with the corresponding transition metal salts in the presence of 1,5-naphthalenedisulfonic acid (1,5-H2NDS). Single- crystal X- ray diffraction analysis of these three coordination polymers has unveiled that the deprotonated 1,5-NDS²⁻ anions play a pivotal role in their self - assembly. Within these complexes, 1,5-NDS²⁻ anions facilitate the direct coordination of Ni2+/Co2+/Zn2+ with the carbonyl oxygen atoms at the ports of Q[5], leading to the formation of one - dimensional (1D) supramolecular chains. Moreover, the non - covalent interactions among the 1D chains, along with those arising from the interplay between 1,5 - NDS²⁻ anions and the outer surface of Q[5] within the chains, generate a cooperative effect. This cooperative effect, where the combined action of these interactions is more powerful than the simple sum of their individual contributions, drives the further assembly of the 1D chains into a three-dimensional (3D) supramolecular framework featuring specific channel structures. Performance tests reveal that the Q[5]-Ni2+-based supramolecular assembly has high selective recognition for the antibiotic norfloxacin (NFX).
{"title":"1,5-NDS2−-directed synthesis of transition metal based cucurbit[5]uril supramolecular material for efficient NFX antibiotic detection","authors":"Jia-Yu Gu , Xin-Ran Chen , Fei Li , Wen-Ya Ding , Jia Cao , Wei-Wei Ge , Kai Chen","doi":"10.1016/j.molstruc.2026.145517","DOIUrl":"10.1016/j.molstruc.2026.145517","url":null,"abstract":"<div><div>Three new coordination polymers based on cucurbit[5]uril (Q[5]) have been successfully synthesized. Their chemical formulas are {[Ni(H<sub>2</sub>O)<sub>2</sub>(Q[5])]·(1,5-NDS)}·14H<sub>2</sub>O (<strong>1</strong>), {[Co(H<sub>2</sub>O)<sub>2</sub>(Q[5])]·(1,5-NDS)}·15H<sub>2</sub>O (<strong>2</strong>), and {[Zn(H<sub>2</sub>O)<sub>2</sub>(Q[5])]·(1,5-NDS)}·10H<sub>2</sub>O (<strong>3</strong>). These polymers were obtained through the self-assembly of Q[5] with the corresponding transition metal salts in the presence of 1,5-naphthalenedisulfonic acid (1,5-H<sub>2</sub>NDS). Single- crystal X- ray diffraction analysis of these three coordination polymers has unveiled that the deprotonated 1,5-NDS²⁻ anions play a pivotal role in their self - assembly. Within these complexes, 1,5-NDS²⁻ anions facilitate the direct coordination of Ni<sup>2+</sup>/Co<sup>2+</sup>/Zn<sup>2+</sup> with the carbonyl oxygen atoms at the ports of Q[5], leading to the formation of one - dimensional (1D) supramolecular chains. Moreover, the non - covalent interactions among the 1D chains, along with those arising from the interplay between 1,5 - NDS²⁻ anions and the outer surface of Q[5] within the chains, generate a cooperative effect. This cooperative effect, where the combined action of these interactions is more powerful than the simple sum of their individual contributions, drives the further assembly of the 1D chains into a three-dimensional (3D) supramolecular framework featuring specific channel structures. Performance tests reveal that the Q[5]-Ni<sup>2+</sup>-based supramolecular assembly has high selective recognition for the antibiotic norfloxacin (NFX).</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1359 ","pages":"Article 145517"},"PeriodicalIF":4.7,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146171177","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A probe containing 7-azaindole and 1H-pyridin-2-one linked 1,2,3-triazole has been efficiently synthesized by CuAAC method and successfully characterized up to single crystal X-ray diffraction data to establish the structure as 1-[1-(2-pyrrolo[2,3-b]pyridin-1-yl-ethyl)-1H-[1,2,3]triazol-4-ylmethyl]-1H-pyridin-2-one (5). The synthesized probe 5 was examined under UV–Vis analysis, which revealed its specific sensitivity towards Pb2+ ion among other metal ions with LOD of 30 µM and binding constant (Ka) of 8.25 × 103 M−1. Intermolecular interactions of the probe have been studied through Hirshfeld surface analysis and energy framework calculations. Probe showed best potency for A. niger (MIC: 0.0195 µmol/mL) fungal strain which is even less than Fluconazole drug (MIC: 0.0408 µmol/mL) and showed considerable potency for bacterial strains (P. aeruginosa, Escherichia coli, S. aureus, and B. subtilis) including other fungal strain C. albicans. Molecular docking and DFT studies showed agreement with the in-vitro results while establishing extent of binding interactions between probe and metal ion. Furthermore, the in silico pharmacokinetic profile and cytotoxicity predicted results of the probe may attract theoreticians and experimentalist to design and propose development of similar molecules that may satisfy the parameters of orally bioavailable drug.
{"title":"CuAAC derived 7-azaindole and 1H-pyridin-2-one linked 1,2,3-triazole based probe for selective Pb2+ sensing endowed with in vitro and in silico antimicrobial potential","authors":"Kanika Sharma , Bajrang Lal , Ram Kumar Tittal , Riddima Singh , Jandeep Singh , Vijay Kumar , Ramling S. Mathpati","doi":"10.1016/j.molstruc.2026.145515","DOIUrl":"10.1016/j.molstruc.2026.145515","url":null,"abstract":"<div><div>A probe containing 7-azaindole and 1<em>H</em>-pyridin-2-one linked 1,2,3-triazole has been efficiently synthesized by CuAAC method and successfully characterized up to single crystal X-ray diffraction data to establish the structure as 1-[1-(2-pyrrolo[2,3-b]pyridin-1-yl-ethyl)-1<em>H</em>-[1,2,3]triazol-4-ylmethyl]-1<em>H</em>-pyridin-2-one (<strong>5</strong>). The synthesized probe <strong>5</strong> was examined under UV–Vis analysis, which revealed its specific sensitivity towards Pb<sup>2+</sup> ion among other metal ions with LOD of 30 µM and binding constant (<em>K<sub>a</sub></em>) of 8.25 × 10<sup>3</sup> M<sup>−1</sup>. Intermolecular interactions of the probe have been studied through Hirshfeld surface analysis and energy framework calculations. Probe showed best potency for <em>A. niger</em> (MIC: 0.0195 µmol/mL) fungal strain which is even less than Fluconazole drug (MIC: 0.0408 µmol/mL) and showed considerable potency for bacterial strains (<em>P. aeruginosa, Escherichia coli, S. aureus</em>, and <em>B. subtilis</em>) including other fungal strain <em>C. albicans</em>. Molecular docking and DFT studies showed agreement with the <em>in-vitro</em> results while establishing extent of binding interactions between probe and metal ion. Furthermore, the in silico pharmacokinetic profile and cytotoxicity predicted results of the probe may attract theoreticians and experimentalist to design and propose development of similar molecules that may satisfy the parameters of orally bioavailable drug.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1360 ","pages":"Article 145515"},"PeriodicalIF":4.7,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146192480","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-30DOI: 10.1016/j.molstruc.2026.145509
Elizaveta V. Glebova , Denis S. Tereshchenko , Victoria E. Gontcharenko , Ilya O. Glebov , Igor V. Morozov , Andrei V. Shevelkov
Four new oligomeric trifluoroacetate complexes of copper(II) with pyridine (py) and pyridine-like ligands quinoline (quin) and acridine (acr) were crystallized from equimolar methanol solutions of copper trifluoroacetate and a nitrogenous base (py, quin, acr) in the presence of fluoride ions. By single-crystal X-ray structural analysis it was shown that only complex [Cu3(µ3-F)(TFA)5(MeOH)(py)3](MeOH) has a µ3-fluorine ion, whereas a F- ion is not present in the copper coordination sphere in the case of larger analogues of pyridine. Molecular complexes of different nuclearity, [Cu2(TFA)2(OMe)2(acr)2], [Cu3(µ3-OH)(TFA)4(MeOH)(OMe)(quin)3](MeOH), and [Cu4(µ4-O)(TFA)4(OMe)2(quin)4], which contain ions OH-, O2-, or OMe- instead of F- were also synthesized. Also, the crystal structure of the mononuclear complex [Cu(TFA)2(quin)2] was established for the first time. The role of hydrogen bonds and π-stacking interactions in assembling molecular complexes into chains or layers is discussed based on the crystal data and DFT calculations.
{"title":"New oligomeric trifluoroacetate complexes of copper (II) with pyridine, quinoline, and acridine: The effect of an N-containing ligand on the composition and structural features","authors":"Elizaveta V. Glebova , Denis S. Tereshchenko , Victoria E. Gontcharenko , Ilya O. Glebov , Igor V. Morozov , Andrei V. Shevelkov","doi":"10.1016/j.molstruc.2026.145509","DOIUrl":"10.1016/j.molstruc.2026.145509","url":null,"abstract":"<div><div>Four new oligomeric trifluoroacetate complexes of copper(II) with pyridine (py) and pyridine-like ligands quinoline (quin) and acridine (acr) were crystallized from equimolar methanol solutions of copper trifluoroacetate and a nitrogenous base (py, quin, acr) in the presence of fluoride ions. By single-crystal X-ray structural analysis it was shown that only complex [Cu<sub>3</sub>(µ<sub>3</sub>-F)(TFA)<sub>5</sub>(MeOH)(py)<sub>3</sub>](MeOH) has a µ<sub>3</sub>-fluorine ion, whereas a F<sup>-</sup> ion is not present in the copper coordination sphere in the case of larger analogues of pyridine. Molecular complexes of different nuclearity, [Cu<sub>2</sub>(TFA)<sub>2</sub>(OMe)<sub>2</sub>(acr)<sub>2</sub>], [Cu<sub>3</sub>(µ<sub>3</sub>-OH)(TFA)<sub>4</sub>(MeOH)(OMe)(quin)<sub>3</sub>](MeOH), and [Cu<sub>4</sub>(µ<sub>4</sub>-O)(TFA)<sub>4</sub>(OMe)<sub>2</sub>(quin)<sub>4</sub>], which contain ions OH<sup>-</sup>, O<sup>2-</sup>, or OMe<sup>-</sup> instead of F<sup>-</sup> were also synthesized. Also, the crystal structure of the mononuclear complex [Cu(TFA)<sub>2</sub>(quin)<sub>2</sub>] was established for the first time. The role of hydrogen bonds and π-stacking interactions in assembling molecular complexes into chains or layers is discussed based on the crystal data and DFT calculations.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1360 ","pages":"Article 145509"},"PeriodicalIF":4.7,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146192538","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-29DOI: 10.1016/j.molstruc.2026.145516
Weihao Da , Xiaochen Liu , Xia Wu , Lin Zheng , Tian Gao , Alessandro Troisi , Chang-Qi Ma , Yi Lin
In this study, we report the design, synthesis, and comprehensive structural characterization of three novel tetrathienoanthracene (TTA) derivatives (8, 9, and 10) featuring an A-π-D-π-A molecular architecture. An efficient six-step synthetic route was developed, affording the target compounds in overall yields exceeding 20%. We investigated the impact of peripheral halogenation (fluorine vs. chlorine) on the molecular geometry, packing behavior, and optoelectronic properties. Spectroscopic analysis revealed broad absorption in the visible spectrum, with the chlorinated derivative (10) exhibiting a solution-state onset wavelength extending to 712 nm. Notably, upon solid-state film formation, the halogenated derivatives displayed significant bathochromic shifts (>90 nm), attributed to enhanced intermolecular aggregation and planarization of the π-conjugated backbone. Electrochemical measurements, corroborated by Density Functional Theory (DFT) calculations, confirmed that halogen introduction effectively modulates the frontier molecular orbitals, lowering HOMO/LUMO energy levels and narrowing the electrochemical band gap to 1.69 eV. Computational studies further elucidated the torsional profiles and conformational stability of the terminal groups, providing a theoretical basis for the observed structure-property relationships. These results underscore the efficacy of halogenation in fine-tuning the electronic structure and solid-state organization of TTA-based materials.
{"title":"Impact of peripheral halogenation on the structure-property relationships of tetrathienoanthracene (TTA) derivatives: Synthesis, structural characterization, and theoretical studies","authors":"Weihao Da , Xiaochen Liu , Xia Wu , Lin Zheng , Tian Gao , Alessandro Troisi , Chang-Qi Ma , Yi Lin","doi":"10.1016/j.molstruc.2026.145516","DOIUrl":"10.1016/j.molstruc.2026.145516","url":null,"abstract":"<div><div>In this study, we report the design, synthesis, and comprehensive structural characterization of three novel tetrathienoanthracene (TTA) derivatives (<strong>8, 9</strong>, and <strong>10</strong>) featuring an A-π-D-π-A molecular architecture. An efficient six-step synthetic route was developed, affording the target compounds in overall yields exceeding 20%. We investigated the impact of peripheral halogenation (fluorine vs. chlorine) on the molecular geometry, packing behavior, and optoelectronic properties. Spectroscopic analysis revealed broad absorption in the visible spectrum, with the chlorinated derivative (<strong>10</strong>) exhibiting a solution-state onset wavelength extending to 712 nm. Notably, upon solid-state film formation, the halogenated derivatives displayed significant bathochromic shifts (>90 nm), attributed to enhanced intermolecular aggregation and planarization of the π-conjugated backbone. Electrochemical measurements, corroborated by Density Functional Theory (DFT) calculations, confirmed that halogen introduction effectively modulates the frontier molecular orbitals, lowering HOMO/LUMO energy levels and narrowing the electrochemical band gap to 1.69 eV. Computational studies further elucidated the torsional profiles and conformational stability of the terminal groups, providing a theoretical basis for the observed structure-property relationships. These results underscore the efficacy of halogenation in fine-tuning the electronic structure and solid-state organization of TTA-based materials.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1359 ","pages":"Article 145516"},"PeriodicalIF":4.7,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146190347","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A new heterometallic metal‒organic framework, namely [Zn2Na(μ3O)(H₂ATPA)·DMF]n (Zn-Na-ATPA, H₅ATPA = 2′-acetamido-[1,1′:3′,1′'-terphenyl]-3,3′',5,5′,5′'-pentacarboxylic acid) was successfully constructed using a low-symmetry pentacarboxylic acid ligand incorporating an amide group. Single-crystal X-ray analysis reveals that Zn(II) and Na(I) ions are bridged by carboxylate groups and DMF solvent molecules to form a pentanuclear secondary building unit (SBU) consisting of four Zn(II) and two Na(I) ions. These SBUs are further connected by pentacarboxylic acid ligands to construct a three-dimensional framework. It exhibits a new highly connected (5,10)-c topology. The d¹⁰-configured Zn(II) center confers luminescent properties to the framework, enabling it to function as a versatile fluorescent sensor for detecting nitrobenzene (NB) and iodine. It detects NB in DMF via an inner filter effect with a detection limit of 3.7 mM, demonstrating good selectivity and reusability. More notably, it is capable of iodine sensing in both the aqueous and vapor phases, with a rapid response (quenching within 30 s) and high sensitivity (detection limit of 310 μM in solution). Mechanistic studies revealed that the quenching behavior is attributed to a synergistic combination of the inner filter effect and fluorescence resonance energy transfer (FRET). This work not only presents a unique topological MOF structure but also highlights its significant potential as a multifunctional sensory material for environmental monitoring.
{"title":"A new heterometallic Zn/Na-MOF featuring a (5,10)-connected topology: Structural elucidation and applications in fluorescent sensing","authors":"Hai-Dong Huang , Heng Zhang , Zi-Yuan Huang , An-Qi Chen , Ying Feng , Sheng-Run Zheng","doi":"10.1016/j.molstruc.2026.145510","DOIUrl":"10.1016/j.molstruc.2026.145510","url":null,"abstract":"<div><div>A new heterometallic metal‒organic framework, namely [Zn<sub>2</sub>Na(<em>μ</em><sub>3</sub><sub><img></sub>O)(H₂ATPA)·DMF]<sub>n</sub> (Zn-Na-ATPA, H₅ATPA = 2′-acetamido-[1,1′:3′,1′'-terphenyl]-3,3′',5,5′,5′'-pentacarboxylic acid) was successfully constructed using a low-symmetry pentacarboxylic acid ligand incorporating an amide group. Single-crystal X-ray analysis reveals that Zn(II) and Na(I) ions are bridged by carboxylate groups and DMF solvent molecules to form a pentanuclear secondary building unit (SBU) consisting of four Zn(II) and two Na(I) ions. These SBUs are further connected by pentacarboxylic acid ligands to construct a three-dimensional framework. It exhibits a new highly connected (5,10)-c topology. The d¹⁰-configured Zn(II) center confers luminescent properties to the framework, enabling it to function as a versatile fluorescent sensor for detecting nitrobenzene (NB) and iodine. It detects NB in DMF via an inner filter effect with a detection limit of 3.7 mM, demonstrating good selectivity and reusability. More notably, it is capable of iodine sensing in both the aqueous and vapor phases, with a rapid response (quenching within 30 s) and high sensitivity (detection limit of 310 μM in solution). Mechanistic studies revealed that the quenching behavior is attributed to a synergistic combination of the inner filter effect and fluorescence resonance energy transfer (FRET). This work not only presents a unique topological MOF structure but also highlights its significant potential as a multifunctional sensory material for environmental monitoring.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1359 ","pages":"Article 145510"},"PeriodicalIF":4.7,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146171084","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-29DOI: 10.1016/j.molstruc.2026.145511
Amer Alhaj Zen , Ebraheem Abdu Musad Saleh , Abdulrahman A. Almehizia , Egambergan. Xudaynazarov , Hussein Ali Al-Bahrani , Ibrahim K. Alsulami , Abdullah Yahya Abdullah Alzahrani , Elyor Berdimurodov , Rustamkhon Kuryazov , Dilafruz Kholmurodova , Raouf Hassan
Reduction reactions mediated by Zn play a crucial role in organic and pharmaceutical chemistry due to Zn unique properties such as low toxicity, cost-effectiveness, and environmental friendliness. Nevertheless, this reaction exhibits several disadvantages, including the consumption of 3 moles of Zn, the production of waste water, and a significant amount of waste byproducts. In this study, to overcome the identified challenges and mitigate urban waste, furan-2,5-dicarboxylic acid (FDA) was initially synthesized through the hydrolysis of PEF and a novel method for Zn-based MOF was subsequently designed and constructed using FDA as the organic linker. Comprehensive characterization of the synthesized MOF including its morphology, surface area, elemental composition, and electrochemical properties was performed using FT-IR, XRD, BET, SEM, TEM, EDS, EDX, TGA, XPS, and cyclic voltammetry (CV) analyses. The catalytic activity of the Zn-FDA MOF was assessed in the reductive transformation of nitrobenzene as well as in a multicomponent reaction involving nitrobenzenes 1(a-e), malononitrile 2(a), benzaldehydes 3(a-g) and dimedone 4(a). Under optimized electro-synthesis conditions room temperature, 2-hour reaction time, an applied current of 10 mA, and employing Urea/ChCl as a DES functioning simultaneously as solvent, electrolyte, and cocatalyst a series of hexahydroquinoline-3-carbonitrile derivatives 5(a–k) were efficiently synthesized with isolated yields ranging from 91 to 97%. The synthesized products were further confirmed by melting point determination, 1H NMR spectroscopy, and CHN elemental analysis.
{"title":"Development of a novel zinc-based (Zn-FDA) MOF through PEF hydrolysis and application as a sustainable, recyclable SPE electrode in electro-organic production of hexahydroquinoline-3-carbonitriles","authors":"Amer Alhaj Zen , Ebraheem Abdu Musad Saleh , Abdulrahman A. Almehizia , Egambergan. Xudaynazarov , Hussein Ali Al-Bahrani , Ibrahim K. Alsulami , Abdullah Yahya Abdullah Alzahrani , Elyor Berdimurodov , Rustamkhon Kuryazov , Dilafruz Kholmurodova , Raouf Hassan","doi":"10.1016/j.molstruc.2026.145511","DOIUrl":"10.1016/j.molstruc.2026.145511","url":null,"abstract":"<div><div>Reduction reactions mediated by Zn play a crucial role in organic and pharmaceutical chemistry due to Zn unique properties such as low toxicity, cost-effectiveness, and environmental friendliness. Nevertheless, this reaction exhibits several disadvantages, including the consumption of 3 moles of Zn, the production of waste water, and a significant amount of waste byproducts. In this study, to overcome the identified challenges and mitigate urban waste, furan-2,5-dicarboxylic acid (FDA) was initially synthesized through the hydrolysis of PEF and a novel method for Zn-based MOF was subsequently designed and constructed using FDA as the organic linker. Comprehensive characterization of the synthesized MOF including its morphology, surface area, elemental composition, and electrochemical properties was performed using FT-IR, XRD, BET, SEM, TEM, EDS, EDX, TGA, XPS, and cyclic voltammetry (CV) analyses. The catalytic activity of the Zn-FDA MOF was assessed in the reductive transformation of nitrobenzene as well as in a multicomponent reaction involving nitrobenzenes <strong>1(a-e)</strong>, malononitrile <strong>2(a)</strong>, benzaldehydes <strong>3(a-g)</strong> and dimedone <strong>4(a)</strong>. Under optimized electro-synthesis conditions room temperature, 2-hour reaction time, an applied current of 10 mA, and employing Urea/ChCl as a DES functioning simultaneously as solvent, electrolyte, and cocatalyst a series of hexahydroquinoline-3-carbonitrile derivatives <strong>5(a–k</strong>) were efficiently synthesized with isolated yields ranging from 91 to 97%. The synthesized products were further confirmed by melting point determination, <sup>1</sup>H NMR spectroscopy, and CHN elemental analysis.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1360 ","pages":"Article 145511"},"PeriodicalIF":4.7,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146192401","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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