Journal of Molecular Structure最新文献

英文中文

Constructing low-dimensional phosphorescent MOFs by site-selective coordination engineering

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2025-02-24 DOI: 10.1016/j.molstruc.2025.141861

Dan Zhang , Jingpeng Hu , Yuqi Zhu , Mengyao Wang , Jing Liu , Hongfeng Li , Tianyang Li , Zhongyi Liu , Jinpeng Li , Wenlei Zhang

Low-dimensional (LD) metal–organic framework materials (MOFs) have garnered increased attention due to their inheritance of MOF advantages, such as regular pores and tailorable structures, as well as the unique physicochemical properties of LD materials, including good mechanical properties, flexibility, and enhanced electrical conductivity. In this work, we developed a site-selective coordination engineering (SSCE) strategy to construct novel LD MOFs, including a two-dimensional Zn–binc MOF and a one-dimensional Cd–binc MOF. The former is prepared by coordinating Zn ions with all three heterogeneous coordination sites on 2-(1H-benzimidazol-1-yl)nicotinic acid (Hbinc), whereas the latter is formed by selective coordination between Cd ions and two of these sites. These MOF modules further self-assemble into 3D Zn–binc and 2D Cd–binc supramolecular structures through weak intermolecular hydrogen bonds. The constructed LD MOFs display remarkable room-temperature phosphorescence (RTP) properties, with long phosphorescence lifetimes of 123 ms for Zn–binc and 188 ms for Cd–binc. These outstanding RTP performances are primarily attributed to the large torsion angles and dense stacking of the Hbinc linkers within the Zn–binc and Cd–binc crystals, which significantly promotes the intersystem crossing process from the singlet to the triplet state and effectively inhibits non-radiative transitions of triplet excitons. This study not only enriches the library of LD MOFs, but also provides an efficient SSCE strategy for constructing new LD MOFs.

{"title":"Constructing low-dimensional phosphorescent MOFs by site-selective coordination engineering","authors":"Dan Zhang , Jingpeng Hu , Yuqi Zhu , Mengyao Wang , Jing Liu , Hongfeng Li , Tianyang Li , Zhongyi Liu , Jinpeng Li , Wenlei Zhang","doi":"10.1016/j.molstruc.2025.141861","DOIUrl":"10.1016/j.molstruc.2025.141861","url":null,"abstract":"<div><div>Low-dimensional (LD) metal–organic framework materials (MOFs) have garnered increased attention due to their inheritance of MOF advantages, such as regular pores and tailorable structures, as well as the unique physicochemical properties of LD materials, including good mechanical properties, flexibility, and enhanced electrical conductivity. In this work, we developed a site-selective coordination engineering (SSCE) strategy to construct novel LD MOFs, including a two-dimensional Zn–binc MOF and a one-dimensional Cd–binc MOF. The former is prepared by coordinating Zn ions with all three heterogeneous coordination sites on 2-(1H-benzimidazol-1-yl)nicotinic acid (Hbinc), whereas the latter is formed by selective coordination between Cd ions and two of these sites. These MOF modules further self-assemble into 3D Zn–binc and 2D Cd–binc supramolecular structures through weak intermolecular hydrogen bonds. The constructed LD MOFs display remarkable room-temperature phosphorescence (RTP) properties, with long phosphorescence lifetimes of 123 ms for Zn–binc and 188 ms for Cd–binc. These outstanding RTP performances are primarily attributed to the large torsion angles and dense stacking of the Hbinc linkers within the Zn–binc and Cd–binc crystals, which significantly promotes the intersystem crossing process from the singlet to the triplet state and effectively inhibits non-radiative transitions of triplet excitons. This study not only enriches the library of LD MOFs, but also provides an efficient SSCE strategy for constructing new LD MOFs.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1334 ","pages":"Article 141861"},"PeriodicalIF":4.0,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143511780","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}

引用次数: 0

Small molecule regulation of iron homeostasis: design and optimization of novel iron chelators based on a thiosemicarbazone scaffold

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2025-02-24 DOI: 10.1016/j.molstruc.2025.141859

Christian S. Parry , Yue Li , Samuel Kojo Kwofie , Josh Valencia , Cynthia A．Tope Niedermaier , Timothy R. Ramadhar , Sergei Nekhai , Michael D. Wilson , Raymond J. Butcher

Disrupted iron balance causes anemia and iron overload leading to hypoxia and systemic oxidative stress. Iron overload may arise from red blood cell disorders such as sickle cell disease, thalassemia major and primary hemochromatosis, or from treatment with multiple transfusions. These hematological disorders are characterized by constant red blood cell hemolysis and the release of iron. Hemolysis is a continuous source of reactive oxygen species whose accumulation changes the redox potential in the erythrocyte, the endothelium and other tissue causing damage to organ systems. Iron overload and its consequences can be treated with iron chelating therapy. We have carried out structural studies of small molecule ligands that were previously reported for their iron chelating ability. The chelators were analyzed using mass spectrometry, proton nuclear magnetic resonance and infrared spectroscopy. The iron chelators, 2-benzoylpyridine-4,4-dimethyl-3-thiosemicarbazone, 3-ethyl-1-{[2-phenyl-1-(pyridin-2-yl)ethylidene]amino}thiourea and 1-{[2-phenyl-1-(pyridin-2-yl)ethylidene]amino}-3-(prop‑2-en-1-yl)thiourea in their unbound conformation were crystallized and their structures were determined. This work addresses the evolution of a thiosemicarbazone class of iron chelators by analyzing and comparing the structure and properties of a series of closely related molecules, relating these to their in vitro activity thus providing valuable update to the search for newer, better and more effective iron chelators and metal-based therapeutics.

{"title":"Small molecule regulation of iron homeostasis: design and optimization of novel iron chelators based on a thiosemicarbazone scaffold","authors":"Christian S. Parry , Yue Li , Samuel Kojo Kwofie , Josh Valencia , Cynthia A．Tope Niedermaier , Timothy R. Ramadhar , Sergei Nekhai , Michael D. Wilson , Raymond J. Butcher","doi":"10.1016/j.molstruc.2025.141859","DOIUrl":"10.1016/j.molstruc.2025.141859","url":null,"abstract":"<div><div>Disrupted iron balance causes anemia and iron overload leading to hypoxia and systemic oxidative stress. Iron overload may arise from red blood cell disorders such as sickle cell disease, thalassemia major and primary hemochromatosis, or from treatment with multiple transfusions. These hematological disorders are characterized by constant red blood cell hemolysis and the release of iron. Hemolysis is a continuous source of reactive oxygen species whose accumulation changes the redox potential in the erythrocyte, the endothelium and other tissue causing damage to organ systems. Iron overload and its consequences can be treated with iron chelating therapy. We have carried out structural studies of small molecule ligands that were previously reported for their iron chelating ability. The chelators were analyzed using mass spectrometry, proton nuclear magnetic resonance and infrared spectroscopy. The iron chelators, 2-benzoylpyridine-4,4-dimethyl-3-thiosemicarbazone, 3-ethyl-1-{[2-phenyl-1-(pyridin-2-yl)ethylidene]amino}thiourea and 1-{[2-phenyl-1-(pyridin-2-yl)ethylidene]amino}-3-(prop‑2-en-1-yl)thiourea in their unbound conformation were crystallized and their structures were determined. This work addresses the evolution of a thiosemicarbazone class of iron chelators by analyzing and comparing the structure and properties of a series of closely related molecules, relating these to their in vitro activity thus providing valuable update to the search for newer, better and more effective iron chelators and metal-based therapeutics.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1334 ","pages":"Article 141859"},"PeriodicalIF":4.0,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143535066","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}

引用次数: 0

Nickel promoted tandem C-N cross-coupling reaction in water: The synthesis of 2-azido-benzimidazoles and 2-iodoarylcyanamides

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2025-02-24 DOI: 10.1016/j.molstruc.2025.141857

V.V.K. Vasu Juthiga , Megha Balha , Ramana Tamminana

The article describes an efficient method for the synthesis of 2-azidobenzimidazole employing nickel catalyst and DL-alpha-tocopherol methoxypolyethylene glycol succinate solution (TPGS-750-M) as a biodegradable surfactant in water through tandem intra-and inter molecular C-N bond formation. Using of water as a reaction medium and TPGS-750-M as a surfactant obviates the necessity for organic solvents, thereby enhancing the environmental sustainability of the synthesis. Further, this article also accomplishes an approach for aryl cyanamides at room temperature under green conditions. Spectroscopic techniques, including ¹H-NMR, ¹³C-NMR, and IR characterised the target products.

引用次数: 0

Synthesis and structure characterization of boron complexes containing C2-symmetric tertiary amine ligands: Assessment catalytic degradation of dyes and antioxidant properties

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2025-02-23 DOI: 10.1016/j.molstruc.2025.141842

Minggang Hu , Xiaochen Wang , Can Wang , Hongtao Chu , Xinfeng Song , Guohua Dong , Jiyuan Zhang , Jin Xing

In this study, a new and simple method for synthesizing boron complexes was presented. The boron complexes with C₂-symmetric ligands were prepared from in situ generated tertiary amine by the reaction of salicylaldehyde with primary amine in the presence of sodium borohydride. The boron complexes were characterized by ¹H and ¹³C NMR spectroscopy, elemental analysis, and mass spectrometry. The crystal structures of complexes 1 and 2 were determined by single crystal X-ray diffraction method. The complex is a mononuclear boron complex with a tertiary amine ligand. The boron center is tetracoordinated with a distorted tetrahedral geometry. Catalytic activities of the boron complexes in the reduction of dyes, was investigated using sodium borohydride as a reducing agent. Complexes 1 and 2 were effective catalysts for degradation of dyes. Kinetic studies reveal that the reduction of methylene blue is of the first order. Free radical scavenging activities of the boron complexes have been tested using DPPH, ABTS and hydroxyl radicals, respectively. The result shows that the boron complexes have effective antioxidant activity.

{"title":"Synthesis and structure characterization of boron complexes containing C2-symmetric tertiary amine ligands: Assessment catalytic degradation of dyes and antioxidant properties","authors":"Minggang Hu , Xiaochen Wang , Can Wang , Hongtao Chu , Xinfeng Song , Guohua Dong , Jiyuan Zhang , Jin Xing","doi":"10.1016/j.molstruc.2025.141842","DOIUrl":"10.1016/j.molstruc.2025.141842","url":null,"abstract":"<div><div>In this study, a new and simple method for synthesizing boron complexes was presented. The boron complexes with C2-symmetric ligands were prepared from in situ generated tertiary amine by the reaction of salicylaldehyde with primary amine in the presence of sodium borohydride. The boron complexes were characterized by 1H and 13C NMR spectroscopy, elemental analysis, and mass spectrometry. The crystal structures of complexes 1 and 2 were determined by single crystal X-ray diffraction method. The complex is a mononuclear boron complex with a tertiary amine ligand. The boron center is tetracoordinated with a distorted tetrahedral geometry. Catalytic activities of the boron complexes in the reduction of dyes, was investigated using sodium borohydride as a reducing agent. Complexes 1 and 2 were effective catalysts for degradation of dyes. Kinetic studies reveal that the reduction of methylene blue is of the first order. Free radical scavenging activities of the boron complexes have been tested using DPPH, ABTS and hydroxyl radicals, respectively. The result shows that the boron complexes have effective antioxidant activity.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1334 ","pages":"Article 141842"},"PeriodicalIF":4.0,"publicationDate":"2025-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143511784","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}

引用次数: 0

New quinazolinone-1,2,4-triazole analogues: Synthesis, anticancer evaluation, molecular docking, and in silico ADMET prediction

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2025-02-23 DOI: 10.1016/j.molstruc.2025.141850

Anjanareddy Basava Reddy , Tejeswara Rao Allaka , Vidya Sagar Reddy Avuthu , Kalyani Chepuri , Mohammad Z. Ahmed , Honnappa Nagarajaiah

A novel series of 1,2,4-triazole linked quinazolinone derivatives were created and produced as possible anticancer drugs. The structures of all the compounds were characterized by IR, ¹H NMR, ¹³C NMR, and Mass spectrometric techniques. The anticancer activity of all the prepared derivatives was evaluated against three human cancer cell lines: A549 (Lung cancer), MCF–7 and MDA-MB-231 (Breast cancer) by employing of MTT assay method. Doxorubicin used as reference compound and all the derivatives showed exceptional to moderate activity. The novel scaffolds had IC₅₀ values of ranging from 7.30 ± 1.4 µM to 33.44 ± 1.4 µM while the positive control (DXN) exhibited 8.45 ± 1.9 µM to 13.48 ± 0.8 µM respectively. It was shown that the recently created 1,2,4-triazole hybrids connected with substituted quinazolinone exhibited a considerable percentage of inhibition as anticancer drugs. Additionally, to link the in vitro biological activity data evaluated on three human cancer cell lines, the most active synthesized compounds were studied by molecular docking simulation studies with estrogen receptor alpha enzymatic mutation in breast cancer cell (PDB: 7KBS). The newly synthesized conjugates' docking scores ranged from –8.30 kcal/mol to –8.78 kcal/mol, and interacting residues with His-107, Glu-106, Lys-158, Trp-102, Arg-103, Leu-36, Pro-33, Met-66, Ile-95, Val-155, and Gly-151. Further evidence for the in vitro cytotoxicity behavior of the investigated drugs was obtained from in silico predictions, including SwissADME and PkCSM simulations.

{"title":"New quinazolinone-1,2,4-triazole analogues: Synthesis, anticancer evaluation, molecular docking, and in silico ADMET prediction","authors":"Anjanareddy Basava Reddy , Tejeswara Rao Allaka , Vidya Sagar Reddy Avuthu , Kalyani Chepuri , Mohammad Z. Ahmed , Honnappa Nagarajaiah","doi":"10.1016/j.molstruc.2025.141850","DOIUrl":"10.1016/j.molstruc.2025.141850","url":null,"abstract":"<div><div>A novel series of 1,2,4-triazole linked quinazolinone derivatives were created and produced as possible anticancer drugs. The structures of all the compounds were characterized by IR, 1H NMR, 13C NMR, and Mass spectrometric techniques. The anticancer activity of all the prepared derivatives was evaluated against three human cancer cell lines: A549 (Lung cancer), MCF–7 and MDA-MB-231 (Breast cancer) by employing of MTT assay method. Doxorubicin used as reference compound and all the derivatives showed exceptional to moderate activity. The novel scaffolds had IC50 values of ranging from 7.30 ± 1.4 µM to 33.44 ± 1.4 µM while the positive control (DXN) exhibited 8.45 ± 1.9 µM to 13.48 ± 0.8 µM respectively. It was shown that the recently created 1,2,4-triazole hybrids connected with substituted quinazolinone exhibited a considerable percentage of inhibition as anticancer drugs. Additionally, to link the in vitro biological activity data evaluated on three human cancer cell lines, the most active synthesized compounds were studied by molecular docking simulation studies with estrogen receptor alpha enzymatic mutation in breast cancer cell (PDB: 7KBS). The newly synthesized conjugates' docking scores ranged from –8.30 kcal/mol to –8.78 kcal/mol, and interacting residues with His-107, Glu-106, Lys-158, Trp-102, Arg-103, Leu-36, Pro-33, Met-66, Ile-95, Val-155, and Gly-151. Further evidence for the in vitro cytotoxicity behavior of the investigated drugs was obtained from in silico predictions, including SwissADME and PkCSM simulations.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1334 ","pages":"Article 141850"},"PeriodicalIF":4.0,"publicationDate":"2025-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143527566","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}

引用次数: 0

Experimental and computational study of Ni(II) and Zn(II) complexes of isatin-3-thiosemicarbazone: Structure, biological activity and ct-DNA binding study 异靛红-3-硫代氨基甲酮的 Ni(II) 和 Zn(II) 复合物的实验和计算研究：结构、生物活性和 ct-DNA 结合研究

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2025-02-23 DOI: 10.1016/j.molstruc.2025.141846

Qurat Ul Ain , Iqubal Singh , Kamaldeep Paul , Ray J. Butcher , Rekha Sharma

Reaction of ssatin-3-thiosemicarbazone (H₂itsc) with nickel(II) and zinc(II) acetate in a 1:2 (M : L) molar ratio yielded the complexes of stoichiometry, [M(Hitsc)₂] (M = Ni, 1 and Zn, 2). Complexes were characterized using FTIR, elemental analysis, NMR (¹H and ¹³C) spectroscopy, mass spectrophotometry and X-ray crystallography. In complex 1, two isatin-3-thiosemicarbazone ligands are attached to Ni(II) through O, N, S- donor atoms in trans position to form octahedral geometry, whereas in complex 2, two thio- ligands are attached to Zn^II via N, S- atoms to give distroted tetraderal geometry. Compounds were evaluated for various biological activities (anti-tubercular and anticancer activity). Molecular docking studies and DNA (PDB ID: 1BNA) have supported the experimental data with minimum binding energies of -6.6 kcal/mol (H₂itsc), -11.0 kcal/mol (1) and -9.7 kcal/mol (2). The bioavailability of most active compound (2) was confirmed by its strong binding affinities with HSA (binding constant = 2.01×10⁵ M⁻¹). The binding interaction of 2 with ct-DNA was also checked using UV–visible and fluorescence spectroscopy. A high quenching of 91–94 % obtained in emission peak of ct-DNA on addition of 2 indicates its strong binding. A high binding constant of 6.5×10⁵ M⁻¹ with 0.94 binding sites agrees with the experimental anticancer activity.

{"title":"Experimental and computational study of Ni(II) and Zn(II) complexes of isatin-3-thiosemicarbazone: Structure, biological activity and ct-DNA binding study","authors":"Qurat Ul Ain , Iqubal Singh , Kamaldeep Paul , Ray J. Butcher , Rekha Sharma","doi":"10.1016/j.molstruc.2025.141846","DOIUrl":"10.1016/j.molstruc.2025.141846","url":null,"abstract":"<div><div>Reaction of ssatin-3-thiosemicarbazone (H2itsc) with nickel(II) and zinc(II) acetate in a 1:2 (M : L) molar ratio yielded the complexes of stoichiometry, [M(Hitsc)2] (M = Ni, 1 and Zn, 2). Complexes were characterized using FTIR, elemental analysis, NMR (1H and 13C) spectroscopy, mass spectrophotometry and X-ray crystallography. In complex 1, two isatin-3-thiosemicarbazone ligands are attached to Ni(II) through O, N, S- donor atoms in trans position to form octahedral geometry, whereas in complex 2, two thio- ligands are attached to ZnII via N, S- atoms to give distroted tetraderal geometry. Compounds were evaluated for various biological activities (anti-tubercular and anticancer activity). Molecular docking studies and DNA (PDB ID: 1BNA) have supported the experimental data with minimum binding energies of -6.6 kcal/mol (H2itsc), -11.0 kcal/mol (1) and -9.7 kcal/mol (2). The bioavailability of most active compound (2) was confirmed by its strong binding affinities with HSA (binding constant = 2.01×105 M−1). The binding interaction of 2 with ct-DNA was also checked using UV–visible and fluorescence spectroscopy. A high quenching of 91–94 % obtained in emission peak of ct-DNA on addition of 2 indicates its strong binding. A high binding constant of 6.5×105 M−1 with 0.94 binding sites agrees with the experimental anticancer activity.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1335 ","pages":"Article 141846"},"PeriodicalIF":4.0,"publicationDate":"2025-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561719","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}

引用次数: 0

Synthesis and characterization of emissive 1,9,10-anthyridine derivatives with donor and acceptor groups

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2025-02-22 DOI: 10.1016/j.molstruc.2025.141840

Yasufumi Fuchi , Keita Ikeno , Moeka Fujihara , Tomohiro Umeno , Masatoshi Kawahata , Kazuteru Usui , Satoru Karasawa

Push–pull-type emissive 1,9,10-anthyridine derivatives incorporating bis-trifluoromethyl and amino (hydroxy) groups were designed and synthesized through the ring expansion of 1,8-naphthyridine. The X-ray crystallographic analysis of the single crystals of these 1,9,10-anthyridine derivatives, termed “TANA,” revealed the formation of intermolecular hydrogen-bonded complexes or hydration complexes. These TANA derivatives exhibited fluorescence solvatochromic properties and emitted at longer wavelengths compared to 1,8-naphthyridine, despite possessing analogous bis-trifluoromethyl and amino groups. Furthermore, NMR titration experiments revealed that TANA, characterized by an ensemble of three hydrogen-bond acceptors, is capable of forming hydrogen-bonded complexes with protonated diaminopyridine, which contains an array of three hydrogen-bond donors. Therefore, TANA derivatives are excellent fluorescent materials with molecular recognition abilities.

引用次数: 0

Multifunctional imino-amido based asymmetrical ligands with Pd(II) for electrochemical CO2 reduction

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2025-02-22 DOI: 10.1016/j.molstruc.2025.141828

Shazia Hussain , Shabeeb Hussain , Riffat Parveen , Muhammad Nawaz Tahir , Ehsan Ullah Mughal , M. Naveed Zafar

In this work, four new Pd(II) complexes with multifunctional and asymmetrical nitrogen donor chelates are reported for electrochemical CO₂ reduction. The anionic amido and neutral imino ligand arms were connected via rigid aromatic framework in ligand to achieve flexible electron donation for palladium. Further, imino arm of ligand was substituted with various electron donating aryl groups to study the subtle variations of inductive and resonance effects on palladium centred electro-catalysis. The successful synthesis of Pd(II) complexes were verified by various spectroscopic techniques namely ¹H NMR, ¹³C NMR, FTIR, MS and by elemental analysis. It was found out that palladium complexes with extended conjugation and more electron donor substituents on ligands caused an enhancement in electrochemical reduction of CO₂ to synthesis gas (TOF of 282s^-1). Multifunctional ligand features such as proton shuttles and hydrophobic groups were introduced to achieve high selectivity for CO (TOF of 194s^-1 by [Pd(L³)₂] Where L³ = (E)-2-((2-(cyclohexylamino) pyridin-3-ylimino)methyl)naphthalen-2-ol).

{"title":"Multifunctional imino-amido based asymmetrical ligands with Pd(II) for electrochemical CO2 reduction","authors":"Shazia Hussain , Shabeeb Hussain , Riffat Parveen , Muhammad Nawaz Tahir , Ehsan Ullah Mughal , M. Naveed Zafar","doi":"10.1016/j.molstruc.2025.141828","DOIUrl":"10.1016/j.molstruc.2025.141828","url":null,"abstract":"<div><div>In this work, four new Pd(II) complexes with multifunctional and asymmetrical nitrogen donor chelates are reported for electrochemical CO2 reduction. The anionic amido and neutral imino ligand arms were connected via rigid aromatic framework in ligand to achieve flexible electron donation for palladium. Further, imino arm of ligand was substituted with various electron donating aryl groups to study the subtle variations of inductive and resonance effects on palladium centred electro-catalysis. The successful synthesis of Pd(II) complexes were verified by various spectroscopic techniques namely 1H NMR, 13C NMR, FTIR, MS and by elemental analysis. It was found out that palladium complexes with extended conjugation and more electron donor substituents on ligands caused an enhancement in electrochemical reduction of CO2 to synthesis gas (TOF of 282s-1). Multifunctional ligand features such as proton shuttles and hydrophobic groups were introduced to achieve high selectivity for CO (TOF of 194s-1 by [Pd(L3)2] Where L3 = (E)-2-((2-(cyclohexylamino) pyridin-3-ylimino)methyl)naphthalen-2-ol).</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1334 ","pages":"Article 141828"},"PeriodicalIF":4.0,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143479317","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}

引用次数: 0

Two tetranuclear lanthanide complexes respectively featuring magnetocaloric effect and slow magnetization relaxation

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2025-02-22 DOI: 10.1016/j.molstruc.2025.141750

Ming Fang, Ya-Ru Dang, Mei-Hui Ma, Run-Yan Shao, Ya-Hui Luan, Zhen-Huan Tang, Ying-Hao Ma, Bao-Xiang Shi

Two parallelogram-shape tetranuclear rare earth compounds, having the molecular formula {[Ln₄(L)₂(acac)₄(Hthma)₂]·2CH₃OH·4CH₃CN} (Ln = Gd (1), Dy (2); H₂L = N'-(2‑hydroxy-5-methylbenzylidene)-6-(hydroxymethyl) picolinohydrazide, acac = acetylacetone, H₃thma = 1,1,1-tris(hydroxymethyl)methylamine), were constructed and structurally characterized. The [Ln₄O₈] core of compounds 1 and 2 are connected collectively by means of two µ₂ carbonyl O atoms derived from L²⁻ main ligands, two μ₃ as well as two μ₂ hydroxyl O atoms originated from two Hthma²⁻ and two µ₂ O atoms from two acac⁻. Magnetic research concluded that 1 displays magnetocaloric effect (−ΔS_m = 29.91 J K⁻¹ kg⁻¹) and 2 displays extremely weak antiferromagnetic interaction among neighboring rare earth ions. Single molecule magnet behaviors were possibly detected in 2, however no characteristic maximum was reached above 2 K.

{"title":"Two tetranuclear lanthanide complexes respectively featuring magnetocaloric effect and slow magnetization relaxation","authors":"Ming Fang, Ya-Ru Dang, Mei-Hui Ma, Run-Yan Shao, Ya-Hui Luan, Zhen-Huan Tang, Ying-Hao Ma, Bao-Xiang Shi","doi":"10.1016/j.molstruc.2025.141750","DOIUrl":"10.1016/j.molstruc.2025.141750","url":null,"abstract":"<div><div>Two parallelogram-shape tetranuclear rare earth compounds, having the molecular formula {[Ln4(L)2(acac)4(Hthma)2]·2CH3OH·4CH3CN} (Ln = Gd (1), Dy (2); H2L = N'-(2‑hydroxy-5-methylbenzylidene)-6-(hydroxymethyl) picolinohydrazide, acac = acetylacetone, H3thma = 1,1,1-tris(hydroxymethyl)methylamine), were constructed and structurally characterized. The [Ln4O8] core of compounds 1 and 2 are connected collectively by means of two µ2 carbonyl O atoms derived from L2− main ligands, two μ3 as well as two μ2 hydroxyl O atoms originated from two Hthma2− and two µ2 O atoms from two acac−. Magnetic research concluded that 1 displays magnetocaloric effect (−ΔSm = 29.91 J K−1 kg−1) and 2 displays extremely weak antiferromagnetic interaction among neighboring rare earth ions. Single molecule magnet behaviors were possibly detected in 2, however no characteristic maximum was reached above 2 K.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1334 ","pages":"Article 141750"},"PeriodicalIF":4.0,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143507956","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}

引用次数: 0

Computational studies and anticancer activities of newly designed and characterized heteroleptic copper(II) complexes of 1,10-phenanthroline with benzimidazole-imidazopyridine hybrids as DNA groove binders

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2025-02-22 DOI: 10.1016/j.molstruc.2025.141847

Ufuk Yıldız , Bahar Caymaz , Abdurrahman Şengül , Senem Akkoç , Nursel Acar-Selçuki , Zuhal Gerçek , Burak Coban

This study reports the synthesis, characterization, computational analysis, and in vitro anticancer activity of novel heteroleptic copper(II) coordination compounds, [Cu(phen)(ipbi)(H₂O)](NO₃) (1) and [Cu₂(phen)₂(bis-ipbi)(H₂O)₂](NO₃)₂ (2). Here, phen: represents 1,10-phenanthroline, ipbi refers to 2-(imidazo[1,2-a]pyridin-8-yl)benzimidazole (L1), and bis-ipbi (L2) denotes its bis-derivative. Compounds 1 and 2 are five-coordinate copper(II) complexes, where the metal centers bind to the deprotonated nitrogen atom of the benzimidazole ring, the tertiary nitrogen atom of the imidazopyridine ring, and the nitrogen atoms of the phenanthroline ligands. A water molecule occupies the fifth coordination site in each complex. The biological studies revealed that both compounds exhibit DNA binding through groove interactions, DNA cleavage activity, transcription inhibition, and significant cytotoxic activity. Compounds 1 and 2 demonstrated superior inhibitory activity against various cancer cell lines compared to the positive control (Cisplatin) and the parent complex [Cu(phen)₂(H₂O)]²⁺. Specifically, compound 1 showed the most potent IC₅₀ value of 1.23 µM against the triple-negative breast cancer cell line MDA-MB-231. The IC₅₀ values for MDA-MB-231 were 1.23 µM (1) and 1.28 µM (2), compared to 2.77 µM for the reference compound. Similar enhancements were observed against MCF-7 (10.59 and 12.56 µM vs. 9.72 µM), HepG2 (2.57 and 2.77 µM vs. 30.38 µM), DLD-1 (5.25 and 5.57 µM vs. 60.79 µM), and Beas-2B (6.10 and 12.99 µM vs. 11.16 µM). Computational and experimental studies, including UV−vis absorption and FTIR spectroscopy, revealed good agreement. Notably, complex 2 exhibited the smallest chemical hardness and highest electrophilicity, indicating a greater likelihood of electronic transitions. These findings suggest that complexes 1 and 2 are promising candidates for further exploration as anticancer agents.

{"title":"Computational studies and anticancer activities of newly designed and characterized heteroleptic copper(II) complexes of 1,10-phenanthroline with benzimidazole-imidazopyridine hybrids as DNA groove binders","authors":"Ufuk Yıldız , Bahar Caymaz , Abdurrahman Şengül , Senem Akkoç , Nursel Acar-Selçuki , Zuhal Gerçek , Burak Coban","doi":"10.1016/j.molstruc.2025.141847","DOIUrl":"10.1016/j.molstruc.2025.141847","url":null,"abstract":"<div><div>This study reports the synthesis, characterization, computational analysis, and in vitro anticancer activity of novel heteroleptic copper(II) coordination compounds, [Cu(phen)(ipbi)(H2O)](NO3) (1) and [Cu2(phen)2(bis-ipbi)(H2O)2](NO3)2 (2). Here, phen: represents 1,10-phenanthroline, ipbi refers to 2-(imidazo[1,2-a]pyridin-8-yl)benzimidazole (L1), and bis-ipbi (L2) denotes its bis-derivative. Compounds 1 and 2 are five-coordinate copper(II) complexes, where the metal centers bind to the deprotonated nitrogen atom of the benzimidazole ring, the tertiary nitrogen atom of the imidazopyridine ring, and the nitrogen atoms of the phenanthroline ligands. A water molecule occupies the fifth coordination site in each complex. The biological studies revealed that both compounds exhibit DNA binding through groove interactions, DNA cleavage activity, transcription inhibition, and significant cytotoxic activity. Compounds 1 and 2 demonstrated superior inhibitory activity against various cancer cell lines compared to the positive control (Cisplatin) and the parent complex [Cu(phen)2(H₂O)]²⁺. Specifically, compound 1 showed the most potent IC₅₀ value of 1.23 µM against the triple-negative breast cancer cell line MDA-MB-231. The IC₅₀ values for MDA-MB-231 were 1.23 µM (1) and 1.28 µM (2), compared to 2.77 µM for the reference compound. Similar enhancements were observed against MCF-7 (10.59 and 12.56 µM vs. 9.72 µM), HepG2 (2.57 and 2.77 µM vs. 30.38 µM), DLD-1 (5.25 and 5.57 µM vs. 60.79 µM), and Beas-2B (6.10 and 12.99 µM vs. 11.16 µM). Computational and experimental studies, including UV−vis absorption and FTIR spectroscopy, revealed good agreement. Notably, complex 2 exhibited the smallest chemical hardness and highest electrophilicity, indicating a greater likelihood of electronic transitions. These findings suggest that complexes 1 and 2 are promising candidates for further exploration as anticancer agents.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1335 ","pages":"Article 141847"},"PeriodicalIF":4.0,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561721","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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