Pub Date : 2024-12-25DOI: 10.1016/j.poly.2024.117369
Kamelah S. Alrashdi , Bandar A. Babgi , Ehab M.M. Ali , Abdul-Hamid M. Emwas , Abdesslem Jedidi , Shaaban A. Elroby , Bambar Davaasuren , Doaa Domyati , Mariusz Jaremko
Tridentate Schiff base ligand (L) was synthesized from reactions of N-phenyl-1,2-diaminobenzene and 3-ethoxysalicylaldehyde. The Schiff base was hydrogenated by sodium borohydride to produce the second ligand (HL). Complexes with the general formula Pt(N^{NO})Cl were synthesized by reacting K2PtCl4 with the ligands in DMSO/ethanol mixtures, generating L-Pt and HL-Pt complexes. The ligand and its complex were characterized by NMR spectroscopy, mass spectrometry and elemental analysis. The DNA-binding of the platinum(II) compounds were evaluated by following changes induced on the viscosity of ct-DNA, indicating covalent binding mode with ct-DNA. L-Pt is strongly emissive with emission maximum ca. 630 nm, which complicated the evaluation of DNA- and BSA-binding by the fluorescence quenching technique. However, HL-Pt has good binding affinities with ct-DNA with apparent binding constant of 1.0 × 106 while BSA-binding studies indicated static quenching process with binding constant (Kb) value equals to 1.43 × 106. The half maximal inhibitory concentrations (IC50) values against MCF-7 and HepG2 suggest that L-Pt has better cytotoxic effect compared to that of HL-Pt and cisplatin. Although, both L-Pt and HL-Pt were more cytotoxic towards the normal cell line. The flow cytometry assay indicated that L-Pt, HL-Pt and cisplatin induce their cytotoxic effect by apoptosis. However, the cell cycle arrest of L-Pt and HL-Pt on MCF-7 show similar pattern but it is different to that of MCF-7 treated with cisplatin, suggesting different mechanism in activating the cell death. DFT calculations were employed to stimulate the binding of L-Pt and HL-Pt with a fragment of DNA (trimer), highlighting the effect of the ligands. In conclusion, the current study highlight the importance of the azomethine linkage in the ligand on the anticancer properties on the complexes of the type Pt(N^{NO})Cl.
{"title":"Structural-property relationship in Pt(N^{NO})Cl: The effect of hydrogenating the Schiff base ligand on spectral, biomolecule-binding and anticancer properties","authors":"Kamelah S. Alrashdi , Bandar A. Babgi , Ehab M.M. Ali , Abdul-Hamid M. Emwas , Abdesslem Jedidi , Shaaban A. Elroby , Bambar Davaasuren , Doaa Domyati , Mariusz Jaremko","doi":"10.1016/j.poly.2024.117369","DOIUrl":"10.1016/j.poly.2024.117369","url":null,"abstract":"<div><div>Tridentate Schiff base ligand (L) was synthesized from reactions of <em>N</em>-phenyl-1,2-diaminobenzene and 3-ethoxysalicylaldehyde. The Schiff base was hydrogenated by sodium borohydride to produce the second ligand (HL). Complexes with the general formula Pt(N^{NO})Cl were synthesized by reacting K<sub>2</sub>PtCl<sub>4</sub> with the ligands in DMSO/ethanol mixtures, generating L-Pt and HL-Pt complexes. The ligand and its complex were characterized by NMR spectroscopy, mass spectrometry and elemental analysis. The DNA-binding of the platinum(II) compounds were evaluated by following changes induced on the viscosity of ct-DNA, indicating covalent binding mode with ct-DNA. L-Pt is strongly emissive with emission maximum ca. 630 nm, which complicated the evaluation of DNA- and BSA-binding by the fluorescence quenching technique. However, HL-Pt has good binding affinities with ct-DNA with apparent binding constant of 1.0 × 10<sup>6</sup> while BSA-binding studies indicated static quenching process with binding constant (K<sub>b</sub>) value equals to 1.43 × 10<sup>6</sup>. The half maximal inhibitory concentrations (IC<sub>50</sub>) values against MCF-7 and HepG2 suggest that L-Pt has better cytotoxic effect compared to that of HL-Pt and cisplatin. Although, both L-Pt and HL-Pt were more cytotoxic towards the normal cell line. The flow cytometry assay indicated that L-Pt, HL-Pt and cisplatin induce their cytotoxic effect by apoptosis. However, the cell cycle arrest of L-Pt and HL-Pt on MCF-7 show similar pattern but it is different to that of MCF-7 treated with cisplatin, suggesting different mechanism in activating the cell death. DFT calculations were employed to stimulate the binding of L-Pt and HL-Pt with a fragment of DNA (trimer), highlighting the effect of the ligands. In conclusion, the current study highlight the importance of the azomethine linkage in the ligand on the anticancer properties on the complexes of the type Pt(N^{NO})Cl.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"268 ","pages":"Article 117369"},"PeriodicalIF":2.4,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143179668","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 : 2024-12-20DOI: 10.1016/j.poly.2024.117370
Damir A. Safin
<div><div>M. Singh <em>et al</em>. in their article “Novel Macrocyclic Bidentate Schiff’s base Hg (II) Complexes, Hirshfeld surface analysis, NCI analysis, and Antimicrobial activity studies” (Polyhedron 264 (2024) 117194) reported on the synthesis of a new macrocyclic Schiff base named 2,10,12,20-tetrahydroxy-3,6,9,13,16,19-hexaaza-1,11(1,3)-dibenzenacycloicosaphane-2,9,12,19-tetraene-1<sup>5</sup>,11<sup>5</sup>-dicarboxylic acid (<strong>L</strong>), which was obtained through a condensation reaction of two equivalents of trimesic acid and two equivalents of diethylenetriamine. The reported Schiff base <strong>L</strong> was involved in the complexation reaction with an equimolar amount of HgCl<sub>2</sub> and HgBr<sub>2</sub> in a mixture of ethanol and acetonitrile, yielding complexes [HgCl<sub>2</sub>L] (<strong>1</strong>) and [HgBr<sub>2</sub>L] (<strong>2</strong>). It should be mentioned, that the formation of both complexes led to the formation of a doubly deprotonated parent ligand <strong>L</strong><sup>2−</sup>, with the elimination of both NH hydrogen atoms. This, in fact, means the formation of complex anions <strong>1</strong><sup>2−</sup> and <strong>2</strong><sup>2−</sup>, while no cationic counterparts were provided. Although the authors reported some geometrical parameters of the obtained metallocomplexes, no crystal structures of neither the parent ligand <strong>L</strong> nor complexes <strong>1</strong> and <strong>2</strong> were provided. Furthermore, the corresponding request from the Cambridge Structural Database revealed no deposited crystal structures associated with this publication. However, the authors reported the crystal structure of one of the starting reagents, viz., trimesic acid, by providing a calculated powder X-ray diffraction pattern of its methanol solvate, and using the Hirshfeld surface analysis, RDG and NCI plots. Notably, methanol was not applied neither for the synthesis of <strong>L</strong> nor for the fabrication of <strong>1</strong> and <strong>2</strong>, thus, the formation of the methanol solvate of trimesic acid is unclear. It is, in general, unclear the reason to discuss the latter compound in the light of the scope of this work. The authors also discussed the IR and <sup>1</sup>H NMR data for both metallocomplexes although only one IR and one <sup>1</sup>H NMR spectra were provided for one unspecified complex. To be said, the <sup>1</sup>H NMR is completely incorrectly discussed since it does not contain signals for the expected molecules, but only signals for the solvents. Some results of the molecular docking studies were also provided, however, for a doubly charged parent ligand, viz., <strong>H<sub>2</sub>L</strong><sup>2+</sup>, with two quaternary amine nitrogens. This is also unclear, since one would expect studies for <strong>L</strong>, <strong>1</strong> and <strong>2</strong>. Finally, the whole manuscript is dubiously written with a plethora of grammatical and scientific co
{"title":"Comment on “Novel Macrocyclic Bidentate Schiff’s base Hg (II) Complexes, Hirshfeld surface analysis, NCI analysis, and Antimicrobial activity studies” by M. Singh et al. [Polyhedron 264 (2024) 117194]","authors":"Damir A. Safin","doi":"10.1016/j.poly.2024.117370","DOIUrl":"10.1016/j.poly.2024.117370","url":null,"abstract":"<div><div>M. Singh <em>et al</em>. in their article “Novel Macrocyclic Bidentate Schiff’s base Hg (II) Complexes, Hirshfeld surface analysis, NCI analysis, and Antimicrobial activity studies” (Polyhedron 264 (2024) 117194) reported on the synthesis of a new macrocyclic Schiff base named 2,10,12,20-tetrahydroxy-3,6,9,13,16,19-hexaaza-1,11(1,3)-dibenzenacycloicosaphane-2,9,12,19-tetraene-1<sup>5</sup>,11<sup>5</sup>-dicarboxylic acid (<strong>L</strong>), which was obtained through a condensation reaction of two equivalents of trimesic acid and two equivalents of diethylenetriamine. The reported Schiff base <strong>L</strong> was involved in the complexation reaction with an equimolar amount of HgCl<sub>2</sub> and HgBr<sub>2</sub> in a mixture of ethanol and acetonitrile, yielding complexes [HgCl<sub>2</sub>L] (<strong>1</strong>) and [HgBr<sub>2</sub>L] (<strong>2</strong>). It should be mentioned, that the formation of both complexes led to the formation of a doubly deprotonated parent ligand <strong>L</strong><sup>2−</sup>, with the elimination of both NH hydrogen atoms. This, in fact, means the formation of complex anions <strong>1</strong><sup>2−</sup> and <strong>2</strong><sup>2−</sup>, while no cationic counterparts were provided. Although the authors reported some geometrical parameters of the obtained metallocomplexes, no crystal structures of neither the parent ligand <strong>L</strong> nor complexes <strong>1</strong> and <strong>2</strong> were provided. Furthermore, the corresponding request from the Cambridge Structural Database revealed no deposited crystal structures associated with this publication. However, the authors reported the crystal structure of one of the starting reagents, viz., trimesic acid, by providing a calculated powder X-ray diffraction pattern of its methanol solvate, and using the Hirshfeld surface analysis, RDG and NCI plots. Notably, methanol was not applied neither for the synthesis of <strong>L</strong> nor for the fabrication of <strong>1</strong> and <strong>2</strong>, thus, the formation of the methanol solvate of trimesic acid is unclear. It is, in general, unclear the reason to discuss the latter compound in the light of the scope of this work. The authors also discussed the IR and <sup>1</sup>H NMR data for both metallocomplexes although only one IR and one <sup>1</sup>H NMR spectra were provided for one unspecified complex. To be said, the <sup>1</sup>H NMR is completely incorrectly discussed since it does not contain signals for the expected molecules, but only signals for the solvents. Some results of the molecular docking studies were also provided, however, for a doubly charged parent ligand, viz., <strong>H<sub>2</sub>L</strong><sup>2+</sup>, with two quaternary amine nitrogens. This is also unclear, since one would expect studies for <strong>L</strong>, <strong>1</strong> and <strong>2</strong>. Finally, the whole manuscript is dubiously written with a plethora of grammatical and scientific co","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"268 ","pages":"Article 117370"},"PeriodicalIF":2.4,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143179669","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 : 2024-12-19DOI: 10.1016/j.poly.2024.117361
Mahmoud Tarek , Tamer K. Khatab , Abdulrahman A. Almehizia , Ahmed M. Naglah , Amer A. Zen , Gehad E. Said
Nicotinic acid or vit-B3 has a lot of important biological uses. It can also be presented as Metal-Organic Framework (MOF) with copper which is presented as a catalyst after the physicochemical characterization of its structure and morphological properties by IR, SEM, EDX, TEM, XRD and DFT calculation. 1-((Benzo[d]thiazol-2-ylamino)(phenyl)methyl) naphthalen-2-ol derivatives were successfully prepared by one-pot catalytic synthesis through the reaction between 2-aminobenzothiazole, aromatic aldehyde and 2-naphthol in the presence of Cu/NA-MOF as a catalyst under solvent-free conditions. The prepared products undergo docking and in vitro evaluation as acetylcholine esterase inhibitors (AChE inhibitors) and are compared with Donepezil as a reference Alzheimer’s drug. The data obtained explained that compound 4-((benzo[d]thiazol-2-ylamino)(2-hydroxynaphthalen-1-yl)methyl)phenyl 4-methylbenzoate (4i) gives promising records.
{"title":"A proficient MOF-catalyzed multicomponent one-pot synthesis of 1-((benzo[d]thiazol-2-ylamino)(phenyl)methyl)naphthalen-2-ol derivatives with in vitro anti-Alzheimer validation and DFT calculations","authors":"Mahmoud Tarek , Tamer K. Khatab , Abdulrahman A. Almehizia , Ahmed M. Naglah , Amer A. Zen , Gehad E. Said","doi":"10.1016/j.poly.2024.117361","DOIUrl":"10.1016/j.poly.2024.117361","url":null,"abstract":"<div><div>Nicotinic acid or vit-B<sub>3</sub> has a lot of important biological uses. It can also be presented as Metal-Organic Framework (MOF) with copper which is presented as a catalyst after the physicochemical characterization of its structure and morphological properties by IR, SEM, EDX, TEM, XRD and DFT calculation. 1-((Benzo[<em>d</em>]thiazol-2-ylamino)(phenyl)methyl) naphthalen-2-ol derivatives were successfully prepared by one-pot catalytic synthesis through the reaction between 2-aminobenzothiazole, aromatic aldehyde and 2-naphthol in the presence of Cu/NA-MOF as a catalyst under solvent-free conditions. The prepared products undergo docking and <em>in vitro</em> evaluation as <em>acetylcholine esterase</em> inhibitors (<em>AChE</em> inhibitors) and are compared with Donepezil as a reference Alzheimer’s drug. The data obtained explained that compound 4-((benzo[<em>d</em>]thiazol-2-ylamino)(2-hydroxynaphthalen-1-yl)methyl)phenyl 4-methylbenzoate (<strong>4i</strong>) gives promising records.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"268 ","pages":"Article 117361"},"PeriodicalIF":2.4,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143178833","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 : 2024-12-07DOI: 10.1016/j.poly.2024.117356
Shu Wang
The synthesis of 3,4-dihydropyrimidin-2(1H)-ones and highly functionalized piperidines is an attractive challenge among synthetic chemists because these compounds are precious from a pharmacological and biological point of view. In this method, we want to show that the Fe3O4@SiO2-Serine-Ni(II) catalyst in glycerol solvent is an efficient and environmentally friendly catalytic system for the preparation of a library of 3,4-dihydropyridine-2 (1H)-ones and highly functionalized piperidines. In these reactions, various substrates such as benzaldehydes with electron-donating and electron-withdrawing substituents, heterocyclic aldehydes, and amines were evaluated, and the desired products were synthesized with good to excellent yields in a very short period of time. The recovery tests showed that the Fe3O4@SiO2-Serine-Ni(II) catalyst still has high efficiency and stability despite being reused 9 times. The structure, shape, stability and magnetic properties of the Fe3O4@SiO2-Serine-Ni(II) catalyst were evaluated both in the fresh state and after recovery by a series of spectroscopic analyses such as FT-IR, VSM, TGA, XRD, SEM, TEM, EDX, ICP-OES and elemental mapping techniques. This method has the following features compared to previously reported methods: performing reactions in glycerol solvent (environmentally friendly) and synthesis of products with high efficiency in a short period of time, the feasibility of the catalytic system for a wide range of substrates, the use of a green and recoverable catalyst, and the high reusability of the catalyst.
{"title":"Fe3O4@SiO2-Serine-Ni(II) nanocomposite: A novel end efficient magnetically reusable nanocatalyst for synthesis of heterocycles","authors":"Shu Wang","doi":"10.1016/j.poly.2024.117356","DOIUrl":"10.1016/j.poly.2024.117356","url":null,"abstract":"<div><div>The synthesis of 3,4-dihydropyrimidin-2(1H)-ones and highly functionalized piperidines is an attractive challenge among synthetic chemists because these compounds are precious from a pharmacological and biological point of view. In this method, we want to show that the Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>-Serine-Ni(II) catalyst in glycerol solvent is an efficient and environmentally friendly catalytic system for the preparation of a library of 3,4-dihydropyridine-2 (1H)-ones and highly functionalized piperidines. In these reactions, various substrates such as benzaldehydes with electron-donating and electron-withdrawing substituents, heterocyclic aldehydes, and amines were evaluated, and the desired products were synthesized with good to excellent yields in a very short period of time. The recovery tests showed that the Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>-Serine-Ni(II) catalyst still has high efficiency and stability despite being reused 9 times. The structure, shape, stability and magnetic properties of the Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>-Serine-Ni(II) catalyst were evaluated both in the fresh state and after recovery by a series of spectroscopic analyses such as FT-IR, VSM, TGA, XRD, SEM, TEM, EDX, ICP-OES and elemental mapping techniques. This method has the following features compared to previously reported methods: performing reactions in glycerol solvent (environmentally friendly) and synthesis of products with high efficiency in a short period of time, the feasibility of the catalytic system for a wide range of substrates, the use of a green and recoverable catalyst, and the high reusability of the catalyst.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"268 ","pages":"Article 117356"},"PeriodicalIF":2.4,"publicationDate":"2024-12-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143180416","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 : 2024-12-06DOI: 10.1016/j.poly.2024.117355
Farag M.A. Altalbawy , Ahmed Mohamed Arbab , Jayanti Makasana , S. Renuka Jyothi , Bharti Kumari , Deepak Bhanot , Ali Khelif
This study presents the development of a novel green nanocatalyst, iodine source heterogenized on Fe3O4@SiO2 modified with dopamine (Fe3O4@SiO2-Dop-I3), for the efficient synthesis of 2,4,5-triaryl imidazoles through the reaction of benzil, ammonium acetate, and benzaldehyde in water under mild conditions. The catalyst combines the magnetic properties of Fe3O4 with the stability and enhanced surface area provided by silica, while dopamine modification facilitates effective iodine immobilization, thereby improving catalytic performance. The reaction was conducted under mild conditions, yielding high selectivity and significant yields of the desired imidazole derivatives. Notably, the Fe3O4@SiO2-Dop-I3 catalyst demonstrated excellent reusability, maintaining its catalytic activity across multiple cycles without substantial loss in efficiency. The reusability results showed that the Fe3O4@SiO2-Dop-I3 catalyst has the ability to be used at least 9 times without reducing its efficiency significantly. This work highlights the potential of this innovative nanocatalyst as a sustainable alternative for organic synthesis, contributing to the advancement of green chemistry methodologies in the preparation of valuable heterocyclic compounds.
{"title":"Iodine source heterogenized on Fe3O4@SiO2 modified with dopamine as a green and reusable nanocatalyst for the synthesis of 2,4,5-triaryl imidazoles","authors":"Farag M.A. Altalbawy , Ahmed Mohamed Arbab , Jayanti Makasana , S. Renuka Jyothi , Bharti Kumari , Deepak Bhanot , Ali Khelif","doi":"10.1016/j.poly.2024.117355","DOIUrl":"10.1016/j.poly.2024.117355","url":null,"abstract":"<div><div>This study presents the development of a novel green nanocatalyst, iodine source heterogenized on Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub> modified with dopamine (Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>-Dop-I<sub>3</sub>), for the efficient synthesis of 2,4,5-triaryl imidazoles through the reaction of benzil, ammonium acetate, and benzaldehyde in water under mild conditions. The catalyst combines the magnetic properties of Fe<sub>3</sub>O<sub>4</sub> with the stability and enhanced surface area provided by silica, while dopamine modification facilitates effective iodine immobilization, thereby improving catalytic performance. The reaction was conducted under mild conditions, yielding high selectivity and significant yields of the desired imidazole derivatives. Notably, the Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>-Dop-I<sub>3</sub> catalyst demonstrated excellent reusability, maintaining its catalytic activity across multiple cycles without substantial loss in efficiency. The reusability results showed that the Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2-</sub>Dop-I<sub>3</sub> catalyst has the ability to be used at least 9 times without reducing its efficiency significantly. This work highlights the potential of this innovative nanocatalyst as a sustainable alternative for organic synthesis, contributing to the advancement of green chemistry methodologies in the preparation of valuable heterocyclic compounds.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"268 ","pages":"Article 117355"},"PeriodicalIF":2.4,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143180417","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 : 2024-11-26DOI: 10.1016/j.poly.2024.117318
Sk Khalid Rahaman , Taposi Chatterjee , Kalamoddin Shaikh , Samim Khan , Masoom Raza Siddiqui , Saikh M. Wabaidur , Md Maidul Islam , Seikh Mafiz Alam , Mohammad Hedayetullah Mir
The present research study is centered around the synthesis, characterization, and biological application of a ternary mixed-ligand based binuclear Cu(II) complex [Cu2(trans-1,4-chdc)(4,4′-Me2-2,2′-bpy)2(5,5′-Me2-2,2′-bpy)2]·2(cis-H21,4-chdc)·2(BF4¯) (1) by meticulous incorporation of 4,4′-dimethyl-2,2′-bipyridine (4,4′-Me2-2,2′-bpy), 5,5′-dimethyl-2,2′-bipyridine (5,5′-Me2-2,2′-bpy) and cis- and trans- mixture of 1,4-cyclohexanedicarboxylic acid (H21,4-chdc). Hirshfeld analysis is employed to validate non-bonded interactions, demonstrating the existence of widespread π···π stacking interactions between adjacent 4,4′-Me2-2,2′-bpy ligands at a distance of 3.757 Å, forming a one-dimensional (1D) supramolecular polymer chain. The biological activity of complex 1 is explored via docking study, driven by the inherent biological inclination of the Cu(II) complexes. Agreeably, the coordination complex 1 displays a favorable binding to DNA, specifically binds to the major groove of DNA and the aromatic pyridine ring of the ligand partially intercalates into the base pairs with a binding constant (Kb) of 1.98 × 105 M−1.
{"title":"Synthesis, structural elucidation, and DNA binding behavior of a ternary copper(II) complex featuring substituted bipyridyl and dicarboxylate ligands","authors":"Sk Khalid Rahaman , Taposi Chatterjee , Kalamoddin Shaikh , Samim Khan , Masoom Raza Siddiqui , Saikh M. Wabaidur , Md Maidul Islam , Seikh Mafiz Alam , Mohammad Hedayetullah Mir","doi":"10.1016/j.poly.2024.117318","DOIUrl":"10.1016/j.poly.2024.117318","url":null,"abstract":"<div><div>The present research study is centered around the synthesis, characterization, and biological application of a ternary mixed-ligand based binuclear Cu(II) complex [Cu<sub>2</sub>(<em>trans</em>-1,4-chdc)(4,4′-Me<sub>2</sub>-2,2′-bpy)<sub>2</sub>(5,5′-Me<sub>2</sub>-2,2′-bpy)<sub>2</sub>]·2(<em>cis</em>-H<sub>2</sub>1,4-chdc)·2(BF<sub>4</sub>¯) (<strong>1</strong>) by meticulous incorporation of 4,4′-dimethyl-2,2′-bipyridine (4,4′-Me<sub>2</sub>-2,2′-bpy), 5,5′-dimethyl-2,2′-bipyridine (5,5′-Me<sub>2</sub>-2,2′-bpy) and <em>cis</em>- and<!--> <em>trans</em>- mixture of 1,4-cyclohexanedicarboxylic acid (H<sub>2</sub>1,4-chdc). Hirshfeld analysis is employed to validate non-bonded interactions, demonstrating the existence of widespread π···π stacking interactions between adjacent 4,4′-Me<sub>2</sub>-2,2′-bpy ligands at a distance of 3.757 Å, forming a one-dimensional (1D) supramolecular polymer chain. The biological activity of complex <strong>1</strong> is explored via docking study, driven by the inherent biological inclination of the Cu(II) complexes. Agreeably, the coordination complex <strong>1</strong> displays a favorable binding to DNA, specifically binds to the major groove of DNA and the aromatic pyridine ring of the ligand partially intercalates into the base pairs with a binding constant (<em>K<sub>b</sub></em>) of 1.98 × 10<sup>5</sup> M<sup>−1</sup>.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"266 ","pages":"Article 117318"},"PeriodicalIF":2.4,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142702862","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 : 2024-11-26DOI: 10.1016/j.poly.2024.117320
Jawher Makhlouf , Youness El Bakri , Chin-Hung Lai , Arto Valkonen , Hatem A. Abuelizz , Rashad Al-Salahi , Wajda Smirani Sta
The cobalt (II) complexes have been synthesized from the reaction of the cationic entities (1-(2-methoxyphenyl) piperazine and the 1-(4-nitrophenyl) piperazine with metallic salt CoCl2·6H2O, then processing the evaporation crystal growth method at room temperature. The synthesized complexes have been fully characterized by single crystal X-ray diffraction, Hirshfeld surface analysis, as well as UV–visible, FTIR spectroscopy, Photoluminescence, and TGA/TDA analysis, and theoretical studies were also performed, in addition to the antioxidant DPPH+ radical and ABTS+ radical cation assays were performed. The crystal structural analysis reveals that both complexes crystallize in the orthorhombic system. The vibrational absorption bands were identified by infrared spectroscopy. The solid-state UV–visible absorption spectrum of the title compounds was obtained at room temperature to spotlight the optical properties. In the [300–700 K] range, the thermal behaviors were investigated and showed the decomposition of the two complexes with metal complexes residues. Hirshfeld surface analysis cum 2D fingerprint plots visualize the main intermolecular interactions with their contributions in the solid-state phase. The molecular geometries of both complexes obtained from the crystal structure were used for quantum chemical calculation. DPPH+ radical and ABTS+ radical cation assays were used to highlight the interesting antioxidant activity for both complexes, where the IC50 of compound (1) was greater than 45 mg.mL−1 and it was greater than 49 mg.mL−1 for compound (2). The anticancer activities of the complexes studied were also investigated in silico by molecular docking.
{"title":"Highlighting non-covalent interactions to molecular structure, electronic and vibrational spectra in a new hybrid organic–inorganic cobalt complexes: Synthesis, characterization, experimental and computational studies","authors":"Jawher Makhlouf , Youness El Bakri , Chin-Hung Lai , Arto Valkonen , Hatem A. Abuelizz , Rashad Al-Salahi , Wajda Smirani Sta","doi":"10.1016/j.poly.2024.117320","DOIUrl":"10.1016/j.poly.2024.117320","url":null,"abstract":"<div><div>The cobalt (II) complexes have been synthesized from the reaction of the cationic entities (1-(2-methoxyphenyl) piperazine and the 1-(4-nitrophenyl) piperazine with metallic salt CoCl<sub>2</sub>·6H<sub>2</sub>O, then processing the evaporation crystal growth method at room temperature. The synthesized complexes have been fully characterized by single crystal X-ray diffraction, Hirshfeld surface analysis, as well as UV–visible, FTIR spectroscopy, Photoluminescence, and TGA/TDA analysis, and theoretical studies were also performed, in addition to the antioxidant DPPH<sup><img>+</sup> <!-->radical and ABTS<sup><img>+</sup> <!-->radical cation assays were performed. The crystal structural analysis reveals that both complexes crystallize in the orthorhombic system. The vibrational absorption bands were identified by infrared spectroscopy. The solid-state UV–visible absorption spectrum of the title compounds was obtained at room temperature to spotlight the optical properties. In the [300–700 K] range, the thermal behaviors were investigated and showed the decomposition of the two complexes with metal complexes residues. Hirshfeld surface analysis cum 2D fingerprint plots visualize the main intermolecular interactions with their contributions in the solid-state phase. The molecular geometries of both complexes obtained from the crystal structure were used for quantum chemical calculation. DPPH<sup><img>+</sup> <!-->radical and ABTS<sup><img>+</sup> <!-->radical cation assays were used to highlight the interesting antioxidant activity for both complexes, where the IC<sub>50</sub> <!-->of compound (<strong>1</strong>) was greater than 45 mg.mL<sup>−1</sup> <!-->and it was greater than 49 mg.mL<sup>−1</sup> for compound (<strong>2</strong>). The anticancer activities of the complexes studied were also investigated in silico by molecular docking.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"266 ","pages":"Article 117320"},"PeriodicalIF":2.4,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142721119","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 : 2024-11-26DOI: 10.1016/j.poly.2024.117316
Hatice Gamze Sogukomerogullari , Emine Aytar
SNS pincer type ligands (L1-L4) were metallized with RhCl(PPh3)3, yielding new SNS type Rh(I) complexes. Different techniques, including 31P NMR, UV–Vis, XPS, mass, elemental analysis, molar conductivity, and FT-IR were used to analyze the synthesized compounds. According to the spectral data, the molecular structure of Rh(I) complexes has a four-coordinated square planar geometry around the metal center. The complexes’ lack of conductivity properties demonstrates their non-electrolyte nature in solution. The novel SNS-type Rh(I) complexes efficiently catalyzed the coupling of a variety of epoxides and CO2 to create cyclic carbonates in the presence of DMAP as a Lewis base. Diverse cyclic carbonates were also synthesized under ideal conditions with good to perfect yields (2 h, 1.6 MPa, and 100 °C). Following the discovery of new SNS-type Rh(I) catalysts with outstanding catalytic performance, epoxide, the impact of the reaction time, base, CO2 pressure, and temperature was examined for these catalysts. The complex L3-Rh and DMAP displayed the highest catalytic activity (89.6 %) and selectivity (99.4 %) for the coupling of CO2 and ECH under optimum conditions (100 °C, 2 h, and 1.6 MPa).
{"title":"Assessment of four rhodium(I) complexes bearing SNS ligands for the catalytic reaction of chemical CO2 conversion to obtain cyclic carbonates","authors":"Hatice Gamze Sogukomerogullari , Emine Aytar","doi":"10.1016/j.poly.2024.117316","DOIUrl":"10.1016/j.poly.2024.117316","url":null,"abstract":"<div><div>SNS pincer type ligands (L1-L4) were metallized with RhCl(PPh<sub>3</sub>)<sub>3</sub>, yielding new SNS type Rh(I) complexes. Different techniques, including <sup>31</sup>P NMR, UV–Vis, XPS, mass, elemental analysis, molar conductivity, and FT-IR were used to analyze the synthesized compounds. According to the spectral data, the molecular structure of Rh(I) complexes has a four-coordinated square planar geometry around the metal center.<!--> <!-->The complexes’ lack of conductivity properties demonstrates their non-electrolyte nature in solution. The novel SNS-type Rh(I) complexes efficiently catalyzed the coupling of a variety of epoxides and CO<sub>2</sub> to create cyclic carbonates in the presence of DMAP as a Lewis base. Diverse cyclic carbonates were also synthesized under ideal conditions with good to perfect yields (2 h, 1.6 MPa, and 100 °C). Following the discovery of new SNS-type Rh(I) catalysts with outstanding catalytic performance, epoxide, the impact of the reaction time, base, CO<sub>2</sub> pressure, and temperature was examined for these catalysts. The complex <strong>L3-Rh</strong> and DMAP displayed the highest catalytic activity (89.6 %) and selectivity (99.4 %) for the coupling of CO<sub>2</sub> and ECH under optimum conditions (100 °C, 2 h, and 1.6 MPa).</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"267 ","pages":"Article 117316"},"PeriodicalIF":2.4,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142756854","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 : 2024-11-22DOI: 10.1016/j.poly.2024.117313
Joaldo G. Arruda , Iran F. Silva , Wagner M. Faustino , Israel F. Costa , Hermi F. Brito , Albano N. Carneiro Neto , Christian Näther , Huayna Terraschke , Maria Cláudia F.C. Felinto , Victor M. Deflon , Ercules E.S. Teotonio
Three novel lanthanide dipivaloylmethanate (dpm) complexes of general formula [Ln(dpm)(NO3)2(tchpo)2], where Ln: Eu3+, Gd3+ and Tb3+, and tchpo: tricyclohexylphosphine oxide neutral ligand have been prepared and characterized by elemental analyses, absorption infrared spectroscopy, thermalgravimetric analyses, diffuse reflectance, and luminescence spectroscopies. Furthermore, the [Tb(dpm)(NO3)2(tchpo)2] complex was structurally characterized by the single crystal X-ray diffraction analysis. This complex exhibited high luminescence intensity in the green region. On the other hand, the analogous Eu3+-complex exhibited very low luminescence intensity due to an efficient luminescent quenching process via ligand-to-metal charge transfer (LMCT) state. Theoretical studies employing Time-Dependent Density Functional Theory (TD-DFT) calculations along with results obtained from the JOYSpectra platform, support this experimental result. Remarkably, despite the high values of non-radiative intramolecular energy transfer from excited ligand states (S1 and T1) to the excited levels of the Ln3+ ions, in the [Eu(dpm)(NO3)2(tchpo)2], the highest S1-LMCT rate (W = 1.2 × 1010 s−1) emphasizes that the primary luminescence quenching pathway is via depopulation of excited ligand states. Interestingly, the nitrogen atoms from nitrate ions play an essential role in the lanthanide chemical environment, which has been suggested by the analyses of the ligand field parameters charge factors () and effective polarizabilities () values.
{"title":"Luminescence in Ln3+ dipivaloylmethanate complexes: Spectroscopic and theoretical investigation on the energy transfer and LMCT state","authors":"Joaldo G. Arruda , Iran F. Silva , Wagner M. Faustino , Israel F. Costa , Hermi F. Brito , Albano N. Carneiro Neto , Christian Näther , Huayna Terraschke , Maria Cláudia F.C. Felinto , Victor M. Deflon , Ercules E.S. Teotonio","doi":"10.1016/j.poly.2024.117313","DOIUrl":"10.1016/j.poly.2024.117313","url":null,"abstract":"<div><div>Three novel lanthanide dipivaloylmethanate (dpm) complexes of general formula [Ln(dpm)(NO<sub>3</sub>)<sub>2</sub>(tchpo)<sub>2</sub>], where Ln: Eu<sup>3+</sup>, Gd<sup>3+</sup> and Tb<sup>3+</sup>, and tchpo: tricyclohexylphosphine oxide neutral ligand have been prepared and characterized by elemental analyses, absorption infrared spectroscopy, thermalgravimetric analyses, diffuse reflectance, and luminescence spectroscopies. Furthermore, the [Tb(dpm)(NO<sub>3</sub>)<sub>2</sub>(tchpo)<sub>2</sub>] complex was structurally characterized by the single crystal X-ray diffraction analysis. This complex exhibited high luminescence intensity in the green region. On the other hand, the analogous Eu<sup>3+</sup>-complex exhibited very low luminescence intensity due to an efficient luminescent quenching process <em>via</em> ligand-to-metal charge transfer (LMCT) state. Theoretical studies employing Time-Dependent Density Functional Theory (TD-DFT) calculations along with results obtained from the JOYSpectra platform, support this experimental result. Remarkably, despite the high values of non-radiative intramolecular energy transfer from excited ligand states (S<sub>1</sub> and T<sub>1</sub>) to the excited levels of the Ln<sup>3+</sup> ions, in the [Eu(dpm)(NO<sub>3</sub>)<sub>2</sub>(tchpo)<sub>2</sub>], the highest S<sub>1</sub>-LMCT rate (W = 1.2 × 10<sup>10</sup> s<sup>−1</sup>) emphasizes that the primary luminescence quenching pathway is <em>via</em> depopulation of excited ligand states. Interestingly, the nitrogen atoms from nitrate ions play an essential role in the lanthanide chemical environment, which has been suggested by the analyses of the ligand field parameters charge factors (<span><math><mrow><mi>g</mi></mrow></math></span>) and effective polarizabilities (<span><math><mrow><mi>α</mi><mo>′</mo></mrow></math></span>) values.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"267 ","pages":"Article 117313"},"PeriodicalIF":2.4,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747948","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 : 2024-11-20DOI: 10.1016/j.poly.2024.117307
Pierre Thuéry , Youssef Atoini , Jack Harrowfield
2,5-Thiophenedicarboxylic acid (H2tdc) has been reacted with uranyl nitrate hexahydrate under solvo-hydrothermal conditions with N,N-dimethylacetamide (dma) as an organic cosolvent, giving the complex [UO2(tdc)(dma)] (1), isomorphous to the previously reported [UO2(tdc)(nmp)] (nmp = N-methyl-2-pyrrolidone). With tdc2− adopting the bis(μ2-κ1O:κ1O’)-bridging coordination mode, complex 1 crystallizes as a triperiodic framework with the point symbol {42.84}. With acetonitrile as an organic cosolvent and in the presence of [Ni(PPh3)2Br2], triphenylphosphine oxide is formed in situ and it binds to uranyl to give [UO2(tdc)(OPPh3)] (2). Complex 2 is also a triperiodic framework, with the point symbol {4.102}2{42.104} and the dmd topological type with uranium as 3-coordinated (3-c) nodes and tdc2− as either a 4-c node in its bis(μ2-κ1O:κ1O’)-bridging mode, or a simple edge in the bis(κ2O,O’)-chelating mode. In both 1 and 2, as in the previously described nmp complex, but not in [UO2(tdc)(dmf)] (dmf = N,N-dimethylformamide), coordination of a unidentate ligand disrupts the most common formation of diperiodic networks with tdc2− and tris-chelated uranyl, and promotes formation of frameworks in which channels accommodate the pendant, unidentate ligands. Complex 2 has a photoluminescence quantum yield of 3 % in the solid state, and its emission spectrum displays the typical vibronic progression with peak positions in the range usual for complexes with an O5 equatorial uranyl environment; the “hot band” observed at room temperature disappears at 77 K.
{"title":"Triperiodic frameworks in the uranyl–2,5-thiophenedicarboxylate system: Effect of unidentate auxiliary ligands","authors":"Pierre Thuéry , Youssef Atoini , Jack Harrowfield","doi":"10.1016/j.poly.2024.117307","DOIUrl":"10.1016/j.poly.2024.117307","url":null,"abstract":"<div><div>2,5-Thiophenedicarboxylic acid (H<sub>2</sub>tdc) has been reacted with uranyl nitrate hexahydrate under solvo-hydrothermal conditions with <em>N,N</em>-dimethylacetamide (dma) as an organic cosolvent, giving the complex [UO<sub>2</sub>(tdc)(dma)] (<strong>1</strong>), isomorphous to the previously reported [UO<sub>2</sub>(tdc)(nmp)] (nmp = <em>N</em>-methyl-2-pyrrolidone). With tdc<sup>2−</sup> adopting the bis(μ<sub>2</sub>-κ<sup>1</sup><em>O</em>:κ<sup>1</sup><em>O’</em>)-bridging coordination mode, complex <strong>1</strong> crystallizes as a triperiodic framework with the point symbol {4<sup>2</sup>.8<sup>4</sup>}. With acetonitrile as an organic cosolvent and in the presence of [Ni(PPh<sub>3</sub>)<sub>2</sub>Br<sub>2</sub>], triphenylphosphine oxide is formed <em>in situ</em> and it binds to uranyl to give [UO<sub>2</sub>(tdc)(OPPh<sub>3</sub>)] (<strong>2</strong>). Complex <strong>2</strong> is also a triperiodic framework, with the point symbol {4.10<sup>2</sup>}<sub>2</sub>{4<sup>2</sup>.10<sup>4</sup>} and the <strong>dmd</strong> topological type with uranium as 3-coordinated (3-c) nodes and tdc<sup>2−</sup> as either a 4-c node in its bis(μ<sub>2</sub>-κ<sup>1</sup><em>O</em>:κ<sup>1</sup><em>O’</em>)-bridging mode, or a simple edge in the bis(κ<sup>2</sup><em>O</em>,<em>O’</em>)-chelating mode. In both <strong>1</strong> and <strong>2</strong>, as in the previously described nmp complex, but not in [UO<sub>2</sub>(tdc)(dmf)] (dmf = <em>N,N</em>-dimethylformamide), coordination of a unidentate ligand disrupts the most common formation of diperiodic networks with tdc<sup>2−</sup> and tris-chelated uranyl, and promotes formation of frameworks in which channels accommodate the pendant, unidentate ligands. Complex <strong>2</strong> has a photoluminescence quantum yield of 3 % in the solid state, and its emission spectrum displays the typical vibronic progression with peak positions in the range usual for complexes with an O<sub>5</sub> equatorial uranyl environment; the “hot band” observed at room temperature disappears at 77 K.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"266 ","pages":"Article 117307"},"PeriodicalIF":2.4,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142702194","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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