Inorganica Chimica Acta最新文献

英文中文

Synthesis, photophysical properties and DFT calculation of four novel iridium(III) complexes based on dibenzothiophene

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2025-01-23 DOI: 10.1016/j.ica.2025.122562

Mengyun Wang , Boyang Cheng , Mengting Zhao , Sijia Yang , Tianjiao Hou , Xuan Shen

To investigate the DR/NIR luminescent properties of iridium complexes enlarging by the conjugation of 2-phenylpyridine (ppy), and to assess the substituent effects on the characteristics of iridium complexes, we employed 5-R-2-(dibenzo[b,d]thiophen-3-yl)pyridine (R = -H, F, -CF₃, and -CH₃) as the primary ligand in the design and synthesis of four novel iridium(III) complexes. Single-crystal X-ray structures verified the definitive coordination geometry as well as the intramolecular and intermolecular interactions present in Ir2-Ir4. Subsequent to the incorporation of dibenzothiophene into the primary ligand, Ir1(H) exhibits a redshift compared to Ir(ppy)₂tmd. It is proposed that the slight redshift may be attributed to changes in the electron cloud distribution resulting from structural modifications to the ligand. Besides, Ir3 (-CF₃) and Ir2 (F) show a bathochromic relative to Ir1 (H), while Ir4 (-CH₃) leads to a minor blueshift. These results are in consistent with density functional theory (DFT) calculations. This study highlights the crucial role of ligand structure in influencing the photophysical properties of iridium(III) complexes, potentially offering new avenues for their design and synthesis.

{"title":"Synthesis, photophysical properties and DFT calculation of four novel iridium(III) complexes based on dibenzothiophene","authors":"Mengyun Wang , Boyang Cheng , Mengting Zhao , Sijia Yang , Tianjiao Hou , Xuan Shen","doi":"10.1016/j.ica.2025.122562","DOIUrl":"10.1016/j.ica.2025.122562","url":null,"abstract":"<div><div>To investigate the DR/NIR luminescent properties of iridium complexes enlarging by the conjugation of 2-phenylpyridine (ppy), and to assess the substituent effects on the characteristics of iridium complexes, we employed 5-R-2-(dibenzo[b,d]thiophen-3-yl)pyridine (R = -H, <img>F, -CF3, and -CH3) as the primary ligand in the design and synthesis of four novel iridium(III) complexes. Single-crystal X-ray structures verified the definitive coordination geometry as well as the intramolecular and intermolecular interactions present in Ir2-Ir4. Subsequent to the incorporation of dibenzothiophene into the primary ligand, Ir1(<img>H) exhibits a redshift compared to Ir(ppy)2tmd. It is proposed that the slight redshift may be attributed to changes in the electron cloud distribution resulting from structural modifications to the ligand. Besides, Ir3 (-CF3) and Ir2 (<img>F) show a bathochromic relative to Ir1 (<img>H), while Ir4 (-CH3) leads to a minor blueshift. These results are in consistent with density functional theory (DFT) calculations. This study highlights the crucial role of ligand structure in influencing the photophysical properties of iridium(III) complexes, potentially offering new avenues for their design and synthesis.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"579 ","pages":"Article 122562"},"PeriodicalIF":2.7,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143353677","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}

引用次数: 0

Dinuclear Nickel (II) 2,2′-Bibenzimidazole Bridged Complexes: Synthesis, Structure, Magnetic, and Electrochemical Properties

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2025-01-23 DOI: 10.1016/j.ica.2025.122555

Alexey A. Kagilev , Zufar N. Gafurov , Artem S. Evdokimov , Il’yas F. Sakhapov , Alexey B. Dobrynin , Vladimir I. Morozov , Ruslan B. Zaripov , Ekaterina M. Zueva , Artem S. Bogomyakov , Artyom O. Kantyukov , Nataliya A. Zhukova , Oleg G. Sinyashin , Vakhid A. Mamedov , Dmitry G. Yakhvarov

The reaction of [NiBr₂(bpy)₂] (bpy = 2,2′-bipyridine) with 2,2′-bibenzimidazole or 5,5′,6,6′-tetramethyl-2,2′-bibenzimidazole (bbim) in the presence of AgBF₄ and Et₃N results in the formation of dinuclear nickel(II) complexes with bridging bbim ligands. The crystal structures of the obtained complexes [Ni₂(μ-bbim)(bpy)₄][(BF₄)₂] have been determined. Variable-temperature EPR as well as magnetometry experiments indicate antiferromagnetic interactions between the nickel atoms in the complex molecule at low temperatures. Density functional theory (DFT) calculations confirm these findings. Cyclic voltammetry and in situ EPR spectroelectrochemistry demonstrated that these complexes can be electrochemically reduced resulting in the formation of Ni(I) and Ni(0) derivatives. This can be considered as a strategy for controlling the electronic state of these dinuclear nickel complexes, thus providing a way to design magnetic materials with switchable properties.

{"title":"Dinuclear Nickel (II) 2,2′-Bibenzimidazole Bridged Complexes: Synthesis, Structure, Magnetic, and Electrochemical Properties","authors":"Alexey A. Kagilev , Zufar N. Gafurov , Artem S. Evdokimov , Il’yas F. Sakhapov , Alexey B. Dobrynin , Vladimir I. Morozov , Ruslan B. Zaripov , Ekaterina M. Zueva , Artem S. Bogomyakov , Artyom O. Kantyukov , Nataliya A. Zhukova , Oleg G. Sinyashin , Vakhid A. Mamedov , Dmitry G. Yakhvarov","doi":"10.1016/j.ica.2025.122555","DOIUrl":"10.1016/j.ica.2025.122555","url":null,"abstract":"<div><div>The reaction of [NiBr2(bpy)2] (bpy = 2,2′-bipyridine) with 2,2′-bibenzimidazole or 5,5′,6,6′-tetramethyl-2,2′-bibenzimidazole (bbim) in the presence of AgBF4 and Et3N results in the formation of dinuclear nickel(II) complexes with bridging bbim ligands. The crystal structures of the obtained complexes [Ni2(μ-bbim)(bpy)4][(BF4)2] have been determined. Variable-temperature EPR as well as magnetometry experiments indicate antiferromagnetic interactions between the nickel atoms in the complex molecule at low temperatures. Density functional theory (DFT) calculations confirm these findings. Cyclic voltammetry and in situ EPR spectroelectrochemistry demonstrated that these complexes can be electrochemically reduced resulting in the formation of Ni(I) and Ni(0) derivatives. This can be considered as a strategy for controlling the electronic state of these dinuclear nickel complexes, thus providing a way to design magnetic materials with switchable properties.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"579 ","pages":"Article 122555"},"PeriodicalIF":2.7,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143303712","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}

引用次数: 0

Synthesis, structure, physico-chemical properties and biological activity of copper(II) ketoiminate complexes derived from N-naphthyl- and N-quinolyl-β-aminovinyl ketones

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2025-01-23 DOI: 10.1016/j.ica.2025.122560

Ali I. Uraev , Milica R. Milenković , Valery G. Vlasenko , Konstantin A. Lyssenko , Oleg P. Demidov , Anastasia A. Shiryaeva , Michael P. Bubnov , Pavel A. Knyazev , Dmitrii A. Garnovskii , Anatolii S. Burlov , Alexander A. Zubenko

Four novel copper(II) complexes of N-quinolyl or N-naphthyl substituted β-aminovinyl ketones, derivatives of either benzoylacetaldehyde or benzoylacetone were synthesized. Their structures and physico-chemical properties were studied using single-crystal XRD analysis, XANES and EXAFS, IR, EPR, and UV–Vis spectroscopy, magnetic measurements, and DFT calculations. All investigated metal chelates have the ML₂ composition. The square-planar coordination geometry in the N-naphthyl substituted copper(II) ketoiminate complexes is formed by bidentate NO coordination of the deprotonated β-aminovinyl ketones. Both copper(II) N-quinolyl substituted ketoiminate complexes have square-pyramidal coordination geometry with one of two deprotonated β-aminovinyl ketone ligands coordinated as NNO tridentate. In the copper(II) complex of N-quinolyl substituted β-aminovinyl ketone derived from benzoylacetaldehyde, the remaining coordination sites are occupied with the enamine and quinoline nitrogen atoms of the second ligand. On the other hand, in the copper(II) complex prepared from its β-methyl derivative the second ligand coordinates through the azomethine nitrogen and the enamine ketone oxygen. Antibacterial, antifungal, and protistocidal activity of compounds was tested. The β-methyl substituted N-quinolyl-β-aminovinyl ketone and its copper(II) complex exhibit the most pronounced biological activity.

{"title":"Synthesis, structure, physico-chemical properties and biological activity of copper(II) ketoiminate complexes derived from N-naphthyl- and N-quinolyl-β-aminovinyl ketones","authors":"Ali I. Uraev , Milica R. Milenković , Valery G. Vlasenko , Konstantin A. Lyssenko , Oleg P. Demidov , Anastasia A. Shiryaeva , Michael P. Bubnov , Pavel A. Knyazev , Dmitrii A. Garnovskii , Anatolii S. Burlov , Alexander A. Zubenko","doi":"10.1016/j.ica.2025.122560","DOIUrl":"10.1016/j.ica.2025.122560","url":null,"abstract":"<div><div>Four novel copper(II) complexes of N-quinolyl or N-naphthyl substituted β-aminovinyl ketones, derivatives of either benzoylacetaldehyde or benzoylacetone were synthesized. Their structures and physico-chemical properties were studied using single-crystal XRD analysis, XANES and EXAFS, IR, EPR, and UV–Vis spectroscopy, magnetic measurements, and DFT calculations. All investigated metal chelates have the ML2 composition. The square-planar coordination geometry in the N-naphthyl substituted copper(II) ketoiminate complexes is formed by bidentate NO coordination of the deprotonated β-aminovinyl ketones. Both copper(II) N-quinolyl substituted ketoiminate complexes have square-pyramidal coordination geometry with one of two deprotonated β-aminovinyl ketone ligands coordinated as NNO tridentate. In the copper(II) complex of N-quinolyl substituted β-aminovinyl ketone derived from benzoylacetaldehyde, the remaining coordination sites are occupied with the enamine and quinoline nitrogen atoms of the second ligand. On the other hand, in the copper(II) complex prepared from its β-methyl derivative the second ligand coordinates through the azomethine nitrogen and the enamine ketone oxygen. Antibacterial, antifungal, and protistocidal activity of compounds was tested. The β-methyl substituted N-quinolyl-β-aminovinyl ketone and its copper(II) complex exhibit the most pronounced biological activity.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"579 ","pages":"Article 122560"},"PeriodicalIF":2.7,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143303670","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}

引用次数: 0

Molecular complexes of iodine with pyrazine and 4,4’-bipyridine: Structure, bonding and thermal stability

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2025-01-23 DOI: 10.1016/j.ica.2025.122564

Elena I. Davydova, Alena N. Antonova, Anna V. Shevchenko, Dar’ya V. Spiridonova, Artem S. Zavgorodnii, Dmitrii A. Doinikov, Elizaveta I. Kondrashkina, Mariya A. Kryukova, Anna V. Pomogaeva, Alexey Y. Timoshkin

Results of the joint experimental and computational studies of structural features, bonding and thermodynamic properties of molecular complexes of iodine with bidentate nonchelated N-containing donors pyrazine and 4,4′-bipyridine are reported. Irrespective of the starting ratio of the components, complexes of 2:1 composition are predominantly formed in the solid state. Molecular structures of new molecular complex of I₂ with pyrazine and a new polymorph of complex of 4,4′-bipyridine of 2:1 composition have been determined by single crystal structural analysis. In both complexes, ligand serves as bifunctional donor connecting two molecules of I₂. All IN distances are shorter than the sum of van der Waals radii and the I-I-N angles are close to 180°. To reveal the stability of the complexes of different compositions and the nature of NI bond, the DFT computations were performed. Stability and volatility of compounds upon heating in vacuum were studied using static tensimetry method with membrane null-manometer. Thermodynamic characteristics of the complex dissociation processes were estimated.

{"title":"Molecular complexes of iodine with pyrazine and 4,4’-bipyridine: Structure, bonding and thermal stability","authors":"Elena I. Davydova, Alena N. Antonova, Anna V. Shevchenko, Dar’ya V. Spiridonova, Artem S. Zavgorodnii, Dmitrii A. Doinikov, Elizaveta I. Kondrashkina, Mariya A. Kryukova, Anna V. Pomogaeva, Alexey Y. Timoshkin","doi":"10.1016/j.ica.2025.122564","DOIUrl":"10.1016/j.ica.2025.122564","url":null,"abstract":"<div><div>Results of the joint experimental and computational studies of structural features, bonding and thermodynamic properties of molecular complexes of iodine with bidentate nonchelated N-containing donors pyrazine and 4,4′-bipyridine are reported. Irrespective of the starting ratio of the components, complexes of 2:1 composition are predominantly formed in the solid state. Molecular structures of new molecular complex of I2 with pyrazine and a new polymorph of complex of 4,4′-bipyridine of 2:1 composition have been determined by single crystal structural analysis. In both complexes, ligand serves as bifunctional donor connecting two molecules of I2. All I<img>N distances are shorter than the sum of van der Waals radii and the I-I-N angles are close to 180°. To reveal the stability of the complexes of different compositions and the nature of N<img>I bond, the DFT computations were performed. Stability and volatility of compounds upon heating in vacuum were studied using static tensimetry method with membrane null-manometer. Thermodynamic characteristics of the complex dissociation processes were estimated.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"579 ","pages":"Article 122564"},"PeriodicalIF":2.7,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143303706","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}

引用次数: 0

N-Amidothiourea fluorescence sensor for sensitive detection of Zn2+ ions and cell imaging: A tool for plasma membrane analysis

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2025-01-21 DOI: 10.1016/j.ica.2025.122551

Kaitlin Ricks , Muneeb Akhtar , Sergio Mendez , Crystal Liu , Ian Lian , Zhi-Fo Guo

We present the development of an innovative “turn-on” fluorescent chemosensor, L1, specifically designed for the selective detection of Zn²⁺ ions in biological settings. L1 exhibited enhanced fluorescence upon the addition of both Zn²⁺ and Cd²⁺ ions, with compositional analysis revealing a 2:1 ligand-to-Zn²⁺ stoichiometry. The chemosensor demonstrated significant selectivity for Zn²⁺, effectively minimizing interference from other metal ions, particularly heavy metals. Comprehensive characterization techniques, including FT-IR, ¹H NMR, mass spectrometry (MS), and Density Functional Theory (DFT) calculations, confirmed the formation and binding mechanism of the complex. Notably, fluorescence intensity was optimized at a pH range of 7.0 to 7.5, aligning with physiological conditions. Imaging studies using HEK293 cells validated the chemosensor’s capability to visualize Zn²⁺, primarily at the plasma membrane, highlighting its potential as a valuable tool in cellular signaling research. This study emphasizes the potential of N-amidothiourea-based fluorescent sensors in the exploration of Zn²⁺ dynamics in biological systems.

{"title":"N-Amidothiourea fluorescence sensor for sensitive detection of Zn2+ ions and cell imaging: A tool for plasma membrane analysis","authors":"Kaitlin Ricks , Muneeb Akhtar , Sergio Mendez , Crystal Liu , Ian Lian , Zhi-Fo Guo","doi":"10.1016/j.ica.2025.122551","DOIUrl":"10.1016/j.ica.2025.122551","url":null,"abstract":"<div><div>We present the development of an innovative “turn-on” fluorescent chemosensor, L1, specifically designed for the selective detection of Zn2+ ions in biological settings. L1 exhibited enhanced fluorescence upon the addition of both Zn2+ and Cd2+ ions, with compositional analysis revealing a 2:1 ligand-to-Zn2+ stoichiometry. The chemosensor demonstrated significant selectivity for Zn2+, effectively minimizing interference from other metal ions, particularly heavy metals. Comprehensive characterization techniques, including FT-IR, 1H NMR, mass spectrometry (MS), and Density Functional Theory (DFT) calculations, confirmed the formation and binding mechanism of the complex. Notably, fluorescence intensity was optimized at a pH range of 7.0 to 7.5, aligning with physiological conditions. Imaging studies using HEK293 cells validated the chemosensor’s capability to visualize Zn2+, primarily at the plasma membrane, highlighting its potential as a valuable tool in cellular signaling research. This study emphasizes the potential of N-amidothiourea-based fluorescent sensors in the exploration of Zn2+ dynamics in biological systems.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"578 ","pages":"Article 122551"},"PeriodicalIF":2.7,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143347207","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}

引用次数: 0

Cobalt nanoparticle catalyzed synthesis of α-thio-β-diketones via aerobic oxidative CS Cross-Coupling

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2025-01-20 DOI: 10.1016/j.ica.2025.122558

Ning Wang , Ya-Fei Guo , Feng-Min Wu , Sajid Mahmood , Jie Luo , Kun Liu , Le Dong , Wen-Xuan Liang , Hao-Yan Xu , Shu-Xiao Feng , Jun-Ying Ma

Cobalt nanoparticle-supported on nitrogen-doped mesoporous carbon derived from metal ionic liquids have been developed as heterogeneous catalysts for aerobic oxidative CS cross-coupling. This catalytic system allows the smooth conversion of various thiols and acetylacetones to corresponding α-thio-β-diketone derivatives under mild conditions. The preparation of the catalyst is simple and convenient, and it can be recycled for six times with negligible loss of activity. The cobalt nanoparticles were identified as catalytic active sites by catalyst characterisation and controlled experiments. Preliminary mechanistic studies suggest a radical mechanism with disulfides as intermediates.

引用次数: 0

Syntheses, crystal structures, and magnetic properties of three [Fe2Co2] cyanidometallate squares

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2025-01-20 DOI: 10.1016/j.ica.2025.122552

Qiuyue Cao , Jing Xi , Tingting Xu , Binling Yao , Dong Shao , Yi-Fei Deng , Yuan-Zhu Zhang

Three cyanido-bridged square complexes, (1, with X = [BF₄]⁻ and sol = 4MeOH; 2, with X = [ClO₄]⁻ and sol = 2H₂O·2.5MeCN; 3, with X = [PF₆]⁻ and sol = 4MeOH; where Tp* denotes hydrotris(3,5-dimethylpyrazol-1-yl)borate; PyPz₃ = 2-(di(1H-pyrazol-1-yl)methyl)-6(1H-pyrazol-1-yl)pyridine), were successfully constructed and characterized structurally and magnetically. Single crystal diffraction revealed that the changes in the counterions led to alterations in symmetry and coordination environment of the central metal ions, affecting crystal packing and intermolecular metal distances. Magnetic studies revealed that three complexes exhibit ferromagnetic interactions between the cyanide bridged Fe^III and Co^II ions, with exchange coupling constant of +4.67, +5.35 and +3.93 cm⁻¹, respectively. This study provides an insight into the relationship between changes in the coordination environment caused by counterions and magnetic properties.

{"title":"Syntheses, crystal structures, and magnetic properties of three [Fe2Co2] cyanidometallate squares","authors":"Qiuyue Cao , Jing Xi , Tingting Xu , Binling Yao , Dong Shao , Yi-Fei Deng , Yuan-Zhu Zhang","doi":"10.1016/j.ica.2025.122552","DOIUrl":"10.1016/j.ica.2025.122552","url":null,"abstract":"<div><div>Three cyanido-bridged square complexes, (1, with X = [BF4]− and sol = 4MeOH; 2, with X = [ClO4]− and sol = 2H2O·2.5MeCN; 3, with X = [PF6]− and sol = 4MeOH; where Tp* denotes hydrotris(3,5-dimethylpyrazol-1-yl)borate; PyPz3 = 2-(di(1H-pyrazol-1-yl)methyl)-6(1H-pyrazol-1-yl)pyridine), were successfully constructed and characterized structurally and magnetically. Single crystal diffraction revealed that the changes in the counterions led to alterations in symmetry and coordination environment of the central metal ions, affecting crystal packing and intermolecular metal distances. Magnetic studies revealed that three complexes exhibit ferromagnetic interactions between the cyanide bridged FeIII and CoII ions, with exchange coupling constant of +4.67, +5.35 and +3.93 cm−1, respectively. This study provides an insight into the relationship between changes in the coordination environment caused by counterions and magnetic properties.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"579 ","pages":"Article 122552"},"PeriodicalIF":2.7,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143303377","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}

引用次数: 0

Kinetics and mechanism of the reactions of alkanediamine-linked dinuclear platinum(II) complexes with some biorelevant-nucleophiles

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2025-01-19 DOI: 10.1016/j.ica.2025.122545

Gerald Enos Shija , Deogratius Jaganyi , Allen Mambanda

The kinetics and mechanism of substitition reactions of dinuclear platinum(II) complexes of the general formula [{Pt(H₂O)}₂(N,N,N′,N′-tetrakis(2-pyridylmethyl)-N(CH₂)_n-N](ClO₄)₄,viz., n = 2 (PtEn); 3 (PtProp); 6 (PtHex); 8 (PtOct) and 10 (PtDec) were investigated in 0.10 M aqueous perchloric acid medium as a function of concentration of l-glutathione (Glu) and dl-penicilliamine (Pen) nucleophiles and temperature under pseudo first-order conditions using UV–visible spectrophotometry. The reactivity data of the dinuclear Pt(II) complexes were compared with those of their mononuclear analogues of the form [Pt(H₂O)(N,N-bis(2-pyridylmethyl)-N(CH₂)_n-CH₃](ClO₄)₂, n = 1 (Ptbpea); 2 (Ptbppa); 5 (Ptbpha) and 9 (Ptbpda) under the same experimental conditions. The observed rate constants for the substitution of the aqua ligands follow the simple rate law: k_obs = k₂[Nu]. The reactivity of the complexes increases as the chain length of the linker or tail increases except Prop which showed a higher reactivity towards the nucleophiles than the rest of the complexes. The overall trend of reactivity for the dinuclear platinum(II) complexes is PtEn < PtHex < PtOct < PtDec < PtProp. The reactivity of the mononuclear complexes follows the same trend as the dinuclears and increases in the order Ptbpea < Ptbppa < Ptbpha < Ptbpda. In all cases, mononuclear complexes are more reactive than their dinuclear analogues, which is an indication of the steric retardation on the rate of substitution due to the conformations of the dinuclear platinum(II) complexes. Glu was found to be a better nucleophile than Pen. The relatively small and positive values for the enthalpy of activation, negative values for entropy of activation and the dependence of the second-order rate constants on the concentration of entering nucleophiles supports an associatively activated mechanism.

{"title":"Kinetics and mechanism of the reactions of alkanediamine-linked dinuclear platinum(II) complexes with some biorelevant-nucleophiles","authors":"Gerald Enos Shija , Deogratius Jaganyi , Allen Mambanda","doi":"10.1016/j.ica.2025.122545","DOIUrl":"10.1016/j.ica.2025.122545","url":null,"abstract":"<div><div>The kinetics and mechanism of substitition reactions of dinuclear platinum(II) complexes of the general formula [{Pt(H2O)}2(N,N,N′,N′-tetrakis(2-pyridylmethyl)-N(CH2)n-N](ClO4)4,viz., n = 2 (PtEn); 3 (PtProp); 6 (PtHex); 8 (PtOct) and 10 (PtDec) were investigated in 0.10 M aqueous perchloric acid medium as a function of concentration of l-glutathione (Glu) and dl-penicilliamine (Pen) nucleophiles and temperature under pseudo first-order conditions using UV–visible spectrophotometry. The reactivity data of the dinuclear Pt(II) complexes were compared with those of their mononuclear analogues of the form [Pt(H2O)(N,N-bis(2-pyridylmethyl)-N(CH2)n-CH3](ClO4)2, n = 1 (Ptbpea); 2 (Ptbppa); 5 (Ptbpha) and 9 (Ptbpda) under the same experimental conditions. The observed rate constants for the substitution of the aqua ligands follow the simple rate law: kobs = k2[Nu]. The reactivity of the complexes increases as the chain length of the linker or tail increases except Prop which showed a higher reactivity towards the nucleophiles than the rest of the complexes. The overall trend of reactivity for the dinuclear platinum(II) complexes is PtEn < PtHex < PtOct < PtDec < PtProp. The reactivity of the mononuclear complexes follows the same trend as the dinuclears and increases in the order Ptbpea < Ptbppa < Ptbpha < Ptbpda. In all cases, mononuclear complexes are more reactive than their dinuclear analogues, which is an indication of the steric retardation on the rate of substitution due to the conformations of the dinuclear platinum(II) complexes. Glu was found to be a better nucleophile than Pen. The relatively small and positive values for the enthalpy of activation, negative values for entropy of activation and the dependence of the second-order rate constants on the concentration of entering nucleophiles supports an associatively activated mechanism.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"578 ","pages":"Article 122545"},"PeriodicalIF":2.7,"publicationDate":"2025-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143347211","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}

引用次数: 0

Ruthenium(II)furoic hydrazone complexes in effective catalytic transfer hydrogenation of aldehydes to alcohols

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2025-01-18 DOI: 10.1016/j.ica.2025.122557

Jayapratha Gunasekaran , Sounthararajan Muniyan , Gayathri Dhanasekaran , Denzil Britto Christopher Leslee , Narmatha Venkatesan , Luis G. Alves , Ana M. Martins , Shanmuga Bharathi Kuppannan

A series of [Ru(ɳ⁶-p-cymene)(Cl)(L^1-3)] complexes based on three different furoic hydrazone ligands (HL^1-3) were developed for the catalytic application in the effective and simple methodology for the synthesis of benzyl and aliphatic alcohols through transfer hydrogenation of benzaldehyde or aliphatic aldehydes, respectively. The solid-state molecular structures of the three ruthenium complexes were determined by single-crystal X-ray diffraction revealing pseudo-octahedral three-legged piano-stool geometries. Complex [Ru(ɳ⁶-p-cymene)(Cl)(pyrene-furoichydrazone) showed the higher catalytic performance over others due to the hyperconjugation effect of the pyrene moiety that facilitates the transfer hydrogenation reaction. The catalytic experiments afforded the desired products in good to excellent yields and were performed through an effective methodology using isopropanol as solvent, using a 1 mol% of catalyst loading under room temperature. The catalyst demonstrates a wide range of substrate scope being able to catalyze the transfer hydrogenation of 17 different substrates that includes aromatic, heterocyclic and aliphatic aldehydes with electron donating and/or withdrawing substituent groups.

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引用次数: 0

Binding and stabilizing effects of ruthenium(II) polypyridyl complexes [Ru(bpy)2(6-L-dppz)]2+ (L = F and CH3) toward duplex RNA poly(A)·poly(U) under molecular crowding conditions

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta

Pub Date : 2025-01-17 DOI: 10.1016/j.ica.2025.122556

Keliang Wan , Zhiqiang Tan , Lifeng Tan

The binding behaviors of two ruthenium(II) polypyridyl complexes [Ru(phen)₂(6-F-dppz)]²⁺ (Ru1, phen = 1,10-o-phenanthroline, 6-F-dppz = 10-fluoroquinoxalino[2,3-f][1,10]phenanthroline) and [Ru(phen)₂(6-CH₃-dppz)²⁺ (Ru2, 6-CH₃-dppz = 10-methylquinoxalino[2,3-f][1,10]phenanthroline) with double-stranded RNA poly(A)·poly(U) in dilute solution and molecular crowding conditions were studied by a variety of spectroscopic and viscosity measurement methods in this work. The hypochromic effect and bathochromic shift of the absorption spectra of the two complexes interacting with A·U in dilute solution and molecular crowding conditions indicate that their main binding to A·U may be by intercalation under the two conditions. Through comparing the binding parameters obtained in UV–vis absorption spectroscopy titration experiments, it was found that molecular crowding would weaken the binding affinity of the two Ru(Ⅱ) complexes to A·U, but the binding affinity of Ru1 with strong electron-withdrawing groups to A·U is still stronger than that of Ru2, which suggests that the impact of the substituent effect of the Ru(Ⅱ) complex on its binding and stabilizing A·U is still effective under molecular crowding conditions. The measurement results of Steady-state luminescence spectroscopy, circular dichroism spectroscopy, thermal denaturation and viscosity also support the above conclusions. The results of this work indicate that in addition to the structures of Ru(II) polypyridyl complexes, the solution environment is also an important factor affecting the binding properties of Ru(II) polypyridyl complexes to RNA poly(A)·poly(U).

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引用次数: 0

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