Pub Date : 2024-09-18DOI: 10.1016/j.ica.2024.122377
Alkaline direct ethanol fuel cells (ADEFCs) offer a promising solution to reduce reliance on fossil fuels. Despite their advantages over hydrogen and methanol fuel cells, the anodic ethanol oxidation reaction (EOR) in ADEFCs faces challenges such as sluggish kinetics and high overpotentials, leading to reduced efficiency. To address these issues, highly active electrocatalysts are essential. This review highlights recent advancements in Pd-based high-entropy materials (HEMs) and single-atom catalysts (SACs) for EOR. Additionally, MXenes, a novel family of two-dimensional materials, have shown promise as supports for these electrocatalysts. We discuss the fundamental principles of EOR, the unique properties of these emerging materials, and their applications in EOR electrocatalysis. Finally, we provide an outlook on future research directions to enhance the commercialization of Pd-based electrocatalysts for ADEFC technologies.
{"title":"Emerging Pd-based electrocatalysts and supports for ethanol oxidation reaction: High-entropy and single-atom materials","authors":"","doi":"10.1016/j.ica.2024.122377","DOIUrl":"10.1016/j.ica.2024.122377","url":null,"abstract":"<div><div>Alkaline direct ethanol fuel cells (ADEFCs) offer a promising solution to reduce reliance on fossil fuels. Despite their advantages over hydrogen and methanol fuel cells, the anodic ethanol oxidation reaction (EOR) in ADEFCs faces challenges such as sluggish kinetics and high overpotentials, leading to reduced efficiency. To address these issues, highly active electrocatalysts are essential. This review highlights recent advancements in Pd-based high-entropy materials (HEMs) and single-atom catalysts (SACs) for EOR. Additionally, MXenes, a novel family of two-dimensional materials, have shown promise as supports for these electrocatalysts. We discuss the fundamental principles of EOR, the unique properties of these emerging materials, and their applications in EOR electrocatalysis. Finally, we provide an outlook on future research directions to enhance the commercialization of Pd-based electrocatalysts for ADEFC technologies.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004687/pdfft?md5=11ea236b5a7ba43c1521aea7dc205f92&pid=1-s2.0-S0020169324004687-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142312506","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}
Pub Date : 2024-09-18DOI: 10.1016/j.ica.2024.122379
This research article encompasses the synthesis of two novel mononuclear cobalt(III) complexes of ONO donor tridentate Schiff base ligands, [Co(HL)2]∙(HCDA) (1) and [Co(L1)2]∙(5H2O)∙(Et3NH) (2) [H2L = (E)-2-((1-hydroxybutan-2-ylimino)methyl)-6-methoxyphenol)), HCDA = 1,4-cyclohexanemonocarboxylate, H2L1 = 3-[(2-hydroxy-3-methoxy-benzylidine)-amino]-propionic acid, Et3NH = protonated triethylamine] and characterization of these compounds through the spectroscopic studies and X-ray diffraction techniques. Structural determination reveals that both the complexes crystallize in the triclinic system with space group P-1 and exhibits six coordinated distorted octahedral geometry. DFT as well as TD-DFT calculations were performed using WB97XD/DGTZVP method to understand the electronic properties and stability of the complexes. The computational results are in accordance with the experimental results. Based on the results of quantum chemical parameters, it is found that complex 1 is more reactive, more electrophile less hard and has higher electronegativity value than that of complex 2. The binding efficacy and binding mode of these complexes with bovine serum albumin and human serum albumin are investigated through experimental and computational approaches, including molecular docking studies to assess their potential biological applications. The hyperchromism in electronic absorption spectra and quenching of fluorescence intensities of serum albumins with various complex concentrations illustrate the presence of strong interaction between the serum albumins and the studied complexes. Kinetic parameters of interactions reveal that the binding affinities of the tested complexes are comparable with the reported Schiff base coordinated cobalt complexes. Molecular docking results show that both the complexes, selectively binds with the bovine serum albumin at the active site Tyr 149 and with human serum albumin at the active site Tyr 411 via hydrophobic, electrostatic and hydrogen bonding interactions. The binding affinity of the complexes with serum albumins follow the order 2 > 1 which may be due to the higher HOMO energy of 2 is capable to donate electrons easily to the receptors.
{"title":"Tridentate chelating ligand coordinated Co(III) complexes: Synthesis, crystal structure, DFT/TD-DFT calculation, studies of interaction with proteins and molecular docking","authors":"","doi":"10.1016/j.ica.2024.122379","DOIUrl":"10.1016/j.ica.2024.122379","url":null,"abstract":"<div><div>This research article encompasses the synthesis of two novel mononuclear cobalt(III) complexes of ONO donor tridentate Schiff base ligands, [Co(HL)<sub>2</sub>]∙(HCDA) (<strong>1</strong>) and [Co(L<sup>1</sup>)<sub>2</sub>]∙(5H<sub>2</sub>O)∙(Et<sub>3</sub>NH) (<strong>2</strong>) [H<sub>2</sub>L = (E)-2-((1-hydroxybutan-2-ylimino)methyl)-6-methoxyphenol)), HCDA = 1,4-cyclohexanemonocarboxylate, H<sub>2</sub>L<sup>1</sup> = 3-[(2-hydroxy-3-methoxy-benzylidine)-amino]-propionic acid, Et<sub>3</sub>NH = protonated triethylamine] and characterization of these compounds through the spectroscopic studies and X-ray diffraction techniques. Structural determination reveals that both the complexes crystallize in the triclinic system with space group <em>P</em>-1 and exhibits six coordinated distorted octahedral geometry. DFT as well as TD-DFT calculations were performed using WB97XD/DGTZVP method to understand the electronic properties and stability of the complexes. The computational results are in accordance with the experimental results. Based on the results of quantum chemical parameters, it is found that complex <strong>1</strong> is more reactive, more electrophile less hard and has higher electronegativity value than that of complex <strong>2</strong>. The binding efficacy and binding mode of these complexes with bovine serum albumin and human serum albumin are investigated through experimental and computational approaches, including molecular docking studies to assess their potential biological applications. The hyperchromism in electronic absorption spectra and quenching of fluorescence intensities of serum albumins with various complex concentrations illustrate the presence of strong interaction between the serum albumins and the studied complexes. Kinetic parameters of interactions reveal that the binding affinities of the tested complexes are comparable with the reported Schiff base coordinated cobalt complexes. Molecular docking results show that both the complexes, selectively binds with the bovine serum albumin at the active site Tyr 149 and with human serum albumin at the active site Tyr 411 via hydrophobic, electrostatic and hydrogen bonding interactions. The binding affinity of the complexes with serum albumins follow the order <strong>2</strong> > <strong>1</strong> which may be due to the higher HOMO energy of <strong>2</strong> is capable to donate electrons easily to the receptors.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142323040","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 : 2024-09-16DOI: 10.1016/j.ica.2024.122383
This study investigates the impact of the type and arrangement of metal centers on the electronic transitions of multimetallic complexes through a combined experimental and computational approach. At first, homo- and hetero-metallic [Mn(TPPZ)n+1]2n+ complexes (M = Ru(Ⅱ) and Os(Ⅱ), TPPZ = 2,3,5,6-tetrakis(2-pyridyl)pyrazine, and n = 1 and 2) were synthesized and fully characterized. Then, density functional theory (DFT) and time-dependent DFT calculations were performed to explore the geometries, electronic structures, excited states, and spectroscopic properties of mono-, bi-, and trimetallic complexes. The comparison between experimental and computational spectra of mono- and bimetallic complexes showed excellent agreement, particularly in peak intensities and absorption energies. The visible region bands were attributed to metal-to-ligand charge-transfer (MLCT) transitions. This study offers insights into how the quantity, type, and arrangement of metal centers influence the frontier orbital energy levels and electronic spectra in homo- and heteronuclear complexes.
{"title":"The effect of metal centers on the electronic transitions of HOMO- and heteronuclear Ru(Ⅱ) and Os(Ⅱ) complexes with 2,3,5,6-tetrakis(2-pyridyl) pyrazine: A combined theoretical and experimental study","authors":"","doi":"10.1016/j.ica.2024.122383","DOIUrl":"10.1016/j.ica.2024.122383","url":null,"abstract":"<div><p>This study investigates the impact of the type and arrangement of metal centers on the electronic transitions of multimetallic complexes through a combined experimental and computational approach. At first, homo- and hetero-metallic [Mn(TPPZ)<sub>n+1</sub>]<sup>2n+</sup> complexes (M = Ru(Ⅱ) and Os(Ⅱ), TPPZ = 2,3,5,6-tetrakis(2-pyridyl)pyrazine, and n = 1 and 2) were synthesized and fully characterized. Then, density functional theory (DFT) and time-dependent DFT calculations were performed to explore the geometries, electronic structures, excited states, and spectroscopic properties of mono-, bi-, and trimetallic complexes. The comparison between experimental and computational spectra of mono- and bimetallic complexes showed excellent agreement, particularly in peak intensities and absorption energies. The visible region bands were attributed to metal-to-ligand charge-transfer (MLCT) transitions. This study offers insights into how the quantity, type, and arrangement of metal centers influence the frontier orbital energy levels and electronic spectra in homo- and heteronuclear complexes.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004742/pdfft?md5=18f871d8b66137fe7809251b6f44d560&pid=1-s2.0-S0020169324004742-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142241447","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}
Pub Date : 2024-09-14DOI: 10.1016/j.ica.2024.122373
The sulfoxide-containing Schiff base (E)-2-((2-(methylsulfinylphenyl)imino) methyl) phenol (HL) was synthesized by aldolamine condensation and oxidation. In the presence of triethylamine, equal amounts of [RuCl2(CO)2]n, [RuHCl(CO)(PPh3)3], cis-[RuCl2(dmso)4] (dmso = dimethylsulfoxide) and [RuCl2(PPh3)3] were reacted with HL to give the ruthenium(II) complexes [RuCl(L)(CO)2] (1), [RuCl(L)(CO)(PPh3)] (2), [RuCl(L)(dmso)2] (3), and [RuCl(L)(PPh3)2] (4), respectively. Compound 4 converted to be [RuCl(L)(PPh3)(CH3CN)] (4′) by recrystallization in acetonitrile. The structures of HL, 1, 2, 3 and 4′ have been confirmed by single crystal X-ray crystallography. In addition, the UV–visible, infrared and fluorescence spectra of HL and its ruthenium complexes 1–4 along with their electrochemical properties were investigated. The catalytic properties of complexes 1–4 for the cyclopropylation of styrene were also presented.
{"title":"Ruthenium(II) complexes bearing tridentate 2-(methylsulfoxide)-phenylsalicylaldimine Schiff-base ligands","authors":"","doi":"10.1016/j.ica.2024.122373","DOIUrl":"10.1016/j.ica.2024.122373","url":null,"abstract":"<div><p>The sulfoxide-containing Schiff base (<em>E</em>)-2-((2-(methylsulfinylphenyl)imino) methyl) phenol (<strong>HL</strong>) was synthesized by aldolamine condensation and oxidation. In the presence of triethylamine, equal amounts of [RuCl<sub>2</sub>(CO)<sub>2</sub>]<sub>n</sub>, [RuHCl(CO)(PPh<sub>3</sub>)<sub>3</sub>], <em>cis</em>-[RuCl<sub>2</sub>(dmso)<sub>4</sub>] (dmso = dimethylsulfoxide) and [RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub>] were reacted with <strong>HL</strong> to give the ruthenium(II) complexes [RuCl(<strong>L</strong>)(CO)<sub>2</sub>] (<strong>1</strong>), [RuCl(<strong>L</strong>)(CO)(PPh<sub>3</sub>)] (<strong>2</strong>), [RuCl(<strong>L</strong>)(dmso)<sub>2</sub>] (<strong>3</strong>), and [RuCl(<strong>L</strong>)(PPh<sub>3</sub>)<sub>2</sub>] (<strong>4</strong>), respectively. Compound <strong>4</strong> converted to be [RuCl(<strong>L</strong>)(PPh<sub>3</sub>)(CH<sub>3</sub>CN)] (<strong>4′</strong>) by recrystallization in acetonitrile. The structures of <strong>HL</strong>, <strong>1</strong>, <strong>2</strong>, <strong>3</strong> and <strong>4′</strong> have been confirmed by single crystal X-ray crystallography. In addition, the UV–visible, infrared and fluorescence spectra of <strong>HL</strong> and its ruthenium complexes <strong>1</strong>–<strong>4</strong> along with their electrochemical properties were investigated. The catalytic properties of complexes <strong>1</strong>–<strong>4</strong> for the cyclopropylation of styrene were also presented.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S002016932400464X/pdfft?md5=a20fb8abd525bca5acdc7bf7312d19ff&pid=1-s2.0-S002016932400464X-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142232521","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}
Pub Date : 2024-09-14DOI: 10.1016/j.ica.2024.122382
This work presents the synthesis of new cationic bis-(P,P)-chelate copper(I) tetrafluoroborate and hexafluorophosphate complexes with 1,5,3,7-diazadiphosphacyclooctanes with various para-alkylphenyl substituents (alkyl – methyl, isopropyl and octyl) at nitrogen atoms to assess their effect on the therapeutic potential of these complexes. Structure-dependent aggregation of these complexes is observed in the aqueous medium simulating nutrient media, with the octyl-substituted complex exhibiting the most pronounced aggregation. The generation of reactive oxygen species (ROS) by the complexes in an aqueous environment does not correlate with their oxidation potentials but is significantly suppressed by their aggregation. The luminescence of the complexes in the aqueous environment enables the visualization of their cellular uptake. This allows to correlate the cellular uptake of the complexes with their structure-dependent aggregation. The cytotoxicity of the complexes measured in a range of cancer and normal cells depends on their structure, which can be explained by their structure-dependent aggregation and ROS generation. The anticancer specificity of the complexes with isopropylphenyl and methylphenyl substituents are comparable, while these values are higher compared to the octyl-substituted complex. Therefore, these groups are optimal for ensuring the anticancer specificity of Cu(I) bis-chelates, which is likely due to the formation of aggregates with sufficient chemical and colloidal stability in aqueous media.
{"title":"Structure-dependent aggregation and ROS-generation in aqueous media of new cationic copper(I) complexes based on 1,5,3,7-diazadiphosphacyclooctanes","authors":"","doi":"10.1016/j.ica.2024.122382","DOIUrl":"10.1016/j.ica.2024.122382","url":null,"abstract":"<div><p>This work presents the synthesis of new cationic bis-(P,P)-chelate copper(I) tetrafluoroborate and hexafluorophosphate complexes with 1,5,3,7-diazadiphosphacyclooctanes with various <em>para</em>-alkylphenyl substituents (alkyl – methyl, isopropyl and octyl) at nitrogen atoms to assess their effect on the therapeutic potential of these complexes. Structure-dependent aggregation of these complexes is observed in the aqueous medium simulating nutrient media, with the octyl-substituted complex exhibiting the most pronounced aggregation. The generation of reactive oxygen species (ROS) by the complexes in an aqueous environment does not correlate with their oxidation potentials but is significantly suppressed by their aggregation. The luminescence of the complexes in the aqueous environment enables the visualization of their cellular uptake. This allows to correlate the cellular uptake of the complexes with their structure-dependent aggregation. The cytotoxicity of the complexes measured in a range of cancer and normal cells depends on their structure, which can be explained by their structure-dependent aggregation and ROS generation. The anticancer specificity of the complexes with isopropylphenyl and methylphenyl substituents are comparable, while these values are higher compared to the octyl-substituted complex. Therefore, these groups are optimal for ensuring the anticancer specificity of Cu(I) bis-chelates, which is likely due to the formation of aggregates with sufficient chemical and colloidal stability in aqueous media.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004730/pdfft?md5=fe6712f6776959a047dcfb7f841f8778&pid=1-s2.0-S0020169324004730-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142232523","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}
Pub Date : 2024-09-14DOI: 10.1016/j.ica.2024.122376
Prediction of the lowest energy structure for transition metal clusters and related systems is fundamental in cluster science. Advances in the structure search methods have reduced the computer time for structure prediction, standing on the performance of density functional theory (DFT) calculations. This perspective summarizes recent advances in the employed strategies to tackle geometrical determination of small and large metallic clusters via structure identification and rationalization of the resulting properties. Particularly, we pay attention to coinage metal clusters and noble metals due to their potential technological applications. The basics and recent achievements in structure search methods and related challenges are summarized, towards determining structural evolution accounting contributing to further development on efficient catalytic materials among other applications of technological interest.
{"title":"Structure search for transition metal clusters. Towards a rational understanding of their size-dependent properties","authors":"","doi":"10.1016/j.ica.2024.122376","DOIUrl":"10.1016/j.ica.2024.122376","url":null,"abstract":"<div><div>Prediction of the lowest energy structure for transition metal clusters and related systems is fundamental in cluster science. Advances in the structure search methods have reduced the computer time for structure prediction, standing on the performance of density functional theory (DFT) calculations. This perspective summarizes recent advances in the employed strategies to tackle geometrical determination of small and large metallic clusters via structure identification and rationalization of the resulting properties. Particularly, we pay attention to coinage metal clusters and noble metals due to their potential technological applications. The basics and recent achievements in structure search methods and related challenges are summarized, towards determining structural evolution accounting contributing to further development on efficient catalytic materials among other applications of technological interest.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142319072","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 : 2024-09-13DOI: 10.1016/j.ica.2024.122380
The syntheses, crystal structures, spectral characterization, electrochemical, photoredox properties and biological studies of three sodium coordination polymers viz. (ImH)4[(µ2-HMo7O24)Na(H2O)8]∙7H2O 1 (Im = Imidazole), [(TEAH)Na5(H2O)12(µ5-Mo7O24)] 2 (TEA=triethanolamine) and [Na2(PyrH)2(µ2-Mo8O26)(H2O)7]∙8H2O 3 (Pyr = pyrazole) are reported. The unique Na atom in 1 exhibits ten coordination unlike hexa coordination observed in 2 and 3. The µ2-bridging heptamolybdate (or octamolybdate) anion in 1 (or 3) links the sodium cations into an infinite chain resulting in a one-dimensional coordination polymer. In 2, the heptamolybdate anion exhibits an unprecedented µ5-nonadentate binding resulting in a three- dimensional (3D) structure. Compounds 1–3 exhibit characteristic Raman bands. Solar irradiation of 2 results in photodimerization, which is further supported by electrochemical studies. Compounds 1–3 exhibit antibacterial activity, with 3 being the most effective against S. Pyogenes, followed by P. aeruginosa, S.typhi and S. aureus. Compound 3 exhibits excellent antidiabetic and anti-inflammatory properties. A comparative study of the binding modes of several heptamolybdates and octamolybdates based compounds is presented.
{"title":"Synthesis, crystal structures and properties of three sodium coordination polymers based on bridging polyoxometalate ligands","authors":"","doi":"10.1016/j.ica.2024.122380","DOIUrl":"10.1016/j.ica.2024.122380","url":null,"abstract":"<div><p>The syntheses, crystal structures, spectral characterization, electrochemical, photoredox properties and biological studies of three sodium coordination polymers viz. (ImH)<sub>4</sub>[(µ<sub>2</sub>-HMo<sub>7</sub>O<sub>24</sub>)Na(H<sub>2</sub>O)<sub>8</sub>]∙7H<sub>2</sub>O <strong>1</strong> (Im = Imidazole), [(TEAH)Na<sub>5</sub>(H<sub>2</sub>O)<sub>12</sub>(<em>µ<sub>5</sub></em>-Mo<sub>7</sub>O<sub>24</sub>)] <strong>2</strong> (TEA=triethanolamine) and [Na<sub>2</sub>(PyrH)<sub>2</sub>(<em>µ<sub>2</sub></em>-Mo<sub>8</sub>O<sub>26</sub>)(H<sub>2</sub>O)<sub>7</sub>]∙8H<sub>2</sub>O <strong>3</strong> (Pyr = pyrazole) are reported. The unique Na atom in <strong>1</strong> exhibits ten coordination unlike hexa coordination observed in <strong>2</strong> and <strong>3</strong>. The µ<sub>2</sub>-bridging heptamolybdate (or octamolybdate) anion in <strong>1</strong> (or <strong>3</strong>) links the sodium cations into an infinite chain resulting in a one-dimensional coordination polymer. In <strong>2,</strong> the heptamolybdate anion exhibits an unprecedented <em>µ<sub>5</sub></em>-nonadentate binding resulting in a three- dimensional (3D) structure. Compounds <strong>1</strong>–<strong>3</strong> exhibit characteristic Raman bands. Solar irradiation of <strong>2</strong> results in photodimerization, which is further supported by electrochemical studies. Compounds <strong>1</strong>–<strong>3</strong> exhibit antibacterial activity, with <strong>3</strong> being the most effective against <em>S. Pyogenes</em>, followed by <em>P. aeruginosa</em>, <em>S.typhi</em> and <em>S. aureus</em>. Compound <strong>3</strong> exhibits excellent antidiabetic and anti-inflammatory properties. A comparative study of the binding modes of several heptamolybdates and octamolybdates based compounds is presented.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004717/pdfft?md5=47e792addf54a098e197e056965c7fa7&pid=1-s2.0-S0020169324004717-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142241446","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}
Pub Date : 2024-09-13DOI: 10.1016/j.ica.2024.122378
The reaction in water between RbOH and isocyanuric acid (CYH3) leads, under mild reaction conditions (pH = 10, T = 20 °C), to the formation of crystals of good quality of the complex [Rb3(CYH2)3(CYH3)(H2O)4]. The ordered structure of [Rb3(CYH2)3(CYH3)(H2O)4] was refined from X-ray diffraction data, using a super-structure unit cell with a = 13.1315(1), b = 16.6198(1), c = 23.6865(1) Å, β = 99.751(1)°, and space group I2/a. The asymmetric unit of [Rb3(CYH2)3(CYH3)(H2O)4] contains three independent Rb+ cations, three CYH2− anions, one CYH3 and four water molecules, all located in the unit cell in general position. The Rb+ cations with the water molecules are arranged to form layers intercalated by ribbons made by the CYH2− anions and CYH3 molecules, in their keto-tautomeric form, that are coordinated to the cations through their oxygen atom, and interact each other and with the water molecules through hydrogen bonds. FT-IR and ATR-IR spectra of complex [Rb3(CYH2)3(CYH3)(H2O)4] are reported. Hirshfeld surface analysis (dnorm, shape index, curvedness) was also used to visualize the intermolecular interactions in the crystal structure. The low value of void percent in the crystal packing, to which the presence of water molecules contribute, indicates a compact crystal packing.
{"title":"Synthesis and crystal structure of the complex [Rb3(CYH2)3(CYH3)(H2O)4] (CYH3 = isocyanuric acid): An interesting case of disordered sub-structure, ordered super-structure","authors":"","doi":"10.1016/j.ica.2024.122378","DOIUrl":"10.1016/j.ica.2024.122378","url":null,"abstract":"<div><div>The reaction in water between RbOH and isocyanuric acid (CYH<sub>3</sub>) leads, under mild reaction conditions (pH = 10, <em>T</em> = 20 °C), to the formation of crystals of good quality of the complex [Rb<sub>3</sub>(CYH<sub>2</sub>)<sub>3</sub>(CYH<sub>3</sub>)(H<sub>2</sub>O)<sub>4</sub>]. The ordered structure of [Rb<sub>3</sub>(CYH<sub>2</sub>)<sub>3</sub>(CYH<sub>3</sub>)(H<sub>2</sub>O)<sub>4</sub>] was refined from X-ray diffraction data, using a super-structure unit cell with <em>a</em> = 13.1315(1), <em>b</em> = 16.6198(1), <em>c</em> = 23.6865(1) Å, β = 99.751(1)°, and space group <em>I</em>2<em>/a</em>. The asymmetric unit of [Rb<sub>3</sub>(CYH<sub>2</sub>)<sub>3</sub>(CYH<sub>3</sub>)(H<sub>2</sub>O)<sub>4</sub>] contains three independent Rb<sup>+</sup> cations, three CYH<sub>2</sub><sup>−</sup> anions, one CYH<sub>3</sub> and four water molecules, all located in the unit cell in general position. The Rb<sup>+</sup> cations with the water molecules are arranged to form layers intercalated by ribbons made by the CYH<sub>2</sub><sup>−</sup> anions and CYH<sub>3</sub> molecules, in their keto-tautomeric form, that are coordinated to the cations through their oxygen atom, and interact each other and with the water molecules through hydrogen bonds. FT-IR and ATR-IR spectra of complex [Rb<sub>3</sub>(CYH<sub>2</sub>)<sub>3</sub>(CYH<sub>3</sub>)(H<sub>2</sub>O)<sub>4</sub>] are reported. Hirshfeld surface analysis (<em>d</em><sub>norm</sub>, shape index, curvedness) was also used to visualize the intermolecular interactions in the crystal structure. The low value of void percent in the crystal packing, to which the presence of water molecules contribute, indicates a compact crystal packing.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004699/pdfft?md5=aa4857fdcb392ca39fc19841d28829af&pid=1-s2.0-S0020169324004699-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142314794","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}
Pub Date : 2024-09-12DOI: 10.1016/j.ica.2024.122370
The nature and strength of metal–ligand bonds in organotransition-metal complexes are crucial to the understanding of organometallic reactions and catalysis. Quantum chemical calculations at different levels of theory have been used to investigate heterolytic Fe-N bond energies of meta-substituted anilinyldicarbonyl(η5-cyclopentadienyl)iron [m-G-C6H4NH(η5-C5H5)Fe(CO)2, abbreviated as m-G-C6H4NHFp (1), where G=NO2, CN, COMe, CO2Me, CF3, Br, Cl, F, H, Me, MeO and NMe2] and meta-substituted α-acetylanilinyldicarbonyl(η5-cyclopentadienyl)iron [m-G-C6H4N(COMe)(η5-C5H5)Fe(CO)2, abbreviated as m-G-C6H4N(COMe)Fp (2)] complexes. The results show that BP86 and TPSSTPSS can provide the best price/performance ratio and more accurate predictions in the study of ΔHhet(Fe-N)′s. ΔΔHhet(Fe-N)′s (1 and 2) conform to the captodative principle. There are excellent linear free energy relations among ΔΔHhet(Fe-N)′s and the experimental and computational substituent effects on acidities of m-G-C6H4NH2, the differences of acidic dissociation constants (ΔpKas) of NH bonds for m-G-C6H4NH2 for series 1 or the substituent σm constants. The former correlations imply that the govering factors for these bond scissions are similar; the latter ones suggest that polar effects of meta-substituents show the dominant role to the magnitudes of ΔHhet(Fe-N)′s. And these correlations are in accordance with Hammett linear free energy relationships. The Fe-N bonds in series 1 are stronger than those in series 2. Therefore m-G-C6H4N(COMe)- are more stable than m-G-C6H4NH-. The absolute magnitudes of AEs, AEα-COMes and AEα-COMe,para-Gs are far larger than MEs, MEα-COMes and MEα-COMe,para-Gs. The influences of MEs, MEα-COMes and MEα-COMe,para-Gs are subtle. A better understanding of organometallic bond energies can suggest whether proposed new catalytic systems may work well.
{"title":"Density functional theory study of substituent effects on gas-phase heterolytic Fe-N bond energies of m-G-C6H4NHFe(CO)2(η5-C5H5) and m-G-C6H4N(COMe)Fe(CO)2(η5-C5H5)","authors":"","doi":"10.1016/j.ica.2024.122370","DOIUrl":"10.1016/j.ica.2024.122370","url":null,"abstract":"<div><div>The nature and strength of metal–ligand bonds in organotransition-metal complexes are crucial to the understanding of organometallic reactions and catalysis. Quantum chemical calculations at different levels of theory have been used to investigate heterolytic Fe-N bond energies of <em>meta</em>-substituted anilinyldicarbonyl(η<sup>5</sup>-cyclopentadienyl)iron [<em>m</em>-G-C<sub>6</sub>H<sub>4</sub>NH(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Fe(CO)<sub>2</sub>, abbreviated as <em>m</em>-G-C<sub>6</sub>H<sub>4</sub>NHFp (<strong>1</strong>), where G=NO<sub>2</sub>, CN, COMe, CO<sub>2</sub>Me, CF<sub>3</sub>, Br, Cl, F, H, Me, MeO and NMe<sub>2</sub>] and <em>meta</em>-substituted α-acetylanilinyldicarbonyl(η<sup>5</sup>-cyclopentadienyl)iron [<em>m</em>-G-C<sub>6</sub>H<sub>4</sub>N(COMe)(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Fe(CO)<sub>2</sub>, abbreviated as <em>m</em>-G-C<sub>6</sub>H<sub>4</sub>N(COMe)Fp (<strong>2</strong>)] complexes. The results show that BP86 and TPSSTPSS can provide the best price/performance ratio and more accurate predictions in the study of Δ<em>H</em><sub>het</sub>(Fe-N)′s. ΔΔ<em>H</em><sub>het</sub>(Fe-N)′s (<strong>1</strong> and <strong>2</strong>) conform to the captodative principle. There are excellent linear free energy relations among ΔΔ<em>H</em><sub>het</sub>(Fe-N)′s and the experimental and computational substituent effects on acidities of <em>m</em>-G-C<sub>6</sub>H<sub>4</sub>NH<sub>2</sub>, the differences of acidic dissociation constants (Δp<em>K</em><sub>a</sub>s) of N<img>H bonds for <em>m</em>-G-C<sub>6</sub>H<sub>4</sub>NH<sub>2</sub> for series <strong>1</strong> or the substituent σ<sub>m</sub> constants. The former correlations imply that the govering factors for these bond scissions are similar; the latter ones suggest that polar effects of <em>meta</em>-substituents show the dominant role to the magnitudes of Δ<em>H</em><sub>het</sub>(Fe-N)′s. And these correlations are in accordance with Hammett linear free energy relationships. The Fe-N bonds in series <strong>1</strong> are stronger than those in series <strong>2</strong>. Therefore <em>m</em>-G-C<sub>6</sub>H<sub>4</sub>N(COMe)<sup>-</sup> are more stable than <em>m</em>-G-C<sub>6</sub>H<sub>4</sub>NH<sup>-</sup>. The absolute magnitudes of AEs, AE<sub>α-COMe</sub>s and AE<sub>α-COMe,</sub> <em><sub>para</sub></em><sub>-G</sub>s are far larger than MEs, ME<sub>α-COMe</sub>s and ME<sub>α-COMe,</sub> <em><sub>para</sub></em><sub>-G</sub>s. The influences of MEs, ME<sub>α-COMe</sub>s and ME<sub>α-COMe,</sub> <em><sub>para</sub></em><sub>-G</sub>s are subtle. A better understanding of organometallic bond energies can suggest whether proposed new catalytic systems may work well.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142445863","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 : 2024-09-12DOI: 10.1016/j.ica.2024.122372
Exploring the catalytic activity of the copper(II) complex of pentadentate ligand in oxidizing o-aminophenol (OAP) has not been extensively studied. To scrutinize the least explored domain, we synthesized and characterized the copper(II) complex of pentadentate ligand, 3-(bis(pyridin-2-ylmethyl)amino)-N-(quinolin-8-yl)propanamide. Further, the complex was allowed to react with OAP to form 2-aminophenoxazin-3-one (APX) via oxidative coupling reaction, the resultant product is a functional analogue of phenoxazinone synthase (PHS), an active enzyme, relevant to the industrial production of a widely recognized antibiotic called Actinomycin D. Furthermore, kinetic studies were performed to comprehend the path of the reaction which unveiled the formation of the complex-substrate adduct. It is worth noticing that the complex displayed an impressive turnover number of 6.4 × 104 h−1 under atmospheric conditions in methanol. To the best of our knowledge, the present complex is the first copper(II) complex with pentadentate N5 ligand showing PHS mimicking catalytic activity.
{"title":"Copper(II) complex of pentadentate N5 ligand as catalyst for2-aminophenol oxidation","authors":"","doi":"10.1016/j.ica.2024.122372","DOIUrl":"10.1016/j.ica.2024.122372","url":null,"abstract":"<div><p>Exploring the catalytic activity of the copper(II) complex of pentadentate ligand in oxidizing <em>o</em>-aminophenol (OAP) has not been extensively studied. To scrutinize the least explored domain, we synthesized and characterized the copper(II) complex of pentadentate ligand, 3-(bis(pyridin-2-ylmethyl)amino)-<em>N</em>-(quinolin-8-yl)propanamide. Further, the complex was allowed to react with OAP to form 2-aminophenoxazin-3-one (APX) via oxidative coupling reaction, the resultant product is a functional analogue of phenoxazinone synthase (PHS), an active enzyme, relevant to the industrial production of a widely recognized antibiotic called Actinomycin D. Furthermore, kinetic studies were performed to comprehend the path of the reaction which unveiled the formation of the complex-substrate adduct. It is worth noticing that the complex displayed an impressive turnover number of 6.4 × 10<sup>4</sup> h<sup>−1</sup> under atmospheric conditions in methanol. To the best of our knowledge, the present complex is the first copper(II) complex with pentadentate N5 ligand showing PHS mimicking catalytic activity.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004638/pdfft?md5=36a8b4128b39de5f7a96cc38a417b674&pid=1-s2.0-S0020169324004638-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142270637","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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