Pub Date : 2024-09-21DOI: 10.1016/j.ica.2024.122386
Guoqing Lin , Dai Shi , Na Wang , Tong Lu , Yuguang Zhao
Three polyoxometalate-based metal–organic complexes with the ability to treat pollutants in water were obtained under hydrothermal conditions using two flexible bis(triazole) organic ligands, [Cu(bte)2(H2O)]2[SiMo12O40]·2H2O (1), [Cu(btb)2]2[SiMo12O40]·H2O (2) and [Cu(btb)2(H2O)]2[SiMo12O40] (3) (bte = 1,2-bis(1,2,4-triazol-1-yl)ethane; btb = 1,4-bis(1,2,4-triazol-1-yl)butane). In compound 1, Cu2+ ions are linked by bte into a two-dimensional network layer with [SiMo12O40]4- anions filled between the layers as guest molecules. In compound 2, [SiMo12O40]4- anions act as four-connected ligands to coordinate with Cu2+ and fill in the pores of the three-dimensional framework constructed by Cu2+ and btb. In compound 3, [SiMo12O40]4- anions act as guest molecules to fill the channels of the two-dimensional layer formed by Cu2+ and btb. The electrochemical characteristics were studied, such as cyclic voltammetry, electrocatalytic reduction and oxidation of water contaminants, and current sensing of BrO3-. The photocatalytic degradation of organic dye pollutant MB (methylene blue) performance was also investigated under visible light conditions.
{"title":"Three metal–organic compounds based on [SiMo12O40]4-: Synthesis, structures and properties","authors":"Guoqing Lin , Dai Shi , Na Wang , Tong Lu , Yuguang Zhao","doi":"10.1016/j.ica.2024.122386","DOIUrl":"10.1016/j.ica.2024.122386","url":null,"abstract":"<div><div>Three polyoxometalate-based metal–organic complexes with the ability to treat pollutants in water were obtained under hydrothermal conditions using two flexible bis(triazole) organic ligands, [Cu(bte)<sub>2</sub>(H<sub>2</sub>O)]<sub>2</sub>[SiMo<sub>12</sub>O<sub>40</sub>]·2H<sub>2</sub>O (<strong>1</strong>), [Cu(btb)<sub>2</sub>]<sub>2</sub>[SiMo<sub>12</sub>O<sub>40</sub>]·H<sub>2</sub>O (<strong>2</strong>) and [Cu(btb)<sub>2</sub>(H<sub>2</sub>O)]<sub>2</sub>[SiMo<sub>12</sub>O<sub>40</sub>] (<strong>3</strong>) (bte = 1,2-bis(1,2,4-triazol-1-yl)ethane; btb = 1,4-bis(1,2,4-triazol-1-yl)butane). In compound <strong>1</strong>, Cu<sup>2+</sup> ions are linked by bte into a two-dimensional network layer with [SiMo<sub>12</sub>O<sub>40</sub>]<sup>4-</sup> anions filled between the layers as guest molecules. In compound <strong>2</strong>, [SiMo<sub>12</sub>O<sub>40</sub>]<sup>4-</sup> anions act as four-connected ligands to coordinate with Cu<sup>2+</sup> and fill in the pores of the three-dimensional framework constructed by Cu<sup>2+</sup> and btb. In compound <strong>3</strong>, [SiMo<sub>12</sub>O<sub>40</sub>]<sup>4-</sup> anions act as guest molecules to fill the channels of the two-dimensional layer formed by Cu<sup>2+</sup> and btb. The electrochemical characteristics were studied, such as cyclic voltammetry, electrocatalytic reduction and oxidation of water contaminants, and current sensing of BrO<sup>3-</sup>. The photocatalytic degradation of organic dye pollutant MB (methylene blue) performance was also investigated under visible light conditions.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"574 ","pages":"Article 122386"},"PeriodicalIF":2.7,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004778/pdfft?md5=3c8e2fb4a2897d752837d9a1d3fda2c1&pid=1-s2.0-S0020169324004778-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142312505","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 : 2024-09-20DOI: 10.1016/j.ica.2024.122385
Shalini Rangarajan , Owen A. Beaumont , Maravanji S. Balakrishna , Glen B. Deacon , Victoria L. Blair
Redox protolysis of [YbCp2(dme)] (dme = 1,2-dimethoxyethane) by imidotetraphenyldiphosphinate, ({Ph2PO}2NH) LH yields [YbCp{(Ph2PO)2N}2}(MeCN)] 1 and [Yb{(Ph2PO)2N}3] 2 with the last also obtained by oxidative protolysis of Yb(C6F5)2. The complexes [Ln{(Ph2PO)2N}3] ((Ln = Yb 2, Er 3, Gd 4), [Sm{(Ph2PO)2N}3(MeCN)3] 5 and [Nd{(Ph2 PO)2N}3] 6 have all been prepared by redox transmetallation/protolysis reactions between Yb, Er, Gd, Sm or Nd metals, bispentafluorophenylmercury and proligand LH. Complex 1 is formally eight coordinate with an acetonitrile, cyclopentadienyl (Cp) and two chelating O,O′-(Ph2PO)2N ligands, with the MeCN trans to the Cp ring. Complexes 2 and 4·C7H8 are six coordinate monomers with three chelating O,O′ diphosphinate ligands. By contrast 5 is a highly symmetrical nine-coordinate monomer with three acetonitrile and three chelating O,O′-L ligands. The three-dimensional Hirshfeld surface (3D-HS) analysis and the two-dimensional fingerprint plots (2D-FP) were quantified for different intermolecular interactions in complexes 2 and 4.
{"title":"Imidobis(tetraphenylphosphinato)lanthanoid(III) complexes: Synthesis by oxidative protolysis, and redox transmetallation/protolysis, structural studies and Hirshfeld surface analysis","authors":"Shalini Rangarajan , Owen A. Beaumont , Maravanji S. Balakrishna , Glen B. Deacon , Victoria L. Blair","doi":"10.1016/j.ica.2024.122385","DOIUrl":"10.1016/j.ica.2024.122385","url":null,"abstract":"<div><div>Redox protolysis of [YbCp<sub>2</sub>(dme)] (dme = 1,2-dimethoxyethane) by imidotetraphenyldiphosphinate, ({Ph<sub>2</sub>PO}<sub>2</sub>NH) <strong>LH</strong> yields [YbCp{(Ph<sub>2</sub>PO)<sub>2</sub>N}<sub>2</sub>}(MeCN)] <strong>1</strong> and [Yb{(Ph<sub>2</sub>PO)<sub>2</sub>N}<sub>3</sub>] <strong>2</strong> with the last also obtained by oxidative protolysis of Yb(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>. The complexes [Ln{(Ph<sub>2</sub>PO)<sub>2</sub>N}<sub>3</sub>] ((Ln = Yb <strong>2</strong>, Er <strong>3</strong>, Gd <strong>4</strong>), [Sm{(Ph<sub>2</sub>PO)<sub>2</sub>N}<sub>3</sub>(MeCN)<sub>3</sub>] <strong>5</strong> and [Nd{(Ph<sub>2</sub> PO)<sub>2</sub>N}<sub>3</sub>] <strong>6</strong> have all been prepared by redox transmetallation/protolysis reactions between Yb, Er, Gd, Sm or Nd metals, bispentafluorophenylmercury and proligand <strong>LH</strong>. Complex <strong>1</strong> is formally eight coordinate with an acetonitrile, cyclopentadienyl (Cp) and two chelating <em>O</em>,<em>O</em>′-(Ph<sub>2</sub>PO)<sub>2</sub>N ligands, with the MeCN <em>trans</em> to the Cp ring. Complexes <strong>2</strong> and <strong>4·</strong>C<sub>7</sub>H<sub>8</sub> are six coordinate monomers with three chelating <em>O</em>,<em>O</em>′ diphosphinate ligands. By contrast <strong>5</strong> is a highly symmetrical nine-coordinate monomer with three acetonitrile and three chelating <em>O</em>,<em>O</em>′-<strong>L</strong> ligands. The three-dimensional Hirshfeld surface (3D-HS) analysis and the two-dimensional fingerprint plots (2D-FP) were quantified for different intermolecular interactions in complexes <strong>2</strong> and <strong>4</strong>.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"574 ","pages":"Article 122385"},"PeriodicalIF":2.7,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142326910","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}
The activation of small molecules is a topic of great interest and previously we reported on the easy activation of different types of EH bonds at the dinuclear complex [Re2(CO)8(THF)2] (1) where labile THF molecules coordinate to adjacent rhenium(0) atoms. Here we extend the reactivity of 1 reporting on the oxidative addition of benzene and toluene at room temperature to give [Re2(μ-H)(μ-κC-Ar)(CO)8], Ar = −C6H5 (2) and −C6H4Me (3). Compound 3 is a new example of μ-κC-Ar dinuclear rhenium complex and has been obtained as para and meta isomers (3a,b). It is known from the literature that 2 can activate arenes and heteroarenes via reductive elimination of benzene and oxidative addition of CH bonds to the dinuclear fragment. Here we have studied the reaction of 2 with C6D6 and H2CC(H)Ph and determined the kinetic constants by 1H NMR (1.4 × 10−5 s−1 at 308 K and 1.1 × 10−5 s−1 at 298 K, respectively). The results indicate that the rate-determining step of the reaction is the reductive elimination of benzene, while the oxidative addition is fast. Water and methanol react with 1 in toluene at room temperature to give the hydroxo and methoxo hydrido complexes [Re2(μ-H)(μ-OR)(CO)8], RH (5) and CH3 (6). On reacting 1 with water in deuterated toluene, and monitoring by 1H/2H NMR, a preferential deuteration of the hydride site to give [Re2(μ-D)(μ-OH)(CO)8] is evidenced. This finding excludes the oxidative addition of water on the dinuclear “Re2(CO)8” fragment while supporting a heterolytic addition of water via protonation at the µ-κC-tolyl group, elimination of toluene and addition of OH−. Single crystal X-ray diffraction analyses have been performed for complexes 3a, 5 and 6 and their solid state structures have been determined. In particular, the crystal structure of 5 results in a new polymorphic form (5b) and it is discussed in comparison with the already known one (5a).
{"title":"Facile CH aryl and OH bonds activation at dirhenium site of [Re2(CO)8(THF)2] complex","authors":"Daniela Maggioni, Pierluigi Mercandelli, Lucia Carlucci","doi":"10.1016/j.ica.2024.122384","DOIUrl":"10.1016/j.ica.2024.122384","url":null,"abstract":"<div><div>The activation of small molecules is a topic of great interest and previously we reported on the easy activation of different types of E<img>H bonds at the dinuclear complex [Re<sub>2</sub>(CO)<sub>8</sub>(THF)<sub>2</sub>] (<strong>1</strong>) where labile THF molecules coordinate to adjacent rhenium(0) atoms. Here we extend the reactivity of <strong>1</strong> reporting on the oxidative addition of benzene and toluene at room temperature to give [Re<sub>2</sub>(μ-H)(μ-κ<em>C</em>-Ar)(CO)<sub>8</sub>], Ar = −C<sub>6</sub>H<sub>5</sub> (<strong>2</strong>) and −C<sub>6</sub>H<sub>4</sub>Me (<strong>3</strong>). Compound <strong>3</strong> is a new example of μ-κ<em>C</em>-Ar dinuclear rhenium complex and has been obtained as <em>para</em> and <em>meta</em> isomers (<strong>3a</strong>,<strong>b</strong>). It is known from the literature that <strong>2</strong> can activate arenes and heteroarenes via reductive elimination of benzene and oxidative addition of C<img>H bonds to the dinuclear fragment. Here we have studied the reaction of <strong>2</strong> with C<sub>6</sub>D<sub>6</sub> and H<sub>2</sub>C<img>C(H)Ph and determined the kinetic constants by <sup>1</sup>H NMR (1.4 × 10<sup>−5</sup> s<sup>−1</sup> at 308 K and 1.1 × 10<sup>−5</sup> s<sup>−1</sup> at 298 K, respectively). The results indicate that the rate-determining step of the reaction is the reductive elimination of benzene, while the oxidative addition is fast. Water and methanol react with <strong>1</strong> in toluene at room temperature to give the hydroxo and methoxo hydrido complexes [Re<sub>2</sub>(μ-H)(μ-OR)(CO)<sub>8</sub>], R<img>H (<strong>5</strong>) and CH<sub>3</sub> (<strong>6</strong>). On reacting <strong>1</strong> with water in deuterated toluene, and monitoring by <sup>1</sup>H/<sup>2</sup>H NMR, a preferential deuteration of the hydride site to give [Re<sub>2</sub>(μ-D)(μ-OH)(CO)<sub>8</sub>] is evidenced. This finding excludes the oxidative addition of water on the dinuclear “Re<sub>2</sub>(CO)<sub>8</sub>” fragment while supporting a heterolytic addition of water via protonation at the µ-κ<em>C</em>-tolyl group, elimination of toluene and addition of OH<sup>−</sup>. Single crystal X-ray diffraction analyses have been performed for complexes <strong>3a</strong>, <strong>5</strong> and <strong>6</strong> and their solid state structures have been determined. In particular, the crystal structure of <strong>5</strong> results in a new polymorphic form (<strong>5b</strong>) and it is discussed in comparison with the already known one (<strong>5a</strong>).</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"574 ","pages":"Article 122384"},"PeriodicalIF":2.7,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142319073","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 : 2024-09-18DOI: 10.1016/j.ica.2024.122377
Colani T. Fakude, Aderemi B. Haruna, Kenneth I. Ozoemena
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":"Colani T. Fakude, Aderemi B. Haruna, Kenneth I. Ozoemena","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":"574 ","pages":"Article 122377"},"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
Aparup Paul , Horst Puschmann , Subal Chandra Manna
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":"Aparup Paul , Horst Puschmann , Subal Chandra Manna","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":"574 ","pages":"Article 122379"},"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
Mohammad Kaikhosravi , Hassan Hadadzadeh , Hossein Farrokhpour , Michael J. Sauer , Alexander D. Böth , Robert M. Reich , Fritz E. Kühn
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":"Mohammad Kaikhosravi , Hassan Hadadzadeh , Hossein Farrokhpour , Michael J. Sauer , Alexander D. Böth , Robert M. Reich , Fritz E. Kühn","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":"574 ","pages":"Article 122383"},"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}
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":"Ya-Meng Zhu, Dan-Dan Lu, Zhi-Cui Zhang, Ai-Quan Jia, Qian-Feng Zhang","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":"574 ","pages":"Article 122373"},"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
Bulat A. Faizullin , Yulia S. Spiridonova , Kirill V. Kholin , Mikhail N. Khrizanforov , Igor A. Litvinov , Alexandra D. Voloshina , Andrey A. Parfenov , Elvira I. Musina , Igor D. Strelnik , Andrey A. Karasik , Asiya R. Mustafina
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":"Bulat A. Faizullin , Yulia S. Spiridonova , Kirill V. Kholin , Mikhail N. Khrizanforov , Igor A. Litvinov , Alexandra D. Voloshina , Andrey A. Parfenov , Elvira I. Musina , Igor D. Strelnik , Andrey A. Karasik , Asiya R. Mustafina","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":"574 ","pages":"Article 122382"},"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
Peter L. Rodríguez-Kessler , Alvaro Muñoz-Castro
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":"Peter L. Rodríguez-Kessler , Alvaro Muñoz-Castro","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":"574 ","pages":"Article 122376"},"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
Sudesh M. Morajkar , Delicia A. Barretto , Savita A. Kundaikar
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":"Sudesh M. Morajkar , Delicia A. Barretto , Savita A. Kundaikar","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":"574 ","pages":"Article 122380"},"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}
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