Pub Date : 2024-11-29DOI: 10.1016/j.ica.2024.122458
Emine Özge Karaca , Ebru Mızrak , Nevin Gürbüz , Erdem Çetinkaya , Hüseyin Karcı , Muhammed Dündar , İlknur Özdemir , Ahmet Koç , İsmail Özdemir , Waleed koko , Sadeq M. Al-Hazmy , Naceur Hamdi
In this study, a new series of 1-(2-ethylhexyl)-3-(alkyl)-5,6-dimethylbenzimidazol-2-ylidene]silver(I) complexes has been synthesized and investigated their in vitro antibacterial, antifungal and anticancer properties. All molecules were characterized by 1H NMR, 13C NMR, and IR spectroscopy techniques. In vitro antimicrobial activity of the synthesized compounds investigated in this work was tested against the reference strains: Escherichia coli (ATCC 25922), Staphylococcus aureus (ATCC 29213) and Pseudomonas aeruginosa (ATCC 27853), Candida albicans (ATCC MYA-2876) and Candida glabrata (ATCC 2001). Anticancer properties of samples were evaluated against A549, HCT116 and BEAS-2B cells lines. All silver-NHC complexes showed antibacterial activity against the tested bacterial and fungal strains.
{"title":"Novel N-heterocyclic carbene silver(I) complexes: Synthesis, structural characterization, antimicrobial and cytotoxicity potential studies","authors":"Emine Özge Karaca , Ebru Mızrak , Nevin Gürbüz , Erdem Çetinkaya , Hüseyin Karcı , Muhammed Dündar , İlknur Özdemir , Ahmet Koç , İsmail Özdemir , Waleed koko , Sadeq M. Al-Hazmy , Naceur Hamdi","doi":"10.1016/j.ica.2024.122458","DOIUrl":"10.1016/j.ica.2024.122458","url":null,"abstract":"<div><div>In this study, a new series of 1-(2-ethylhexyl)-3-(alkyl)-5,6-dimethylbenzimidazol-2-ylidene]silver(I) complexes has been synthesized and investigated their in vitro antibacterial, antifungal and anticancer properties. All molecules were characterized by <sup>1</sup>H NMR, <sup>13</sup>C NMR, and IR spectroscopy techniques. In vitro antimicrobial activity of the synthesized compounds investigated in this work was tested against the reference strains: <em>Escherichia coli</em> (ATCC 25922), <em>Staphylococcus aureus</em> (ATCC 29213) and <em>Pseudomonas aeruginosa</em> (ATCC 27853), <em>Candida albicans</em> (ATCC MYA-2876) and <em>Candida glabrata</em> (ATCC 2001). Anticancer properties of samples were evaluated against <em>A549</em>, <em>HCT116</em> and <em>BEAS-2B</em> cells lines. All silver-NHC complexes showed antibacterial activity against the tested bacterial and fungal strains.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"577 ","pages":"Article 122458"},"PeriodicalIF":2.7,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747603","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-28DOI: 10.1016/j.ica.2024.122479
Xin–yu Zhao, Wei Zhang, Ya–shuang Zhu, Xiang Wang
Employing polyoxometalate–based hybrid materials combined from metal–organic complex and polyoxometalate as photocatalysts for pollutant degradation and capacitive electrodes has become a research focus. In order to continue to develop the potential photocatalysts and electrode materials, four octamolybdate–based hybrids constructed from phenanthroline derivative ligands 1, 10 − phenanthroline − 5, 6 − dione (PDO) and 1, 10 − phenanthroline − 5, 6 − diamine (PDA) were isolated. The [β − Mo8O26]4− anions were involved in the structures of 1–3, which were aggregated by Cu ions into a two–dimensional layer decorated by PDO or PDA ligands in 1 and 2, but discrete and coexist with [Co(H2O)2(PDO)2]2+ metal–organic components in 3. 4 featured [α − Mo8O26]4− anions bi–supported by two [Co(H2O)(PDA)2]2+ metal–organic fragments. The introduction of metal–organic complexes of metal/PDO or PDA improved the light absorption, conductivity and electrochemical active surface area of these hybrid compounds. Consequently, compounds 1–4 as photocatalysts showed photocatalytic activity for degradation of organic dyes with good recyclability and stability at least 3 cycles. The possible photocatalytic degradation mechanism was discussed. Additionally, compounds 1–4 employed as electrode materials demonstrated good capacitive performances, especially 4 with the specific capacitance of 1385.3F g−1 at the current density of 1 A/g.
{"title":"Four octamolybdate–based hybrid compounds consisting of phenanthroline derivative ligands with photocatalytic and capacitive performances","authors":"Xin–yu Zhao, Wei Zhang, Ya–shuang Zhu, Xiang Wang","doi":"10.1016/j.ica.2024.122479","DOIUrl":"10.1016/j.ica.2024.122479","url":null,"abstract":"<div><div>Employing polyoxometalate–based hybrid materials combined from metal–organic complex and polyoxometalate as photocatalysts for pollutant degradation and capacitive electrodes has become a research focus. In order to continue to develop the potential photocatalysts and electrode materials, four octamolybdate–based hybrids constructed from phenanthroline derivative ligands 1, 10 − phenanthroline − 5, 6 − dione (PDO) and 1, 10 − phenanthroline − 5, 6 − diamine (PDA) were isolated. The [β − Mo<sub>8</sub>O<sub>26</sub>]<sup>4−</sup> anions were involved in the structures of <strong>1</strong>–<strong>3</strong>, which were aggregated by Cu ions into a two–dimensional layer decorated by PDO or PDA ligands in <strong>1</strong> and <strong>2</strong>, but discrete and coexist with [Co(H<sub>2</sub>O)<sub>2</sub>(PDO)<sub>2</sub>]<sup>2+</sup> metal–organic components in <strong>3</strong>. <strong>4</strong> featured [α − Mo<sub>8</sub>O<sub>26</sub>]<sup>4−</sup> anions bi–supported by two [Co(H<sub>2</sub>O)(PDA)<sub>2</sub>]<sup>2+</sup> metal–organic fragments. The introduction of metal–organic complexes of metal/PDO or PDA improved the light absorption, conductivity and electrochemical active surface area of these hybrid compounds. Consequently, compounds <strong>1</strong>–<strong>4</strong> as photocatalysts showed photocatalytic activity for degradation of organic dyes with good recyclability and stability at least 3 cycles. The possible photocatalytic degradation mechanism was discussed. Additionally, compounds <strong>1</strong>–<strong>4</strong> employed as electrode materials demonstrated good capacitive performances, especially <strong>4</strong> with the specific capacitance of 1385.3F g<sup>−1</sup> at the current density of 1 A/g.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"577 ","pages":"Article 122479"},"PeriodicalIF":2.7,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747600","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-28DOI: 10.1016/j.ica.2024.122474
Daniele Florio, Daniela Marasco, Sara La Manna
Amyloids are abnormal protein aggregates that are associated with several neurodegenerative diseases, such as Alzheimer’s disease, Parkinson’s disease, and prion diseases. The development of neurodrugs able to modulate amyloid aggregation represents a promising avenue for therapeutic intervention in neurodegenerative diseases. In recent years, peptides and metal complexes have emerged as attractive modulators of amyloid aggregation. Peptide-based approaches include the design of inhibitors of the amyloid self-assembly process or inhibitors of amyloid cross-interactions that may target specific regions of the amyloid protein crucial for aggregation. Interactions between metals and amyloidogenic proteins also play a significant role in the formation and stabilization of amyloid aggregates. Thus, metal complexes and metal chelators offer strategies to interfere with these metal-protein interactions and modulate amyloid aggregation. These complexes act by targeting the metal ions involved in amyloid aggregation, thereby disrupting their binding to amyloid peptides, inhibiting aggregation processes, and mitigating associated neurotoxicity. This comprehensive analysis emphasizes the considerable potential of peptides and metal complexes as effective modulators of amyloid aggregation, paving the way for the development of innovative peptide and metal-based neurodrugs with promising therapeutic applications in neurodegenerative disorders.
{"title":"Approaches for developing peptide- and metal complexes- or chelators-based leads for anti-amyloid drugs","authors":"Daniele Florio, Daniela Marasco, Sara La Manna","doi":"10.1016/j.ica.2024.122474","DOIUrl":"10.1016/j.ica.2024.122474","url":null,"abstract":"<div><div>Amyloids are abnormal protein aggregates that are associated with several neurodegenerative diseases, such as Alzheimer’s disease, Parkinson’s disease, and prion diseases. The development of neurodrugs able to modulate amyloid aggregation represents a promising avenue for therapeutic intervention in neurodegenerative diseases. In recent years, peptides and metal complexes have emerged as attractive modulators of amyloid aggregation. Peptide-based approaches include the design of inhibitors of the amyloid self-assembly process or inhibitors of amyloid cross-interactions that may target specific regions of the amyloid protein crucial for aggregation. Interactions between metals and amyloidogenic proteins also play a significant role in the formation and stabilization of amyloid aggregates. Thus, metal complexes and metal chelators offer strategies to interfere with these metal-protein interactions and modulate amyloid aggregation. These complexes act by targeting the metal ions involved in amyloid aggregation, thereby disrupting their binding to amyloid peptides, inhibiting aggregation processes, and mitigating associated neurotoxicity. This comprehensive analysis emphasizes the considerable potential of peptides and metal complexes as effective modulators of amyloid aggregation, paving the way for the development of innovative peptide and metal-based neurodrugs with promising therapeutic applications in neurodegenerative disorders.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"577 ","pages":"Article 122474"},"PeriodicalIF":2.7,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747601","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 synthesis of a small family of copper(I) complexes bound to diimine and phosphine ligands, and their characterization, spectroscopic properties and application as pre-catalyst for azide–alkyne cycloaddition reaction are reported. Reaction of bis-(N-aryl)glyoxaldimine (p-R-C6H4NC(H)(H)CNC6H4-R-p; R = OCH3, CH3 and Cl; abbreviated as L-R) with [Cu(PPh3)2(NO3)] in refluxing methanol affords a group of three mixed-ligand copper(I) complexes of type [Cu(PPh3)2(L-R)]NO3, depicted respectively as complex 1 (R = OCH3), 2 (R = CH3) and 3 (R = Cl). Crystal structures of 1–3 have been determined by X-ray diffraction analysis. In each complex, the copper(I) center is nested in a nearly tetrahedral N2P2 coordination environment. Complexes 1–3 exhibit two intense absorptions spanning over the visible and ultraviolet regions. Origin of these absorptions was probed with DFT and TDDFT calculations, which revealed that the lower energy absorption at 346–380 nm is due to an allowed copper-to-diimine charge-transfer transition, and the second absorption near 270 nm is largely due to an intra-phosphine charge-transfer transition. These complexes also show prominent emission spectra while excited at 320 nm. These copper(I) complexes are found to serve as efficient precursor for catalytic azide–alkyne cycloaddition reaction under relatively mild condition, and offering a broad substrate scope.
{"title":"Development of phosphine and diimine stabilized copper(I) catalysts for efficient azide–alkyne cycloaddition","authors":"Suprabha Pradhan , Aparajita Mukherjee , Samaresh Bhattacharya","doi":"10.1016/j.ica.2024.122470","DOIUrl":"10.1016/j.ica.2024.122470","url":null,"abstract":"<div><div>The synthesis of a small family of copper(I) complexes bound to diimine and phosphine ligands, and their characterization, spectroscopic properties and application as pre-catalyst for azide–alkyne cycloaddition reaction are reported. Reaction of bis-(<em>N</em>-aryl)glyoxaldimine (<em>p</em>-R-C<sub>6</sub>H<sub>4</sub>N<img>C(H)(H)C<img>NC<sub>6</sub>H<sub>4</sub>-R-<em>p</em>; R = OCH<sub>3</sub>, CH<sub>3</sub> and Cl; abbreviated as L-R) with [Cu(PPh<sub>3</sub>)<sub>2</sub>(NO<sub>3</sub>)] in refluxing methanol affords a group of three mixed-ligand copper(I) complexes of type [Cu(PPh<sub>3</sub>)<sub>2</sub>(L-R)]NO<sub>3</sub>, depicted respectively as complex <strong>1</strong> (R = OCH<sub>3</sub>), <strong>2</strong> (R = CH<sub>3</sub>) and <strong>3</strong> (R = Cl). Crystal structures of <strong>1</strong>–<strong>3</strong> have been determined by X-ray diffraction analysis. In each complex, the copper(I) center is nested in a nearly tetrahedral N<sub>2</sub>P<sub>2</sub> coordination environment. Complexes <strong>1</strong>–<strong>3</strong> exhibit two intense absorptions spanning over the visible and ultraviolet regions. Origin of these absorptions was probed with DFT and TDDFT calculations, which revealed that the lower energy absorption at 346–380 nm is due to an allowed copper-to-diimine charge-transfer transition, and the second absorption near 270 nm is largely due to an intra-phosphine charge-transfer transition. These complexes also show prominent emission spectra while excited at 320 nm. These copper(I) complexes are found to serve as efficient precursor for catalytic azide–alkyne cycloaddition reaction under relatively mild condition, and offering a broad substrate scope.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"577 ","pages":"Article 122470"},"PeriodicalIF":2.7,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142756864","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-26DOI: 10.1016/j.ica.2024.122472
Yuting Liu , Zixu Zhang , Dawei Yin , Yukai Huang , Ruilin Zheng , Yi Zhou , Jiabao Chen , Chi Dang
Sulfide (S2−), silicate (SiO32−) and dichromate (Cr2O72−) ions are prevalent contaminants in industrial effluents, and their rapid and accurate detection is of critical importance for environmental monitoring. In this study, we utilized an environmentally friendly, highly efficient, and biodegradable deep eutectic solvent (DES) to catalyze the synthesis of 2-(((5-phenyl-1,3,4-thiadiazol-2-yl)imino)methyl)phenol (Probe M). Probe M exhibits excellent selectivity for S2−, SiO32− and Cr2O72−, and the corresponding color changes can be readily detected by the naked eye. Upon addition of S2− and SiO32− to the probe solution, the solution turns a distinct orange-red, while the addition of Cr2O72− results in a pronounced darkening of the solution. The detection of S2− and SiO32− by probe M under alkaline condition is stable, and the detection of Cr2O72− under acidic condition is stable. Fluorescence titration experiments revealed that probe M forms a 1:2 stoichiometric complex with S2−, SiO32− and Cr2O72−, with binding constants of 3.84 × 104 M−1, 1.86 × 104 M−1 and 3.19 × 104 M−1, respectively. The detection limits were determined to be 1.76 × 10−4 M for S2−, 9.15 × 10−5 M for SiO32−, and 2.13 × 10−4 M for Cr2O72−. The dipstick experiment demonstrates the probe M can be used as a solid-state sensor to identify S2−, SiO32− and Cr2O72−.
{"title":"Green synthesis of thiadiazole Schiff bases and specific recognition of Cr2O72−, SiO32− and S2−","authors":"Yuting Liu , Zixu Zhang , Dawei Yin , Yukai Huang , Ruilin Zheng , Yi Zhou , Jiabao Chen , Chi Dang","doi":"10.1016/j.ica.2024.122472","DOIUrl":"10.1016/j.ica.2024.122472","url":null,"abstract":"<div><div>Sulfide (S<sup>2−</sup>), silicate (SiO<sub>3</sub><sup>2−</sup>) and dichromate (Cr<sub>2</sub>O<sub>7</sub><sup>2−</sup>) ions are prevalent contaminants in industrial effluents, and their rapid and accurate detection is of critical importance for environmental monitoring. In this study, we utilized an environmentally friendly, highly efficient, and biodegradable deep eutectic solvent (DES) to catalyze the synthesis of 2-(((5-phenyl-1,3,4-thiadiazol-2-yl)imino)methyl)phenol (Probe M). Probe M exhibits excellent selectivity for S<sup>2−</sup>, SiO<sub>3</sub><sup>2−</sup> and Cr<sub>2</sub>O<sub>7</sub><sup>2−</sup>, and the corresponding color changes can be readily detected by the naked eye. Upon addition of S<sup>2−</sup> and SiO<sub>3</sub><sup>2−</sup> to the probe solution, the solution turns a distinct orange-red, while the addition of Cr<sub>2</sub>O<sub>7</sub><sup>2−</sup> results in a pronounced darkening of the solution. The detection of S<sup>2−</sup> and SiO<sub>3</sub><sup>2−</sup> by probe M under alkaline condition is stable, and the detection of Cr<sub>2</sub>O<sub>7</sub><sup>2−</sup> under acidic condition is stable. Fluorescence titration experiments revealed that probe M forms a 1:2 stoichiometric complex with S<sup>2−</sup>, SiO<sub>3</sub><sup>2−</sup> and Cr<sub>2</sub>O<sub>7</sub><sup>2−</sup>, with binding constants of 3.84 × 10<sup>4</sup> M<sup>−1</sup>, 1.86 × 10<sup>4</sup> M<sup>−1</sup> and 3.19 × 10<sup>4</sup> M<sup>−1</sup>, respectively. The detection limits were determined to be 1.76 × 10<sup>−4</sup> M for S<sup>2−</sup>, 9.15 × 10<sup>−5</sup> M for SiO<sub>3</sub><sup>2−</sup>, and 2.13 × 10<sup>−4</sup> M for Cr<sub>2</sub>O<sub>7</sub><sup>2−</sup>. The dipstick experiment demonstrates the probe M can be used as a solid-state sensor to identify S<sup>2−</sup>, SiO<sub>3</sub><sup>2−</sup> and Cr<sub>2</sub>O<sub>7</sub><sup>2−</sup>.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"577 ","pages":"Article 122472"},"PeriodicalIF":2.7,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747599","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-16DOI: 10.1016/j.ica.2024.122450
Carla Gabriela Martínez-De-León, Aurora Rodríguez-Álvarez, Victor Barba, Herbert Höpfl, Jean-Michel Grévy
Four indole-substituted tridentate iminophosphorane ligands carrying NN’S- and NN’Se-donor atoms, i.e., HLSMe, HLSPh, HLSeMe and HLSePh, were prepared and combined with [Pt(SMe2)2Cl2] to yield complexes of the compositions [Pt(LSMe)Cl] (1a), [Pt(LSPh)Cl] (1b), [Pt(LSeMe)Cl] (2a) and [Pt(LSePh)Cl] (2b). Product characterization by elemental analysis, mass spectrometry, NMR spectroscopy (1H/13C/31P) and single-crystal X-ray diffraction revealed complexes with metal ions embedded in unsymmetrical square-planar coordination environments and largely planar ligand skeletons with extensive π-delocalization. The residual Pt-Cl bond and multiple options for ligand structure modification make this Pt(II) complex class promising for the future development of catalytic and pharmaceutical applications.
{"title":"Unsymmetrical Pt(II) pincer complexes of tridentate NN’S- and NN’Se-mono(iminophosphorane) ligands: Synthesis, characterization and solid state structure","authors":"Carla Gabriela Martínez-De-León, Aurora Rodríguez-Álvarez, Victor Barba, Herbert Höpfl, Jean-Michel Grévy","doi":"10.1016/j.ica.2024.122450","DOIUrl":"10.1016/j.ica.2024.122450","url":null,"abstract":"<div><div>Four indole-substituted tridentate iminophosphorane ligands carrying NN’S- and NN’Se-donor atoms, i.e., HL<em><sup>SMe</sup></em>, HL<em><sup>SPh</sup></em>, HL<em><sup>SeMe</sup></em> and HL<em><sup>SePh</sup></em>, were prepared and combined with [Pt(SMe<sub>2</sub>)<sub>2</sub>Cl<sub>2</sub>] to yield complexes of the compositions [Pt(L<em><sup>SMe</sup></em>)Cl] (<strong>1a</strong>), [Pt(L<em><sup>SPh</sup></em>)Cl] (<strong>1b</strong>), [Pt(L<em><sup>SeMe</sup></em>)Cl] (<strong>2a</strong>) and [Pt(L<em><sup>SePh</sup></em>)Cl] (<strong>2b</strong>). Product characterization by elemental analysis, mass spectrometry, NMR spectroscopy (<sup>1</sup>H/<sup>13</sup>C/<sup>31</sup>P) and single-crystal X-ray diffraction revealed complexes with metal ions embedded in unsymmetrical square-planar coordination environments and largely planar ligand skeletons with extensive π-delocalization. The residual Pt-Cl bond and multiple options for ligand structure modification make this Pt(II) complex class promising for the future development of catalytic and pharmaceutical applications.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"577 ","pages":"Article 122450"},"PeriodicalIF":2.7,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747602","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-16DOI: 10.1016/j.ica.2024.122452
Yuan Zhang , Yong-Qing Qiu , Yuan-Yuan Zhao , E. Yong-Sheng , Shuang-Qi Li , Chang-Wei An
In this work, some triangular monometal complexes and polymetallic alkynyl bipyridine Pt(II) metallacycles are systematically investigated to reveal the effect of the dimensions and combinations of graphyne fragment dehydrobenzo[12]annulene (DBA) modules ligands on the third-order nonlinear optical (NLO) properties via density functional theory. It is found that the insertion of alkynyl- or phenyl-alkynyl into triangular metallacyclic ligand significantly improves the second hyperpolarizability of monometal complexes. Furthermore, the absorption wavelengths are located in the visible region for all complexes, indicating their potential as viable candidates for practical NLO materials. Impressively, the bow-tie type binuclear Pt(II) complex 2a and the linear-shaped trinuclear metallacycle 3a exhibit higher third-order NLO responses compared to other analogues. It is worth noting that the trinuclear Pt(II) metallacycles show significantly large second hyperpolarizabilities up to 35.85 × 105 a.u. and 71.49 × 105 a.u. respectively, which is mainly attributable to small transition energies and the decreased energy gap between the HOMO and LUMO. The take home messages suggest that incorporating intriguing fused DBA ligands into polymetallic complex frameworks is considered an effective method for tuning the third-order NLO responses. Overall, we expect that this study will be helpful in providing valuable guidelines for constructing cost-effective and high-performance organometallic NLO materials.
{"title":"Alkynyl bipyridine Pt(II) metallacycles with various combinations of dehydrobenzo[12]annulenes unit ligands showing high third-order nonlinear optical responses","authors":"Yuan Zhang , Yong-Qing Qiu , Yuan-Yuan Zhao , E. Yong-Sheng , Shuang-Qi Li , Chang-Wei An","doi":"10.1016/j.ica.2024.122452","DOIUrl":"10.1016/j.ica.2024.122452","url":null,"abstract":"<div><div>In this work, some triangular monometal complexes and polymetallic alkynyl bipyridine Pt(II) metallacycles are systematically investigated to reveal the effect of the dimensions and combinations of graphyne fragment dehydrobenzo[12]annulene (DBA) modules ligands on the third-order nonlinear optical (NLO) properties via density functional theory. It is found that the insertion of alkynyl- or phenyl-alkynyl into triangular metallacyclic ligand significantly improves the second hyperpolarizability of monometal complexes. Furthermore, the absorption wavelengths are located in the visible region for all complexes, indicating their potential as viable candidates for practical NLO materials. Impressively, the bow-tie type binuclear Pt(II) complex 2a and the linear-shaped trinuclear metallacycle 3a exhibit higher third-order NLO responses compared to other analogues. It is worth noting that the trinuclear Pt(II) metallacycles show significantly large second hyperpolarizabilities up to 35.85 × 10<sup>5</sup> a.u. and 71.49 × 10<sup>5</sup> a.u. respectively, which is mainly attributable to small transition energies and the decreased energy gap between the HOMO and LUMO. The take home messages suggest that incorporating intriguing fused DBA ligands into polymetallic complex frameworks is considered an effective method for tuning the third-order NLO responses. Overall, we expect that this study will be helpful in providing valuable guidelines for constructing cost-effective and high-performance organometallic NLO materials.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"575 ","pages":"Article 122452"},"PeriodicalIF":2.7,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142702416","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-15DOI: 10.1016/j.ica.2024.122445
Marina A. Uvarova , Fedor M. Dolgushin , Konstantin A. Babeshkin , Nikolay N. Efimov , Natalia V. Gogoleva , Denis N. Nebykov , Anastasia V. Lagutina , Alexandr O. Panov , Vladimir M. Mokhov , Olga B. Bekker , Konstantin O. Titov , Irina A. Lutsenko , Igor L. Eremenko
Series of complexes of the composition [M(L)2(Hdmpz)n] (L = fur, M = CoII, n = 2 (1), n = 4 (2), M = NiII, n = 2 (3), L = tph, M = CoII, n = 2 (4), M = NiII, n = 2 (5), n = 4 (6)) has been obtained by interaction of cobaltII and nickelII acetates with 3-furancarboxylic (Hfur) or 2-thiophencarboxylic (Htph) acids, followed by the addition of 3,5-dimethylpyrazole (Hdmpz). According to the X-ray data in complex 1–6, metal atoms are surrounded by carboxylate anions and two or four monodentately coordinated Hdmpz molecules. Additional stabilization of the complexes is carried out by the inter- and intramolecular hydrogen bonds. Co and Ni catalysts obtained by chemical activation of 1 and 3 exhibit high catalytic activity in a continuous dicyclopentadiene (DCPD) hydrogenation process at atmospheric hydrogen pressure. Slow relaxation of magnetization has been found for complexes by use of ac-magnetometry for compounds 1 and 4 at 1000 Oe dc-field in contrast with 2, 3, 5, 6 exhibiting no slow magnetic relaxation. Biological activity of 1–6 has been determined against a non-pathogenic strain of Mycobacterium smegmatis.
{"title":"Versatile CoII and NiII mononuclear complexes with furoate/thiophencarboxylate anions and 3,5-dimethylpyrazole– Synthesis, structure, magnetic, catalytic and antimycobacterial properties","authors":"Marina A. Uvarova , Fedor M. Dolgushin , Konstantin A. Babeshkin , Nikolay N. Efimov , Natalia V. Gogoleva , Denis N. Nebykov , Anastasia V. Lagutina , Alexandr O. Panov , Vladimir M. Mokhov , Olga B. Bekker , Konstantin O. Titov , Irina A. Lutsenko , Igor L. Eremenko","doi":"10.1016/j.ica.2024.122445","DOIUrl":"10.1016/j.ica.2024.122445","url":null,"abstract":"<div><div>Series of complexes of the composition [M(L)<sub>2</sub>(Hdmpz)<sub>n</sub>] (L = fur, M = Co<sup>II</sup>, n = 2 (<strong>1</strong>), n = 4 (<strong>2</strong>), M = Ni<sup>II</sup>, n = 2 (<strong>3</strong>), L = tph, M = Co<sup>II</sup>, n = 2 (<strong>4</strong>), M = Ni<sup>II</sup>, n = 2 (<strong>5</strong>), n = 4 (<strong>6</strong>)) has been obtained by interaction of cobalt<sup>II</sup> and nickel<sup>II</sup> acetates with 3-furancarboxylic (Hfur) or 2-thiophencarboxylic (Htph) acids, followed by the addition of 3,5-dimethylpyrazole (Hdmpz). According to the X-ray data in complex <strong>1</strong>–<strong>6</strong>, metal atoms are surrounded by carboxylate anions and two or four monodentately coordinated Hdmpz molecules. Additional stabilization of the complexes is carried out by the inter- and intramolecular hydrogen bonds. Co and Ni catalysts obtained by chemical activation of <strong>1</strong> and <strong>3</strong> exhibit high catalytic activity in a continuous dicyclopentadiene (DCPD) hydrogenation process at atmospheric hydrogen pressure<em>.</em> Slow relaxation of magnetization has been found for complexes by use of ac-magnetometry for compounds <strong>1</strong> and <strong>4</strong> at 1000 Oe dc-field in contrast with <strong>2, 3, 5, 6</strong> exhibiting no slow magnetic relaxation. Biological activity of <strong>1</strong>–<strong>6</strong> has been determined against a non-pathogenic strain of <em>Mycobacterium smegmatis.</em></div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"575 ","pages":"Article 122445"},"PeriodicalIF":2.7,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142652515","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-13DOI: 10.1016/j.ica.2024.122449
Li-Ping Na , Tao Zheng , Zhang Cai , Na Tuo , Yi-Fan Ding , Chen Chen , Wen-Kui Dong
Based on salicylaldehyde unit, we designed and synthesized a novel fluorescent chemical probe DSS, which has a flexible long chain and contains ten methylene units. The experimental results showed that the fluorescent probe DSS can efficiently and selectively recognize Cr2O72− anions, having a detection limit LOD of 1.14 × 10−7 M. Additionally, the binding constant (Ka) of the probe was 3.75 × 104 M−1, the minimum quantification limit LOQ was as low as 3.82 × 10−7 M. We systematically studied the recognition mechanism of fluorescence chemical sensor DSS through fluorescence and UV visible spectroscopy. Significantly, the fluorescence of the chemosensor DSS can be remarkably quenched by Cr2O72−via the Internal Filtering Effect (IFE). Based on this phenomenon, a novel salamo-like fluorescence method for detection of Cr2O72− was established. The proposed fluorescent method was successfully applied to the detection of Cr2O72− in rainwater, tap water, and Yellow River water.
{"title":"A flexible ten carbon long-chain salamo-like fluorescent probe for highly efficient and selective recognition of Cr2O72− ions, mechanism and practical application","authors":"Li-Ping Na , Tao Zheng , Zhang Cai , Na Tuo , Yi-Fan Ding , Chen Chen , Wen-Kui Dong","doi":"10.1016/j.ica.2024.122449","DOIUrl":"10.1016/j.ica.2024.122449","url":null,"abstract":"<div><div>Based on salicylaldehyde unit, we designed and synthesized a novel fluorescent chemical probe <strong>DSS</strong>, which has a flexible long chain and contains ten methylene units. The experimental results showed that the fluorescent probe <strong>DSS</strong> can efficiently and selectively recognize Cr<sub>2</sub>O<sub>7</sub><sup>2−</sup> anions, having a detection limit LOD of 1.14 × 10<sup>−7</sup> M. Additionally, the binding constant (<em>Ka</em>) of the probe was 3.75 × 10<sup>4</sup> M<sup>−1</sup>, the minimum quantification limit LOQ was as low as 3.82 × 10<sup>−7</sup> M. We systematically studied the recognition mechanism of fluorescence chemical sensor <strong>DSS</strong> through fluorescence and UV visible spectroscopy. Significantly, the fluorescence of the chemosensor <strong>DSS</strong> can be remarkably quenched by Cr<sub>2</sub>O<sub>7</sub><sup>2−</sup> <em>via</em> the Internal Filtering Effect (IFE). Based on this phenomenon, a novel salamo-like fluorescence method for detection of Cr<sub>2</sub>O<sub>7</sub><sup>2−</sup> was established. The proposed fluorescent method was successfully applied to the detection of Cr<sub>2</sub>O<sub>7</sub><sup>2−</sup> in rainwater, tap water, and Yellow River water.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"575 ","pages":"Article 122449"},"PeriodicalIF":2.7,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142652514","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-13DOI: 10.1016/j.ica.2024.122444
Cristian Pinzón-Vanegas, Josue Valdes-García, Alejandro O. Viviano-Posadas, Juan Pablo León-Gómez, Simón Hernández-Ortega, Alejandro Dorazco-González
The understanding of the non-covalent halogen…halogen interaction inside coordination complexes has special interest as design tools in crystal engineering and coordination chemistry. In this work, we show the use of the supramolecular C-Br…Br-C interactions as a tool in the crystalline organization of a Ni(II) complex and its solvatochromic properties. To do so, we selected the 3,4,5,6-tetrabromophthalate (TBrPh) ligand where the Br atoms pointing outside to favor their self-assembly through these interactions.
Thus, a novel complex, [Ni(tmeda)(TBrPh)(H2O)3]•CH3OH was synthesized by the reaction between [Ni(tmeda)].(NO3)2 (tmeda = N, N, N’, N’-tetramethylethylenediamine) and K2TBrPh. The Ni(II)-complex was structurally analyzed by single-crystal X-ray diffraction, Hirshfeld surfaces, multiple analytical tools and DFT calculations.
Structural analysis shows that Ni(II)-complex has 1D supramolecular chains based on the cooperativity of intra/inter-molecular charged-assisted hydrogen bonds of type Ni-OH2…O and Csp2-Br…Br-Csp2 interactions into 2D networks. These Br…Br interactions organize the crystal packing in the solid state as is evidenced by the molecular electrostatic potential studies and Plot of Hirsfeld surface.
This Ni(II)-complex displays solvatochromism with a wide range of solvents (alcohols, DMF, CH3CN, chlorinated solvents), and solvent-dependent absorption maxima presents linear behavior as a function of their dielectric constant.
{"title":"Exploring supramolecular C-Br…Br-C interactions as organizing tools in a novel Ni(II)-tetrabromophthalate complex. Crystal structure and solvatochromism studies","authors":"Cristian Pinzón-Vanegas, Josue Valdes-García, Alejandro O. Viviano-Posadas, Juan Pablo León-Gómez, Simón Hernández-Ortega, Alejandro Dorazco-González","doi":"10.1016/j.ica.2024.122444","DOIUrl":"10.1016/j.ica.2024.122444","url":null,"abstract":"<div><div>The understanding of the non-covalent halogen<sup>…</sup>halogen interaction inside coordination complexes has special interest as design tools in crystal engineering and coordination chemistry. In this work, we show the use of the supramolecular C-Br<sup>…</sup>Br-C interactions as a tool in the crystalline organization of a Ni(II) complex and its solvatochromic properties. To do so, we selected the 3,4,5,6-tetrabromophthalate (TBrPh) ligand where the Br atoms pointing outside to favor their self-assembly through these interactions.</div><div>Thus, a novel complex, [Ni(tmeda)(TBrPh)(H<sub>2</sub>O)<sub>3</sub>]•CH<sub>3</sub>OH was synthesized by the reaction between [Ni(tmeda)].(NO<sub>3</sub>)<sub>2</sub> (tmeda = <em>N</em>, <em>N</em>, <em>N’</em>, <em>N’</em>-tetramethylethylenediamine) and K<sub>2</sub>TBrPh. The Ni(II)-complex was structurally analyzed by single-crystal X-ray diffraction, Hirshfeld surfaces, multiple analytical tools and DFT calculations.</div><div>Structural analysis shows that Ni(II)-complex has 1D supramolecular chains based on the cooperativity of intra/inter-molecular charged-assisted hydrogen bonds of type Ni-OH<sub>2</sub><sup>…</sup>O and C<em><sub>sp2</sub></em>-Br<sup>…</sup>Br-C<em><sub>sp2</sub></em> interactions into 2D networks. These Br<sup>…</sup>Br interactions organize the crystal packing in the solid state as is evidenced by the molecular electrostatic potential studies and Plot of Hirsfeld surface.</div><div>This Ni(II)-complex displays solvatochromism with a wide range of solvents (alcohols, DMF, CH<sub>3</sub>CN, chlorinated solvents), and solvent-dependent absorption maxima presents linear behavior as a function of their dielectric constant.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"575 ","pages":"Article 122444"},"PeriodicalIF":2.7,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142652513","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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