Pub Date : 2024-11-26DOI: 10.1016/j.poly.2024.117318
Sk Khalid Rahaman , Taposi Chatterjee , Kalamoddin Shaikh , Samim Khan , Masoom Raza Siddiqui , Saikh M. Wabaidur , Md Maidul Islam , Seikh Mafiz Alam , Mohammad Hedayetullah Mir
The present research study is centered around the synthesis, characterization, and biological application of a ternary mixed-ligand based binuclear Cu(II) complex [Cu2(trans-1,4-chdc)(4,4′-Me2-2,2′-bpy)2(5,5′-Me2-2,2′-bpy)2]·2(cis-H21,4-chdc)·2(BF4¯) (1) by meticulous incorporation of 4,4′-dimethyl-2,2′-bipyridine (4,4′-Me2-2,2′-bpy), 5,5′-dimethyl-2,2′-bipyridine (5,5′-Me2-2,2′-bpy) and cis- and trans- mixture of 1,4-cyclohexanedicarboxylic acid (H21,4-chdc). Hirshfeld analysis is employed to validate non-bonded interactions, demonstrating the existence of widespread π···π stacking interactions between adjacent 4,4′-Me2-2,2′-bpy ligands at a distance of 3.757 Å, forming a one-dimensional (1D) supramolecular polymer chain. The biological activity of complex 1 is explored via docking study, driven by the inherent biological inclination of the Cu(II) complexes. Agreeably, the coordination complex 1 displays a favorable binding to DNA, specifically binds to the major groove of DNA and the aromatic pyridine ring of the ligand partially intercalates into the base pairs with a binding constant (Kb) of 1.98 × 105 M−1.
{"title":"Synthesis, structural elucidation, and DNA binding behavior of a ternary copper(II) complex featuring substituted bipyridyl and dicarboxylate ligands","authors":"Sk Khalid Rahaman , Taposi Chatterjee , Kalamoddin Shaikh , Samim Khan , Masoom Raza Siddiqui , Saikh M. Wabaidur , Md Maidul Islam , Seikh Mafiz Alam , Mohammad Hedayetullah Mir","doi":"10.1016/j.poly.2024.117318","DOIUrl":"10.1016/j.poly.2024.117318","url":null,"abstract":"<div><div>The present research study is centered around the synthesis, characterization, and biological application of a ternary mixed-ligand based binuclear Cu(II) complex [Cu<sub>2</sub>(<em>trans</em>-1,4-chdc)(4,4′-Me<sub>2</sub>-2,2′-bpy)<sub>2</sub>(5,5′-Me<sub>2</sub>-2,2′-bpy)<sub>2</sub>]·2(<em>cis</em>-H<sub>2</sub>1,4-chdc)·2(BF<sub>4</sub>¯) (<strong>1</strong>) by meticulous incorporation of 4,4′-dimethyl-2,2′-bipyridine (4,4′-Me<sub>2</sub>-2,2′-bpy), 5,5′-dimethyl-2,2′-bipyridine (5,5′-Me<sub>2</sub>-2,2′-bpy) and <em>cis</em>- and<!--> <em>trans</em>- mixture of 1,4-cyclohexanedicarboxylic acid (H<sub>2</sub>1,4-chdc). Hirshfeld analysis is employed to validate non-bonded interactions, demonstrating the existence of widespread π···π stacking interactions between adjacent 4,4′-Me<sub>2</sub>-2,2′-bpy ligands at a distance of 3.757 Å, forming a one-dimensional (1D) supramolecular polymer chain. The biological activity of complex <strong>1</strong> is explored via docking study, driven by the inherent biological inclination of the Cu(II) complexes. Agreeably, the coordination complex <strong>1</strong> displays a favorable binding to DNA, specifically binds to the major groove of DNA and the aromatic pyridine ring of the ligand partially intercalates into the base pairs with a binding constant (<em>K<sub>b</sub></em>) of 1.98 × 10<sup>5</sup> M<sup>−1</sup>.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"266 ","pages":"Article 117318"},"PeriodicalIF":2.4,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142702862","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-26DOI: 10.1016/j.poly.2024.117320
Jawher Makhlouf , Youness El Bakri , Chin-Hung Lai , Arto Valkonen , Hatem A. Abuelizz , Rashad Al-Salahi , Wajda Smirani Sta
The cobalt (II) complexes have been synthesized from the reaction of the cationic entities (1-(2-methoxyphenyl) piperazine and the 1-(4-nitrophenyl) piperazine with metallic salt CoCl2·6H2O, then processing the evaporation crystal growth method at room temperature. The synthesized complexes have been fully characterized by single crystal X-ray diffraction, Hirshfeld surface analysis, as well as UV–visible, FTIR spectroscopy, Photoluminescence, and TGA/TDA analysis, and theoretical studies were also performed, in addition to the antioxidant DPPH+ radical and ABTS+ radical cation assays were performed. The crystal structural analysis reveals that both complexes crystallize in the orthorhombic system. The vibrational absorption bands were identified by infrared spectroscopy. The solid-state UV–visible absorption spectrum of the title compounds was obtained at room temperature to spotlight the optical properties. In the [300–700 K] range, the thermal behaviors were investigated and showed the decomposition of the two complexes with metal complexes residues. Hirshfeld surface analysis cum 2D fingerprint plots visualize the main intermolecular interactions with their contributions in the solid-state phase. The molecular geometries of both complexes obtained from the crystal structure were used for quantum chemical calculation. DPPH+ radical and ABTS+ radical cation assays were used to highlight the interesting antioxidant activity for both complexes, where the IC50 of compound (1) was greater than 45 mg.mL−1 and it was greater than 49 mg.mL−1 for compound (2). The anticancer activities of the complexes studied were also investigated in silico by molecular docking.
{"title":"Highlighting non-covalent interactions to molecular structure, electronic and vibrational spectra in a new hybrid organic–inorganic cobalt complexes: Synthesis, characterization, experimental and computational studies","authors":"Jawher Makhlouf , Youness El Bakri , Chin-Hung Lai , Arto Valkonen , Hatem A. Abuelizz , Rashad Al-Salahi , Wajda Smirani Sta","doi":"10.1016/j.poly.2024.117320","DOIUrl":"10.1016/j.poly.2024.117320","url":null,"abstract":"<div><div>The cobalt (II) complexes have been synthesized from the reaction of the cationic entities (1-(2-methoxyphenyl) piperazine and the 1-(4-nitrophenyl) piperazine with metallic salt CoCl<sub>2</sub>·6H<sub>2</sub>O, then processing the evaporation crystal growth method at room temperature. The synthesized complexes have been fully characterized by single crystal X-ray diffraction, Hirshfeld surface analysis, as well as UV–visible, FTIR spectroscopy, Photoluminescence, and TGA/TDA analysis, and theoretical studies were also performed, in addition to the antioxidant DPPH<sup><img>+</sup> <!-->radical and ABTS<sup><img>+</sup> <!-->radical cation assays were performed. The crystal structural analysis reveals that both complexes crystallize in the orthorhombic system. The vibrational absorption bands were identified by infrared spectroscopy. The solid-state UV–visible absorption spectrum of the title compounds was obtained at room temperature to spotlight the optical properties. In the [300–700 K] range, the thermal behaviors were investigated and showed the decomposition of the two complexes with metal complexes residues. Hirshfeld surface analysis cum 2D fingerprint plots visualize the main intermolecular interactions with their contributions in the solid-state phase. The molecular geometries of both complexes obtained from the crystal structure were used for quantum chemical calculation. DPPH<sup><img>+</sup> <!-->radical and ABTS<sup><img>+</sup> <!-->radical cation assays were used to highlight the interesting antioxidant activity for both complexes, where the IC<sub>50</sub> <!-->of compound (<strong>1</strong>) was greater than 45 mg.mL<sup>−1</sup> <!-->and it was greater than 49 mg.mL<sup>−1</sup> for compound (<strong>2</strong>). The anticancer activities of the complexes studied were also investigated in silico by molecular docking.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"266 ","pages":"Article 117320"},"PeriodicalIF":2.4,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142721119","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-26DOI: 10.1016/j.poly.2024.117316
Hatice Gamze Sogukomerogullari , Emine Aytar
SNS pincer type ligands (L1-L4) were metallized with RhCl(PPh3)3, yielding new SNS type Rh(I) complexes. Different techniques, including 31P NMR, UV–Vis, XPS, mass, elemental analysis, molar conductivity, and FT-IR were used to analyze the synthesized compounds. According to the spectral data, the molecular structure of Rh(I) complexes has a four-coordinated square planar geometry around the metal center. The complexes’ lack of conductivity properties demonstrates their non-electrolyte nature in solution. The novel SNS-type Rh(I) complexes efficiently catalyzed the coupling of a variety of epoxides and CO2 to create cyclic carbonates in the presence of DMAP as a Lewis base. Diverse cyclic carbonates were also synthesized under ideal conditions with good to perfect yields (2 h, 1.6 MPa, and 100 °C). Following the discovery of new SNS-type Rh(I) catalysts with outstanding catalytic performance, epoxide, the impact of the reaction time, base, CO2 pressure, and temperature was examined for these catalysts. The complex L3-Rh and DMAP displayed the highest catalytic activity (89.6 %) and selectivity (99.4 %) for the coupling of CO2 and ECH under optimum conditions (100 °C, 2 h, and 1.6 MPa).
{"title":"Assessment of four rhodium(I) complexes bearing SNS ligands for the catalytic reaction of chemical CO2 conversion to obtain cyclic carbonates","authors":"Hatice Gamze Sogukomerogullari , Emine Aytar","doi":"10.1016/j.poly.2024.117316","DOIUrl":"10.1016/j.poly.2024.117316","url":null,"abstract":"<div><div>SNS pincer type ligands (L1-L4) were metallized with RhCl(PPh<sub>3</sub>)<sub>3</sub>, yielding new SNS type Rh(I) complexes. Different techniques, including <sup>31</sup>P NMR, UV–Vis, XPS, mass, elemental analysis, molar conductivity, and FT-IR were used to analyze the synthesized compounds. According to the spectral data, the molecular structure of Rh(I) complexes has a four-coordinated square planar geometry around the metal center.<!--> <!-->The complexes’ lack of conductivity properties demonstrates their non-electrolyte nature in solution. The novel SNS-type Rh(I) complexes efficiently catalyzed the coupling of a variety of epoxides and CO<sub>2</sub> to create cyclic carbonates in the presence of DMAP as a Lewis base. Diverse cyclic carbonates were also synthesized under ideal conditions with good to perfect yields (2 h, 1.6 MPa, and 100 °C). Following the discovery of new SNS-type Rh(I) catalysts with outstanding catalytic performance, epoxide, the impact of the reaction time, base, CO<sub>2</sub> pressure, and temperature was examined for these catalysts. The complex <strong>L3-Rh</strong> and DMAP displayed the highest catalytic activity (89.6 %) and selectivity (99.4 %) for the coupling of CO<sub>2</sub> and ECH under optimum conditions (100 °C, 2 h, and 1.6 MPa).</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"267 ","pages":"Article 117316"},"PeriodicalIF":2.4,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142756854","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-22DOI: 10.1016/j.poly.2024.117313
Joaldo G. Arruda , Iran F. Silva , Wagner M. Faustino , Israel F. Costa , Hermi F. Brito , Albano N. Carneiro Neto , Christian Näther , Huayna Terraschke , Maria Cláudia F.C. Felinto , Victor M. Deflon , Ercules E.S. Teotonio
Three novel lanthanide dipivaloylmethanate (dpm) complexes of general formula [Ln(dpm)(NO3)2(tchpo)2], where Ln: Eu3+, Gd3+ and Tb3+, and tchpo: tricyclohexylphosphine oxide neutral ligand have been prepared and characterized by elemental analyses, absorption infrared spectroscopy, thermalgravimetric analyses, diffuse reflectance, and luminescence spectroscopies. Furthermore, the [Tb(dpm)(NO3)2(tchpo)2] complex was structurally characterized by the single crystal X-ray diffraction analysis. This complex exhibited high luminescence intensity in the green region. On the other hand, the analogous Eu3+-complex exhibited very low luminescence intensity due to an efficient luminescent quenching process via ligand-to-metal charge transfer (LMCT) state. Theoretical studies employing Time-Dependent Density Functional Theory (TD-DFT) calculations along with results obtained from the JOYSpectra platform, support this experimental result. Remarkably, despite the high values of non-radiative intramolecular energy transfer from excited ligand states (S1 and T1) to the excited levels of the Ln3+ ions, in the [Eu(dpm)(NO3)2(tchpo)2], the highest S1-LMCT rate (W = 1.2 × 1010 s−1) emphasizes that the primary luminescence quenching pathway is via depopulation of excited ligand states. Interestingly, the nitrogen atoms from nitrate ions play an essential role in the lanthanide chemical environment, which has been suggested by the analyses of the ligand field parameters charge factors () and effective polarizabilities () values.
{"title":"Luminescence in Ln3+ dipivaloylmethanate complexes: Spectroscopic and theoretical investigation on the energy transfer and LMCT state","authors":"Joaldo G. Arruda , Iran F. Silva , Wagner M. Faustino , Israel F. Costa , Hermi F. Brito , Albano N. Carneiro Neto , Christian Näther , Huayna Terraschke , Maria Cláudia F.C. Felinto , Victor M. Deflon , Ercules E.S. Teotonio","doi":"10.1016/j.poly.2024.117313","DOIUrl":"10.1016/j.poly.2024.117313","url":null,"abstract":"<div><div>Three novel lanthanide dipivaloylmethanate (dpm) complexes of general formula [Ln(dpm)(NO<sub>3</sub>)<sub>2</sub>(tchpo)<sub>2</sub>], where Ln: Eu<sup>3+</sup>, Gd<sup>3+</sup> and Tb<sup>3+</sup>, and tchpo: tricyclohexylphosphine oxide neutral ligand have been prepared and characterized by elemental analyses, absorption infrared spectroscopy, thermalgravimetric analyses, diffuse reflectance, and luminescence spectroscopies. Furthermore, the [Tb(dpm)(NO<sub>3</sub>)<sub>2</sub>(tchpo)<sub>2</sub>] complex was structurally characterized by the single crystal X-ray diffraction analysis. This complex exhibited high luminescence intensity in the green region. On the other hand, the analogous Eu<sup>3+</sup>-complex exhibited very low luminescence intensity due to an efficient luminescent quenching process <em>via</em> ligand-to-metal charge transfer (LMCT) state. Theoretical studies employing Time-Dependent Density Functional Theory (TD-DFT) calculations along with results obtained from the JOYSpectra platform, support this experimental result. Remarkably, despite the high values of non-radiative intramolecular energy transfer from excited ligand states (S<sub>1</sub> and T<sub>1</sub>) to the excited levels of the Ln<sup>3+</sup> ions, in the [Eu(dpm)(NO<sub>3</sub>)<sub>2</sub>(tchpo)<sub>2</sub>], the highest S<sub>1</sub>-LMCT rate (W = 1.2 × 10<sup>10</sup> s<sup>−1</sup>) emphasizes that the primary luminescence quenching pathway is <em>via</em> depopulation of excited ligand states. Interestingly, the nitrogen atoms from nitrate ions play an essential role in the lanthanide chemical environment, which has been suggested by the analyses of the ligand field parameters charge factors (<span><math><mrow><mi>g</mi></mrow></math></span>) and effective polarizabilities (<span><math><mrow><mi>α</mi><mo>′</mo></mrow></math></span>) values.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"267 ","pages":"Article 117313"},"PeriodicalIF":2.4,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747948","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-20DOI: 10.1016/j.poly.2024.117307
Pierre Thuéry , Youssef Atoini , Jack Harrowfield
2,5-Thiophenedicarboxylic acid (H2tdc) has been reacted with uranyl nitrate hexahydrate under solvo-hydrothermal conditions with N,N-dimethylacetamide (dma) as an organic cosolvent, giving the complex [UO2(tdc)(dma)] (1), isomorphous to the previously reported [UO2(tdc)(nmp)] (nmp = N-methyl-2-pyrrolidone). With tdc2− adopting the bis(μ2-κ1O:κ1O’)-bridging coordination mode, complex 1 crystallizes as a triperiodic framework with the point symbol {42.84}. With acetonitrile as an organic cosolvent and in the presence of [Ni(PPh3)2Br2], triphenylphosphine oxide is formed in situ and it binds to uranyl to give [UO2(tdc)(OPPh3)] (2). Complex 2 is also a triperiodic framework, with the point symbol {4.102}2{42.104} and the dmd topological type with uranium as 3-coordinated (3-c) nodes and tdc2− as either a 4-c node in its bis(μ2-κ1O:κ1O’)-bridging mode, or a simple edge in the bis(κ2O,O’)-chelating mode. In both 1 and 2, as in the previously described nmp complex, but not in [UO2(tdc)(dmf)] (dmf = N,N-dimethylformamide), coordination of a unidentate ligand disrupts the most common formation of diperiodic networks with tdc2− and tris-chelated uranyl, and promotes formation of frameworks in which channels accommodate the pendant, unidentate ligands. Complex 2 has a photoluminescence quantum yield of 3 % in the solid state, and its emission spectrum displays the typical vibronic progression with peak positions in the range usual for complexes with an O5 equatorial uranyl environment; the “hot band” observed at room temperature disappears at 77 K.
{"title":"Triperiodic frameworks in the uranyl–2,5-thiophenedicarboxylate system: Effect of unidentate auxiliary ligands","authors":"Pierre Thuéry , Youssef Atoini , Jack Harrowfield","doi":"10.1016/j.poly.2024.117307","DOIUrl":"10.1016/j.poly.2024.117307","url":null,"abstract":"<div><div>2,5-Thiophenedicarboxylic acid (H<sub>2</sub>tdc) has been reacted with uranyl nitrate hexahydrate under solvo-hydrothermal conditions with <em>N,N</em>-dimethylacetamide (dma) as an organic cosolvent, giving the complex [UO<sub>2</sub>(tdc)(dma)] (<strong>1</strong>), isomorphous to the previously reported [UO<sub>2</sub>(tdc)(nmp)] (nmp = <em>N</em>-methyl-2-pyrrolidone). With tdc<sup>2−</sup> adopting the bis(μ<sub>2</sub>-κ<sup>1</sup><em>O</em>:κ<sup>1</sup><em>O’</em>)-bridging coordination mode, complex <strong>1</strong> crystallizes as a triperiodic framework with the point symbol {4<sup>2</sup>.8<sup>4</sup>}. With acetonitrile as an organic cosolvent and in the presence of [Ni(PPh<sub>3</sub>)<sub>2</sub>Br<sub>2</sub>], triphenylphosphine oxide is formed <em>in situ</em> and it binds to uranyl to give [UO<sub>2</sub>(tdc)(OPPh<sub>3</sub>)] (<strong>2</strong>). Complex <strong>2</strong> is also a triperiodic framework, with the point symbol {4.10<sup>2</sup>}<sub>2</sub>{4<sup>2</sup>.10<sup>4</sup>} and the <strong>dmd</strong> topological type with uranium as 3-coordinated (3-c) nodes and tdc<sup>2−</sup> as either a 4-c node in its bis(μ<sub>2</sub>-κ<sup>1</sup><em>O</em>:κ<sup>1</sup><em>O’</em>)-bridging mode, or a simple edge in the bis(κ<sup>2</sup><em>O</em>,<em>O’</em>)-chelating mode. In both <strong>1</strong> and <strong>2</strong>, as in the previously described nmp complex, but not in [UO<sub>2</sub>(tdc)(dmf)] (dmf = <em>N,N</em>-dimethylformamide), coordination of a unidentate ligand disrupts the most common formation of diperiodic networks with tdc<sup>2−</sup> and tris-chelated uranyl, and promotes formation of frameworks in which channels accommodate the pendant, unidentate ligands. Complex <strong>2</strong> has a photoluminescence quantum yield of 3 % in the solid state, and its emission spectrum displays the typical vibronic progression with peak positions in the range usual for complexes with an O<sub>5</sub> equatorial uranyl environment; the “hot band” observed at room temperature disappears at 77 K.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"266 ","pages":"Article 117307"},"PeriodicalIF":2.4,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142702194","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-20DOI: 10.1016/j.poly.2024.117312
İbrahim Kani
A carboxylate-bridged dinuclear copper(II) complex, [Cu2(μ2-η2:η1(ppa)2(μ2-η1:η1 (ppa)bpy)2]·ClO4·H2O (ppa (C9H9OO) = 2-phenyl propionate, bpy = 2,2′-bipyridine), was prepared and its structure was determined by X-ray diffraction analysis. The octacoordinated Cu(II) dimer complex exhibits an asymmetric conformation, with the metal centers linked by two distinct modes of the carboxylate group. These include an asymmetric chelating bridging bidentate involving two ppa ligands and a syn-syn bidentate bridging mode involving one ppa ligand. The complex was employed as a catalyst for the oxidation of thymol, demonstrating a high degree of quantitative conversion and selectivity with TBHP across a range of solvents at moderate temperatures. The homogeneous catalytic system, comprising Cu(II)-2-phenyl propionate-bipyridine, tert-butylhydroperoxide (TBHP) as oxidant, and a polar aprotic solvent (acetonitrile or acetone), demonstrated high turnover numbers (TOF) in the absence of any additives. The impact of temperature, solvent, the ratio of thymol to TBHP, different oxidants and the quantity of catalyst on the catalytic activity and product selectivity was examined. Under optimized conditions, the maximum conversion of thymol (100 %) was obtained with 100 % selectivity to thymoquinone with TBHP after 35 min at the thymol to catalyst mole ratio of 267 (TOF = 449 h−1) in acetonitrile (MeCN) at 55 °C. Based on the available evidence, this activity and selectivity to thymoquinone represent the highest reported level of performance achieved by a homogeneously copper-catalysed process.
{"title":"Homogeneous catalytic oxidation of thymol with dinuclear Cu(II)-2-phenyl propionate-bipyridine complex","authors":"İbrahim Kani","doi":"10.1016/j.poly.2024.117312","DOIUrl":"10.1016/j.poly.2024.117312","url":null,"abstract":"<div><div>A carboxylate-bridged dinuclear copper(II) complex, [Cu<sub>2</sub>(μ<sub>2</sub>-η<sup>2</sup>:η<sup>1</sup>(ppa)<sub>2</sub>(μ<sub>2</sub>-η<sup>1</sup>:η<sup>1</sup> (ppa)bpy)<sub>2</sub>]·ClO<sub>4</sub>·H<sub>2</sub>O (ppa (C<sub>9</sub>H<sub>9</sub>OO) = 2-phenyl propionate, bpy = 2,2′-bipyridine), was prepared and its structure was determined by X-ray diffraction analysis. The octacoordinated Cu(II) dimer complex exhibits an asymmetric conformation, with the metal centers linked by two distinct modes of the carboxylate group. These include an asymmetric chelating bridging bidentate involving two ppa ligands and a <em>syn-syn</em> bidentate bridging mode involving one ppa ligand. The complex was employed as a catalyst for the oxidation of thymol, demonstrating a high degree of quantitative conversion and selectivity with TBHP across a range of solvents at moderate temperatures. The homogeneous catalytic system, comprising Cu(II)-2-phenyl propionate-bipyridine, <em>tert</em>-butylhydroperoxide (TBHP) as oxidant, and a polar aprotic solvent (acetonitrile or acetone), demonstrated high turnover numbers (TOF) in the absence of any additives. The impact of temperature, solvent, the ratio of thymol to TBHP, different oxidants and the quantity of catalyst on the catalytic activity and product selectivity was examined. Under optimized conditions, the maximum conversion of thymol (100 %) was obtained with 100 % selectivity to thymoquinone with TBHP after 35 min at the thymol to catalyst mole ratio of 267 (TOF = 449 h<sup>−1</sup>) in acetonitrile (MeCN) at 55 °C. Based on the available evidence, this activity and selectivity to thymoquinone represent the highest reported level of performance achieved by a homogeneously copper-catalysed process.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"266 ","pages":"Article 117312"},"PeriodicalIF":2.4,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142745059","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-20DOI: 10.1016/j.poly.2024.117314
Thomas E. Shaw , Julia G. Knapp , Taylor M. Currie , Stosh A. Kozimor , Titel Jurca , Thomas M. Gilbert , Alfred P. Sattelberger
The bis(diethyl ether) adducts of early transition metal chlorides, MCl4(OEt2)2, serve as excellent precursors for complex inorganic and organometallic compounds due to the lability of the coordinated ethers. Previously reported MCl4(OEt2)2 (M = Zr, Nb, Ta, Mo, W) complexes have crystallized with the ethers in a trans conformation, even though computational studies have predicted that compounds of the type MX4L2 should form cis isomers. Herein, we report the crystal structure of trans-HfCl4(OEt2)2 and the synthesis and structure of cis-ReCl4(OEt2)2. The report of the crystal structure of the Hf analog completes the Groups 4–6 2nd and 3rd row series and provides structural context regarding the trans preference and observations in M-Cl and M-O bond distances that are corroborated by Shannon’s ionic radii of the M(IV) cations. The isolation of the cis-Re analog provides the first structural example of a Group 7 MCl4(OEt2)2 complex, as well as the first cis complex in the presented series. Computational studies were conducted to examine the cis/trans preferences across the entire series in the context of ionic radii, ligand hardness, and steric influence.
{"title":"Synthesis and structure of trans-HfCl4(OEt2)2 and cis-ReCl4(OEt2)2, and computational studies of Group 4 to Group 7 MCl4(OEt2)2 isomer preferences (M = Zr, Hf, Nb, Ta, Mo, W, Re)","authors":"Thomas E. Shaw , Julia G. Knapp , Taylor M. Currie , Stosh A. Kozimor , Titel Jurca , Thomas M. Gilbert , Alfred P. Sattelberger","doi":"10.1016/j.poly.2024.117314","DOIUrl":"10.1016/j.poly.2024.117314","url":null,"abstract":"<div><div>The bis(diethyl ether) adducts of early transition metal chlorides, MCl<sub>4</sub>(OEt<sub>2</sub>)<sub>2</sub>, serve as excellent precursors for complex inorganic and organometallic compounds due to the lability of the coordinated ethers. Previously reported MCl<sub>4</sub>(OEt<sub>2</sub>)<sub>2</sub> (M = Zr, Nb, Ta, Mo, W) complexes have crystallized with the ethers in a <em>trans</em> conformation, even though computational studies have predicted that compounds of the type MX<sub>4</sub>L<sub>2</sub> should form <em>cis</em> isomers. Herein, we report the crystal structure of <em>trans</em>-HfCl<sub>4</sub>(OEt<sub>2</sub>)<sub>2</sub> and the synthesis and structure of <em>cis</em>-ReCl<sub>4</sub>(OEt<sub>2</sub>)<sub>2</sub>. The report of the crystal structure of the Hf analog completes the Groups 4–6 2nd and 3rd row series and provides structural context regarding the <em>trans</em> preference and observations in M-Cl and M-O bond distances that are corroborated by Shannon’s ionic radii of the M(IV) cations. The isolation of the <em>cis</em>-Re analog provides the first structural example of a Group 7 MCl<sub>4</sub>(OEt<sub>2</sub>)<sub>2</sub> complex, as well as the first <em>cis</em> complex in the presented series. Computational studies were conducted to examine the <em>cis</em>/<em>trans</em> preferences across the entire series in the context of ionic radii, ligand hardness, and steric influence.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"267 ","pages":"Article 117314"},"PeriodicalIF":2.4,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142756853","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}
The role of macrocyclic and Schiff base complexes in chemistry and life sciences offers vast opportunities to the researchers. Herein, this review focuses on the recent developments in ruthenium-based macrocyclic complexes and their utilities. Nowadays, ruthenium-based macrocyclic complexes are substantially exploited in copious applications, such as antioxidant, anticancer, antimicrobial, catalysis, sensors, pigments, dyes, etc. are a few of them. This study combines innovations in modelling and employment of these macrocyclic ligands and their complexes with ruthenium that serves as an interaction between the fields of chemistry, physics and biology. Probably Ru(II) and Ru(III) complexes achieve a wider holder of a three-dimensional scaffold through octahedral bonding, which opens up the possibility for a greater level of site diversity for attaching to their biological substrates. This study also expresses a broader overview of the topic and aims to highlight developments in ligand designing, synthetic methods, and potent applications especially as prominent therapeutic agents of these metal complexes in diverse areas. Additionally, some of the Schiff bases complexes with the same metal are also highlighted with their prominent applications.
{"title":"Ruthenium-based macrocyclic and Schiff base complexes as prominent therapeutic agents: Their designing, synthesis and recent perspectives","authors":"Urmila Phageria , Sushama Kumari , Krishna Atal , Swati Bugalia","doi":"10.1016/j.poly.2024.117309","DOIUrl":"10.1016/j.poly.2024.117309","url":null,"abstract":"<div><div>The role of macrocyclic and Schiff base complexes in chemistry and life sciences offers vast opportunities to the researchers. Herein, this review focuses on the recent developments in ruthenium-based macrocyclic complexes and their utilities. Nowadays, ruthenium-based macrocyclic complexes are substantially exploited in copious applications, such as antioxidant, anticancer, antimicrobial, catalysis, sensors, pigments, dyes, etc. are a few of them. This study combines innovations in modelling and employment of these macrocyclic ligands and their complexes with ruthenium that serves as an interaction between the fields of chemistry, physics and biology. Probably Ru(II) and Ru(III) complexes achieve a wider holder of a three-dimensional scaffold through octahedral bonding, which opens up the possibility for a greater level of site diversity for attaching to their biological substrates. This study also expresses a broader overview of the topic and aims to highlight developments in ligand designing, synthetic methods, and potent applications especially as prominent therapeutic agents of these metal complexes in diverse areas. Additionally, some of the Schiff bases complexes with the same metal are also highlighted with their prominent applications.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"266 ","pages":"Article 117309"},"PeriodicalIF":2.4,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142702204","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 : 2024-11-17DOI: 10.1016/j.poly.2024.117308
Eszter Fazekas , Alvaro Etcheverry-Berrios , Gary S. Nichol , Stergios Piligkos , Euan K. Brechin , Jennifer A. Garden
Mono and bimetallic cage-like TrenSal complexes based on rare-earth metals Y and Lu were synthesised and fully characterised by single crystal and powder X-ray diffraction, multinuclear NMR and IR spectroscopy, and MALDI-ToF mass spectrometry. These robust and air-stable complexes are active catalysts for the ring-opening polymerisation of rac-lactide. While the polymerisation activity is low, the complexes remain active in air using unpurified monomers, and are highly unusual examples of metal–organic cages applied in polymerisation. MALDI-ToF mass spectrometry studies of the obtained polymers revealed H and OBn end-capped chains suggesting that an ‘activated monomer’ mechanism predominates when BnOH is used as an exogenous initiator.
通过单晶和粉末 X 射线衍射、多核核磁共振和红外光谱以及 MALDI-ToF 质谱法，合成了基于稀土金属 Y 和 Lu 的单金属笼状 TrenSal 复合物和双金属笼状 TrenSal 复合物，并对其进行了全面表征。这些坚固且在空气中稳定的复合物是 rac-lactide 开环聚合反应的活性催化剂。虽然聚合活性较低，但使用未净化的单体时，这些复合物在空气中仍能保持活性，是将金属有机笼应用于聚合反应的极不寻常的例子。对获得的聚合物进行的 MALDI-ToF 质谱研究显示，H 和 OBn 端封端链表明，当 BnOH 用作外源引发剂时，"活化单体 "机制占主导地位。
{"title":"Robust Y and Lu TrenSal catalysts for ring-opening polymerisation","authors":"Eszter Fazekas , Alvaro Etcheverry-Berrios , Gary S. Nichol , Stergios Piligkos , Euan K. Brechin , Jennifer A. Garden","doi":"10.1016/j.poly.2024.117308","DOIUrl":"10.1016/j.poly.2024.117308","url":null,"abstract":"<div><div>Mono and bimetallic cage-like TrenSal complexes based on rare-earth metals Y and Lu were synthesised and fully characterised by single crystal and powder X-ray diffraction, multinuclear NMR and IR spectroscopy, and MALDI-ToF mass spectrometry. These robust and air-stable complexes are active catalysts for the ring-opening polymerisation of <em>rac</em>-lactide. While the polymerisation activity is low, the complexes remain active in air using unpurified monomers, and are highly unusual examples of metal–organic cages applied in polymerisation. MALDI-ToF mass spectrometry studies of the obtained polymers revealed H and OBn end-capped chains suggesting that an ‘activated monomer’ mechanism predominates when BnOH is used as an exogenous initiator.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"266 ","pages":"Article 117308"},"PeriodicalIF":2.4,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142702195","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 : 2024-11-17DOI: 10.1016/j.poly.2024.117304
Zhen-Ping Liao , Shu-Sheng Xin , Wei Li , Chun-Yang Pan
A series of borates 1–6, have been synthesized under mild conditions, single crystal X-ray diffraction indicates that they possess three types of metal complex configurations in borate crystalline, exemplified as TM-L for 3 and 4, μ2-O-TM for 2, μ3-O-TM for 1, 5 and 6. 5 and 6 exhibit both four-coordinated and six-coordinated metal ions in one single crystal lattice. 1 to 6 are further characterized by powder X-ray diffraction, elemental analysis, IR spectrum and UV–vis spectroscopy. In addition, the ORR activities of them are performed. Among them, cobalt borate-based catalyst exhibits the best catalytic performance, with a half-wave potential of 0.82 V. Furthermore, the relationship between the ORR properties of TM complex borates and their framework densities was explored.
{"title":"Synthesis of series of transition metal-ligand (TM-L), μ2-O-TM, μ3-O-TM-L borates: Characterization and oxygen reduction reaction (ORR) activity property exploration","authors":"Zhen-Ping Liao , Shu-Sheng Xin , Wei Li , Chun-Yang Pan","doi":"10.1016/j.poly.2024.117304","DOIUrl":"10.1016/j.poly.2024.117304","url":null,"abstract":"<div><div>A series of borates <strong>1</strong>–<strong>6</strong>, have been synthesized under mild conditions, single crystal X-ray diffraction indicates that they possess three types of metal complex configurations in borate crystalline, exemplified as TM-L for <strong>3</strong> and <strong>4</strong>, <em>μ</em><sub>2</sub>-O-TM for <strong>2</strong>, <em>μ</em><sub>3</sub>-O-TM for <strong>1</strong>, <strong>5</strong> and <strong>6</strong>. <strong>5</strong> and <strong>6</strong> exhibit both four-coordinated and six-coordinated metal ions in one single crystal lattice. <strong>1</strong> to <strong>6</strong> are further characterized by powder X-ray diffraction, elemental analysis, IR spectrum and UV–vis spectroscopy. In addition, the ORR activities of them are performed. Among them, cobalt borate-based catalyst exhibits the best catalytic performance, with a half-wave potential of 0.82 V. Furthermore, the relationship between the ORR properties of TM complex borates and their framework densities was explored.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"266 ","pages":"Article 117304"},"PeriodicalIF":2.4,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142702197","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}
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