Examinando por Autor "Vega, Andrés"
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Ítem Azo–hydrazone tautomerism in organometallic complexes triggered by a -Re(CO)3(L) core: A spectroscopic and theoretical study(Elsevier Ltd, 2022-01) Maldonado, Tamara; Flores, Erick; Llanos, Leonel; Aravena, Daniel; Vega, Andrés; Godoy, Fernando; Aspée, Alexis; Arancibia-Miranda, Nicolás; Ferraudi, Guillermo; Gómez, AlejandraThe spectroscopic properties and tautomeric behavior of five novel Rhenium (I) tricarbonyl complexes bearing an azo ligand are presented. The organic ligand is stable in solution as the hydrazone tautomer. It remains as hydrazone in different medium conditions (solvent, concentration, pH, etc.) without the formation of detectable amounts of the azo tautomer. However, the complexation of this ligand to the strong electron-withdrawing fragment -Re(CO)3X (X = Cl−, Br−) causes tautomerism to appear in the organic moiety. Two well-defined regions in the electronic spectra for both tautomers were observed, allowing the azo/enol-keto/hydrazone equilibrium to be followed. TD-DFT calculations indicate that for the keto/hydrazone form, the main absorption band is attributed to an IL transition. In contrast, the azo/enol species shows a major contribution of the 1MLCT (dπ(Re) → dπ*(NN)) transition. The tautomeric equilibrium is easily shifted using solvents with different dielectric constant and hydrogen bond donor/acceptor (HBD/HBA) abilities. Also, the tautomerization process is deeply influenced by the electronic properties of the axial ligand. Therefore, this behavior represents a different strategy for the design of novel materials with optical properties. Furthermore, tautomerism is affected by the concentration of complexes and the presence of water in solvents. The acid-base behavior of these compounds in a 50% v/v ethanol-buffer system showed that the azo/enol tautomer is stabilized in acidic media. At the same time, an increase of pH promotes tautomerization toward the keto/hydrazone, followed by forming the anionic form at pH > 8. © 2021 Elsevier LtdÍtem Comparitive study on structural, magnetic and spectroscopic properties of four new copper(II) coordination polymers with 4′-substituted terpyridine ligands(Academic Press Inc., 2017-09) Toledo, Dominique; Vega, Andrés; Pizarro, Nancy; Baggio, Ricardo; Peña, Octavio; Roisnel, Thierry; Pivan, Jean-Yves; Moreno, YankoThe synthesis and characterization of four copper(II) complexes with different terpyridyl ligands have been carried out, their crystal and molecular structures determined and their magnetic and luminescent properties analyzed. The ligands used in the coordination reactions were 4′-(3-methyl-2-thienyl)-4,2′:6′,4''-terpyridine (4-stpy), -4′-(4-quinolinyl)-4,2′:6′,4''-terpyridine (4-qtpy), 4′-(4-quinolinyl)-3,2′:6′,3''-terpyridine (3-qtpy, unreported so far) and 4′-(4-cyanophenyl)-4,2′:6′,4''-terpyridine (4-cntpy); the reaction of these ligands with Cu(II)-hexafluoroacetylacetone (Cu(hfacac)2) gives rise to coordination polymers Cu(4-stpy)(hfacac)2 (I), Cu(4-qtpy)(hfacac)2 (II), Cu(3-qtpy)(hfacac)2 (III) and Cu(4-cntpy)(hfacac)2 (IV). The different location of the nitrogen atom of the outer ring is responsible for the different coordination modes. The emission spectra of dichloromethane solutions are consistent with dissociation of the complexes; the emission maxima simulate those of the free ligands. The emission of I, III and IV in the solid state is essentially quenched upon complexation with Cu(II), whereas for compound II an emission at 420 nm is observed. The interaction between copper centers has been related with the coplanarity of terpyridine rings. Complexes I–III exhibit a paramagnetic behavior, while compound IV, with the smallest torsion angle between pyridine moieties, shows an antiferromagnetic behavior described by a dimeric model, with J=−4.38 cm−1, g =2.06 and ρ=0.07. © 2017 Elsevier Inc.Ítem Crystal structures and Hirshfeld surface analysis of [κ2-P,N-{(C6H5)2(C5H5N)P}Re(CO)3Br]·2CHCl3 and the product of its reaction with piperidine, [P-{(C6H5)2(C5H5N)P}(C5H11N)Re(CO)3Br](Acta Crystallographica Section E: Crystallographic Communications, 2019) Palominos, Franco; Muñoz, Carolina; Oyarzun, Poldie; Saldías, Marianela; Vega, AndrésThe coordination of the ligands with respect to the central atom in the complex bromidotricarbonyl[diphenyl(pyridin-2-yl)phosphane-κ2 N,P]rhenium(I) chloroform disolvate, [ReBr(C17H14NP)(CO)3]·2CHCl3 or [κ2-P,N-{(C6H5)2(C5H5N)P}Re(CO)3Br]·2CHCl3, (I·2CHCl3), is best described as a distorted octahedron with three carbonyls in a facial conformation, a bromide atom, and a biting P,N-diphenylpyridylphosphine ligand. Hirshfeld surface analysis shows that C - Cl⋯H interactions contribute 26%, the distance of these interactions are between 2.895 and 3.213 Å. The reaction between I and piperidine (C5H11N) at 313 K in dichloromethane leads to the partial decoordination of the pyridylphosphine ligand, whose pyridyl group is replaced by a piperidine molecule, and the complex bromidotricarbonyl[diphenyl(pyridin-2-yl)phosphane-κP](piperidine-κN)rhenium(I), [ReBr(C5H11N)(C17H14NP)(CO)3] or [P-{(C6H5)2(C5H5N)P}(C5H11N)Re(CO)3Br] (II). The molecule has an intramolecular N - H⋯N hydrogen bond between the non-coordinated pyridyl nitrogen atom and the amine hydrogen atom from piperidine with D⋯A = 2.992 (9) Å. Thermogravimetry shows that I·2CHCl3 losses 28% of its mass in a narrow range between 318 and 333 K, which is completely consistent with two solvating chloroform molecules very weakly bonded to I. The remaining I is stable at least to 573 K. In contrast, II seems to lose solvent and piperidine (12% of mass) between 427 and 463 K, while the additional 33% loss from this last temperature to 573 K corresponds to the release of 2-pyridylphosphine. The contribution to the scattering from highly disordered solvent molecules in II was removed with the SQUEEZE routine [Spek (2015). Acta Cryst. C71, 9-18] in PLATON. The stated crystal data for M r, μ etc. do not take this solvent into account.Ítem Hexaaquazinc(II) dinitrate bis[5-(pyridinium-3-yl)tetrazol-1-ide](International Union of Crystallography, 2018) Chi-Duran, Ignacio; Enriquez, Javier; Vega, Andrés; Herrera, Felipe; Singh, Dinesh PratapHexaaquazinc(II) dinitrate 5-(pyridinium-3-yl)tetrazol-1-ide, [Zn(H2 O)6](NO 3)2 ·2C6H5 N 5, crystallizes in the space group P. The asymmetric unit contains one zwitterionic 5-(pyridinium-3-yl)tetrazol-1-ide molecule, one NO3-anion and one half of a [Zn(H2 O)6]2+ cation (symmetry). The pyridinium and tetrazolide rings in the zwitterion are nearly coplanar, with a dihedral angle of 5.4 (2)°. Several O-H..N and N-H..O hydrogen-bonding interactions exist between the [Zn(H2 O)6]2+ cation and the N atoms of the tetrazolide ring, and between the nitrate anions and the N-H groups of the pyridinium ring, respectively, giving rise to a three-dimensional network. The 5-(pyridinium-3-yl)tetrazol-1-ide molecules show parallel-displaced π-π stacking interactions; the centroid-centroid distance between adjacent tetrazolide rings is 3.6298 (6) Å and that between the pyridinium and tetrazolide rings is 3.6120 (5) Å. © 2018 Chi-Duran et al.Ítem New Cationic fac-[Re(CO)3(deeb)B2]+ Complex, Where B2 Is a Benzimidazole Derivative, as a Potential New Luminescent Dye for Proteins Separated by SDS-PAGE(Frontiers Media S.A., 2021-03) Carreño, Alexander; Gacitúa, Manuel; Solis Céspedes, Eduardo; Páez Hernández, Dayán; Swords, Wesley B.; Meyer, Gerald J.; Preite, Marcelo D.; Chávez, Ivonne; Vega, Andrés; Fuentes, Juan A.Sodium-dodecyl-sulfate polyacrylamide gel electrophoresis (SDS-PAGE) can be used to separate proteins based mainly on their size such as in denaturing gels. Different staining methods have been reported to observe proteins in the gel matrix, where the most used dyes are generally anionic. Anionic dyes allow for interactions with protonated amino acids, retaining the dye in the proteins. Fluorescent staining is an alternative technique considered to be sensitive, safe, and versatile. Some anionic complexes based on d6 transition metals have been used for this purpose, where cationic dyes have been less explored in this context. In this work, we synthesized and characterized a new monocationic rhenium complex fac-[Re(CO)3(deeb)B2]+ (where deeb is 4,4′-bis(ethoxycarbonyl)-2,2′-bpy and B2 is 2,4-di-tert-butyl-6-(3H-imidazo[4,5-c]pyridine-2-yl)phenol). We carried out a structural characterization of this complex by MS+, FTIR, 1H NMR, D2O exchange, and HHCOSY. Moreover, we carried out UV-Vis, luminescence, and cyclic voltammetry experiments to understand the effect of ligands on the complex’s electronic structure. We also performed relativistic theoretical calculations using the B3LYP/TZ2P level of theory and R-TDDFT within a dielectric continuum model (COSMO) to better understand electronic transitions and optical properties. We finally assessed the potential of fac-[Re(CO)3(deeb)B2]+ (as well as the precursor fac-Re(CO)3(deeb)Br and the free ligand B2) to stain proteins separated by SDS-PAGE. We found that only fac-[Re(CO)3(deeb)B2]+ proved viable to be directly used as a luminescent dye for proteins, presumably due to its interaction with negatively charged residues in proteins and by weak interactions provided by B2. In addition, fac-[Re(CO)3(deeb)B2]+ seems to interact preferentially with proteins and not with the gel matrix despite the presence of sodium dodecyl sulfate (SDS). In future applications, these alternative cationic complexes might be used alone or in combination with more traditional anionic compounds to generate counterion dye stains to improve the process. © Copyright © 2021 Carreño, Gacitúa, Solis-Céspedes, Páez-Hernández, Swords, Meyer, Preite, Chávez, Vega and Fuentes.Ítem Photochemistry of P,N-bidentate rhenium(i) tricarbonyl complexes: Reactive species generation and potential application for antibacterial photodynamic therapy(Royal Society of Chemistry, 2021-09) Acosta, Alison; Antipán, Javier; Fernández, Mariano; Prado, Gaspar; Sandoval-Altamirano, Catalina; Günther, Germán; Gutiérrez-Urrutia, Izabook; Poblete-Castro, Ignacio; Vega, Andrés; Pizarro, NancyIn this work, we describe the photoisomerization of facial rhenium(i) tricarbonyl complexes bearing P,N-bidentate pyridyl/phosphine ligands with different chelating rings and anions: RePNBr, RePNTfO, and RePNNBr, which are triggered under irradiation at 365 nm in solutions. The apparent photodegradation rate constants (kapp) depend on the coordinating ability of the solvent, being lowest in acetonitrile. The kapp value increases as the temperature rises, suggesting a reactive IL excited state thermally populated from the MLCT excited state involved. Using the Eyring equation, positive activation enthalpies (ΔH≠) accompanied by high negative values for the activation entropy (ΔS≠) were obtained. These results suggest whatever the P,N-ligand or anion, the reaction proceeds through a strongly solvated or a compact transition state, which is compatible with an associative mechanism for the photoisomerization. A 100-fold decrease in the log10 CFU value is observed for E. coli and S. aureus in irradiated solutions of the compounds, which follows the same tendency as their singlet oxygen generation quantum yield: RePNBr > RePNTfO > RePNNBr, while no antibacterial activity is observed in the darkness. This result indicates that the generation of singlet oxygen plays a key role in the antibacterial capacity of these complexes. © The Royal Society of Chemistry.Ítem Rhenium(I) bromo tricarbonyl complexes from anthracenyl derivatized ligands(2023-07) Muñoz, José; Rojas, Xavier; Palominos, Franco; Arce, Roxana; Cañas, Francisco; Pizarro, Nancy; Vega, AndrésThe ligand 2-(1H-pyrazol-1-yl)pyrazine (pypyr) was prepared by reaction of 2-bromopyrazine with N-lithium pyrazolate with 92.5% yield, while the anthracenyl derivatives 2-(anthracen-9-yl)-5-(1H-pyrazol-1-yl)pyrazine (pypyr-anthra) and 9,10-bis(5-(1H-pyrazol-1-yl)pyrazin-2-yl)anthracene (pypyr-anthra-pypyr) were prepared by reaction of the 9-anthraceneboronic or bis-boronic acid pinacol ester with 2-bromo-5-(1H-pyrazol-1-yl)pyrazine with medium yields (49.6 and 31.5 % respectively). The respective ReI(CO)3Br complexes: [(pypyr)Re(CO)3Br], [(pypyr-anthra)Re(CO)3Br] and [Br(CO)3Re(pypyr-anthra-pypyr)Re(CO)3Br] were prepared in high yields (94, 84 and 78 % respectively) by reaction with bromotricarbonyl(tetrahydrofuran)rhenium(I) dimer. DFT modelling suggests the anthracenyl moiety is not coplanar with the pyrazolyl-pyrazine fragment, defining a dihedral angle of 65° and 67° for [(pypyr-anthra)Re(CO)3Br] and [Br(CO)3Re(pypyr-anthra-pypyr)Re(CO)3Br] respectively. Each one of the three rhenium(I) molecules shows a quasi-reversible reduction wave around − 1.10 V, assigned by comparison with the uncoordinated ligand, the pypyr fragment, while additional reductions waves related to this core or the anthryl arms are present. UV–Vis spectra show absorption bands and/or shoulders around 400–450 nm for the series of compounds in solution. The respective extinction coefficients (∼4 × 103 M−1cm−1), the sensitivity to solvent polarity and DFT modelling suggest they corresponds to MLCT Redπ → π(pyr)* transitions. Despite their high emissivity, the uncoordinated ligands completely lose their emission upon coordinated to ReI(CO)3Br. The rhenium(I) complexes emit around 650 nm upon excitation, although [(pypyr)Re(CO)3Br] is a moderate emissive molecule, while [(pypyr-anthra)Re(CO)3Br] and [Br(CO)3Re(pypyr-anthra-pypyr)Re(CO)3Br] are very weak ones. In contrast these two last molecules showed a remarkably high yield as singlet oxygen sensitizers. © 2023 Elsevier LtdÍtem Synthesis, characterization and computational studies of (E)-2-{[(2-aminopyridin-3-yl)imino]-methyl}-4,6-di-tert-butylphenol(Sociedade Brasileira de Química, 2014) Carreño, Alexander; Vega, Andrés; Zarate, Ximena; Schott, Eduardo; Gacitúa, Manuel; Valenzuela, Ninnette; Preite, Marcelo; Manríquez, Juan M.; Chávez, Ivonne(E)-2-{[(2-Aminopyridin-3-yl)imino]-methyl}-4,6-di-tert-butyl-phenol ( 3: ), a ligand containing an intramolecular hydrogen bond, was prepared according to a previous literature report, with modifications, and was characterized by UV-vis, FTIR, 1H-NMR, 13C-NMR, HHCOSY, TOCSY and cyclic voltammetry. Computational analyses at the level of DFT and TD-DFT were performed to study its electronic and molecular structures. The results of these analyses elucidated the behaviors of the UV-vis and electrochemical data. Analysis of the transitions in the computed spectrum showed that the most important band is primarily composed of a HOMO→LUMO transition, designated as an intraligand (IL) charge transfer.Ítem The binuclear dual emitter [Br(CO)3Re(P⋯N)(N⋯P)Re(CO)3Br] (P⋯N): 3-chloro-6-(4-diphenylphosphinyl)butoxypyridazine, a new bridging: P, N -bidentate ligand resulting from the ring opening of tetrahydrofuran(Royal Society of Chemistry, 2017) Saldías, Marianela; Manzur, Jorge; Palacios, Rodrigo E.; Gómez, María L.; Fuente, Julio De La; Günther, Germán; Pizarro, Nancy; Vega, AndrésLithium diphenylphosphide unexpectedly provokes the ring-opening of tetrahydrofuran (THF) and by reaction with 3,6-dichloropyridazine leads to the formation of the ligand 3-chloro-6-(4-diphenylphosphinyl)butoxypyridazine (P⋯N), which was isolated. The reaction of this ligand with the (Re(CO)3(THF)Br)2 dimer yields the novel complex [Br(CO)3Re(μ-3-chloro-6-(4-diphenylphosphinyl)butoxypyridazine)2Re(CO)3Br] (BrRe(P⋯N)(N⋯P)ReBr), which was crystallized in the form of a chloroform solvate, (C46H40Br2Cl2N4O8P2Re2)·(CHCl3). The monoclinic crystal (P21/n) displays a bimetallic cage structure with a symmetry inversion centre in the middle of the rhenium to rhenium line. The molecule shows two oxidation signals occurring at +1.50 V and +1.76 V which were assigned to the ReI/ReII and ReII/ReIII metal-centered couples, respectively, while signals observed at -1.38 V and -1.68 V were assigned to ligand centered reductions. Experimental and DFT/TDDFT results indicate that the UV-Vis absorption maximum of BrRe(P⋯N)(N⋯P)ReBr occurring near 380 nm displays a metal to ligand charge transfer (MLCT) character, which is consistent with CV results. Upon excitation at this wavelength, a weak emission (Φem < 1 × 10-3) is observed around 580 nm (in dichloromethane) which decays with two distinct lifetimes τ1 and τ2 of 24 and 4.7 ns, respectively. The prevalence of non-radiative deactivation pathways is consistent with efficient internal conversion induced by the high conformational flexibility of the P⋯N ligand's long carbon chain. Measurements in a frozen solvent at 77 K, where vibrational deactivation is hindered, show intense emission associated with the 3MLCT state. These results demonstrate that BrRe(P⋯N)(N⋯P)ReBr preserves the dual emitting nature previously reported for the mononuclear complex RePNBr, with emission associated with and states. © 2017 The Royal Society of Chemistry.Ítem Trichromatic color tuning strategy for emission of heterometallic EuIII/TbIII coordination polymers with triazolyl-substituted 4-methyl-phenoxo ligand(Journal of Rare Earths, 2025, 2025) Perez-Obando, Juliana; Manzur, Jorge; Fuentealba, Pablo; Morales, Jeannette; Vega, Andrés; Costa de Santana, Ricardo; Carneiro Neto, Albano N.; Spodine, EvgeniaThis study presents the microwave-assisted synthesis and characterization of a series of heterometallic coordination polymers (HMCPs) with a 4-methyl-2,6-di[(1H-1,2,4-triazol-1-yl)]phenoxo ligand with varying EuIII/TbIII ratios. Single crystal X-ray diffraction reveals a double-chain structure bridged by triazolyl groups. Powder X-ray diffraction confirms the isostructural nature of the synthesized HMCPs. The photophysical properties depend on lanthanide ion concentration and excitation wavelength, leading to a color shift from green to blue as the proportion of TbIII decreases and EuIII increases. White light generation is achieved in the 8/2 EuIII/TbIII HMCP (CIE: 0.293, 0.326) under 335 nm excitation. The study suggests energy transfer from TbIII to EuIII, but both experimental and theoretical calculations indicate that this transfer is orders of magnitude lower than the sensitization through ligand states. © 2024 The Authors