Browsing by Author "Hidalgo-Rosa, Yoan"

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    Adsorption properties of M-UiO-66 (M = Zr(iv); Hf(iv) or Ce(iv)) with BDC or PDC linker
    (Royal Society of Chemistry, 2024) González, Diego; Pazo Carballo, César Alexander; Camú Macaya, Esteban Alonso; Hidalgo-Rosa, Yoan; Zarate, Ximena; Escalona, Néstor; Schott Verdugo, Eduardo
    The increasing CO2 emissions and their direct impact on climate change due to the greenhouse effect are environmental issues that must be solved as soon as possible. Metal-organic frameworks (MOFs) are one class of crystalline adsorbent materials that are thought to have enormous potential in CO2 capture applications. In this research, the effect of changing the metal center between Zr(iv), Ce(iv), and Hf(iv), and the linker between BDC and PDC has been fully studied. Thus, the six UiO-66 isoreticular derivatives have been synthesized and characterized by FTIR, PXRD, TGA, and N2 adsorption. We also report the BET surface area, CO2 adsorption capacities, kinetics, and the adsorption isosteric heat (Q(st)) of the UiO-66 derivatives mentioned family. The CO2 adsorption kinetics were evaluated using pseudo-first order, pseudo-second order, Avrami's kinetic models, and the rate-limiting step with Boyd's film diffusion, interparticle diffusion, and intraparticle diffusion models. The isosteric heats of CO2 adsorption using various MOFs are in the range 20-65 kJ mol(-1) observing differences in adsorption capacities between 1.15 and 4.72 mmol g(-1) at different temperatures due to the electrostatic interactions between CO2 and extra-framework metal ions. The isosteric heat of adsorption calculation in this report, which accounts for the unexpectedly high heat released from Zr-UiO-66-PDC, is finally represented as an increase in the interaction of CO2 with the PDC linker and an increase in Q(st) with defects.
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    Assessing the electronic properties of bimetallic complexes with N-M-N-M cycle (M = Ag, Au and Cu)
    (2024) Zarate, Ximena; Treto-Suárez, Manuel A.; Hidalgo-Rosa, Yoan; Schott Verdugo, Eduardo Enrique
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    Catalytic evaluation of MOF-808 with metallic centers of Zr(IV), Hf(IV) and Ce(IV) in the acetalization of benzaldehyde with methanol
    (Royal Society Chemistry, 2024) Arellano Valderrama, Yazmin Anay; Pazo Carballo, César Alexander; Roa, Vanesa; Hidalgo-Rosa, Yoan; Zarate, Ximena; Llanos, Jaime; Escalona Burgos, Nestor Guillermo; Schott, Eduardo
    In the context of climate change, it is of utmost importance to replace the use of fossil fuels as raw material in areas of industrial interest, for example, in the production of chemical inputs. In this context, a viable option is biomass, since by subjecting it to chemical processes such as pyrolysis, it is possible to obtain platform molecules that are the basis for the generation of value-added chemical products. Acetals are molecules obtained from biomass derIVatIVes, which have various applications in cosmetic chemistry, in the pharmaceutical industry as intermediates or final compounds, food additIVes, among others. Different catalysts have been used in the acetalization reaction, including MOFs, which have the advantage of being porous materials with high surface area values. The large surface area translates into a greater number of catalytically actIVe sites available for the reaction. Among the MOFs that have been used for this purpose is MOF-808, which is characterized by having a lower number of ligands attached to its metal cluster, therefore, it has a greater exposure of the metals that make up its structure. In this context, the work carried out studied the catalytic performance of MOF-808 when its Zr(IV) metal centers are replaced by Hf(IV) and Ce(IV) atoms in the acetalization reaction of benzaldehyde with methanol. The MOFs obtained by solvothermal synthesis were characterized by powder X-ray diffraction, N-2 adsorption and desorption, FT-IR spectroscopy, acid-base potentiometric titration, XPS and thermogravimetric analysis. The results of the catalysis indicate that the MOF with the best performance was MOF-808-Ce, which achieved conversions greater than 80% in a period of ten minutes. MOF-808-Ce exhibits a higher number of defects and therefore a higher availability of catalytic sites for the reaction to occur, which explains the better performance. Finally, the performance of MOF-808 in the acetalization of benzaldehyde with methanol was also supported by density functional theory (DFT) calculations.
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    Exploring the adsorption of five emerging pollutants on activated carbon: A theoretical approach
    (2024) Gonzalez-Rodriguez, Lisdelys; Yanez, Osvaldo; Mena-Ulecia, Karel; Hidalgo-Rosa, Yoan; Garcia-Carmona, Ximena; Ulloa-Tesser, Claudia
    The identification and management of contaminants of emerging concern (CECs) in water systems is crucial for protecting public and environmental health. This paper reports a theoretical approach to studying the adsorption of five CECs: Atrazine (ATZ), Caffeine (CAF), Carbamazepine (CBZ), Sulfamethoxazole (SMX), and Ibuprofen (IBU) - onto Activated Carbon (AC). A set of computational methods, including electrostatic molecular potential maps, conceptual density functional theory, Fukui functions, thermodynamic analysis, and tight-binding molecular dynamics simulations, were employed to analyze the electronic/energetic interactions and mechanisms involved in the adsorption of CECs on AC. The theoretical methodology offered valuable predictions on reactivity sites, stability, and binding mechanisms. Results showed that adsorption primarily occurred through non-covalent interactions like pi-pi electron donor-acceptor interactions, van der Waals forces, and hydrophobic interactions. Thermodynamic properties suggested the adsorption process was spontaneous and exothermic. However, for the AC/SMX system, the Gibbs free energy reveals that adsorption may be unfavorably compared to the other study systems. Molecular dynamics simulations validated the kinetic stability in the following order CAF (0.13 & Aring;)>CBZ (0.23 & Aring;)>ATZ (0.75 & Aring;)> IBU (1.28 & Aring;)>SMX (1.54 & Aring;). This exploratory theoretical study provides a deep understanding of the interactions between AC and five CECs, aiding in the rational design and optimization of AC-based treatment systems for environmental and industrial applications.
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    Fluorescent B(III) and Sn(IV) Schiff base: Synthesis, photophysical properties, emergent behavior, applications, and fluorescence mechanism
    (Elsevier Ltd., 2026) Ibarra-Rodríguez, Marisol; Jiménez-Pérez, Víctor M.; Lara-Cerón, Jesús A.; Molina-Paredes, Areli A.; Hidalgo-Rosa, Yoan ; Schott Verdugo, Eduardo; Paez-Hernández, Dayán; Treto-Suárez, Manuel A.; Zárate, Ximena; Muñoz-Flores, Blanca M.
    In this review, we describe the preparation methods, photophysical properties, and applications of fluorescent Boron(III) and Tin(IV) Schiff base. Although Schiff base have been known for a long time, Boron(III) and Tin(IV) compounds derived from them have gained significant attention in materials chemistry in recent decades. Remarkably, fluorescent organoboron and organotin complexes offer several advantages, such as being synthesized via green methods and exhibiting desirable physical and optical properties. Notably, the low cytotoxicity of organoboron compounds makes them excellent fluorescence dyes for in vitro and in vivo bioimaging. We present the most recent studies of Boron(III) and Tin(IV) compounds and highlight the favorable photophysical and physicochemical properties. Furthermore, we discuss materials that respond to various stimuli -physical, chemical and biological. Some fluorescent organoboron and tin complexes behave as smart materials, showing multi-stimuli responsiveness through processes such as mechanochromism, thermochromism, piezochromism, and vapochromism, most of which are observed in the solid-state. We also include several quantum chemical studies aimed at understanding the electronic structures and optical properties of these fluorescent Schiff base complexes.
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    Furfural adsorption on V2O5 surface: A combined experimental-theoretical study
    (2024) Lizana, Ignacio; Schott, Eduardo; Saavedra-Torres, Mario; Hidalgo-Rosa, Yoan; Pecchi, Gina; Karelovic, Alejandro; Zarate, Ximena
    The adsorption of furfural on the V 2 O 5 surface was investigated using experimental and theoretical methods. In situ Diffuse Reflectance Infrared Fourier-Transform Spectroscopy results show the presence of physi- and chemisorption phenomena, where trans -furfural is mostly chemisorbed at the beginning of the adsorption process. These results are in agreement with theoretical DFT results, as the most thermodynamically favored configurations corresponds to the chemisorbed trans -furfural (T1) and cis -furfural (C1) with binding energies of -1.83 and -2.05 eV.
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    Methylxanthines for halogen bonded cocrystals with 1,4-diiodotetrafluorobenzene: green synthesis, structure, photophysics and DFT studies
    (2024) Benito, Monica; Nunez, Rosario; Sinha, Sohini; Roscini, Claudio; Hidalgo-Rosa, Yoan; Schott, Eduardo; Zarate, Ximena; Molins, Elies
    Four new halogen-bonded cocrystals of biological methylxanthines, named caffeine, theophylline and theobromine, have been prepared with 1,4-diiodotetrafluorobenzene as a halogen bond donor by mechanochemical and solution processes. For theophylline, N & ctdot;I and N & ctdot;O interactions were observed, while for caffeine and theobromine, only N & ctdot;I was detected. The solids were characterized by PXRD, SC-XRD, FTIR and thermal methods (TGA-DSC analyses). In addition, the solid-state photoluminescence properties of the methylxanthines and their respective cocrystals have been studied and quantum chemistry calculations have been performed to rationalise and understand the electronic and optical properties of all compounds. This work provides a triad of natural methylxanthines capable of forming halogen-bonded multicomponent systems that can give rise to a cocrystal-to-crystal transformation with off-on luminescence activation.
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    Quantum chemical elucidation of the luminescence mechanism in a europium(iii) co-doped UiO-66 chemosensor selective to mercury(ii)
    (2025) Hidalgo-Rosa, Yoan; Echevarría-Valdés, Yoslainy; Saavedra-Torres, Mario; Paez-Hernández, Dayán; Schott Verdugo, Eduardo Enrique; Zárate, Ximena
    Lanthanide(iii) ions can be incorporated into metal-organic frameworks (MOFs) to form Ln@MOFs through post-synthetic procedures. This makes the MOFs efficient luminescent chemical sensors for detecting trace amounts of heavy metals. In this report, a quantum chemical theoretical protocol has been carried out to elucidate the detection principle of the turn-off luminescence mechanism in a Eu@UiO-66(DPA)-type MOF selective to Hg2+ ions. UiO-66(DPA) is an iso-reticular MOF of UiO-66 constructed from the Zr6-cluster [Zr6(μ3-O)4(μ3-OH)4]12+ and the ligands 1,4-benzenedicarboxylate (BDC) and 2,6-pyridinedicarboxylate (DPA) as linkers. The sensitization and energy transfer (ET) in UiO-66(DPA) doped with Eu3+ were analyzed using multireference ab initio CASSCF/NEVPT2 methods and time-dependent density functional theory (TD-DFT). The cluster model used in the calculations comprises the Z6-cluster/BDC/DPA fragments with the DPA ligand coordinating to Eu3+ or Hg2+ ions. The proposed sensitization pathway involves intersystem crossing from S1(DPA) to T1(DPA), a plausible subsequent energy transfer from T1(DPA) to the 5D1 state of Eu3+, and then vibrational relaxation to the emissive 5D0 state. These results also suggest that the electronic states of the BDC ligand can be strengthened by the population of the T1 electronic states of the DPA antenna via ET. Periodic DFT calculations confirm the electronic state mixture of BDC and DPA linkers in the conduction bands, just above the electronic state of Eu3+ ions, which is in concordance with the proposed Eu3+ sensitization pathways. The assessed optical properties (absorption and emission) of Hg2+@UIO-66(DPA) explain the experimental behavior of this chemosensor when the Hg2+ ion replaces the Eu3+ ion and the luminescence diminishes.
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    Sulfate-modified MOF-808 as a superacid catalyst: a performance evaluation of Zr(iv) and Hf(iv) analogues in acetalization reactions
    (2025) Roa Gómez, Vanesa Belen; Cea, Sebastián; Pazo Carballo, César Alexander; Llanos, Jaime; Olivares, Douglas; Escalona, Néstor; Leiva Campusano, Ángel; Hidalgo-Rosa, Yoan; Zarate, Ximena; Dongil, Ana Belén; Schott Verdugo, Eduardo
    In this study, we report the synthesis and characterization of MOF-808-SO4-M (M = Zr(IV), Hf(IV)), derived from MOF-808-M precursors. The introduction of sulfate groups enhances the Brønsted acidity of these materials, significantly improving their catalytic performance in the benzaldehyde acetalization reaction. The materials were characterized using powder X-ray diffraction (PXRD), Fourier-transform infrared spectroscopy (FT-IR), nitrogen adsorption–desorption analysis, thermogravimetric analysis (TGA), energy-dispersive spectroscopy (EDS), and Hammett indicator tests. Catalytic evaluation revealed that MOF-808-SO4-Zr exhibited significantly higher conversion compared to its Hf-based analogue, a difference attributed to its greater density of acid sites, as confirmed by temperature-programmed surface reaction (TPSR) analysis. These experimental results were further supported by density functional theory (DFT) calculations, which provided insights into the acidic properties and catalytic behavior of the materials.
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    Theoretical and Experimental Study for Cross-Coupling Aldol Condensation over Mono- and Bimetallic UiO-66 Nanocatalysts
    (2023) Pazo Carballo, César Alexander; Blanco, Elodie; Camu, Esteban; Leiva Campusano, Ángel; Hidalgo-Rosa, Yoan; Zarate, Ximena; Dongil, Ana Belén; Schott Verdugo, Eduardo Enrique; Escalona, Néstor
    Mono- and bimetallic UiO-66 nanocatalysts were synthesized using the solvothermal synthesis method and evaluated in the aldol condensation reaction of benzaldehyde and acetone in a batch reactor. N2 physisorption, thermogravimetric analysis, temperature-programmed desorption of ammonia, X-ray diffraction, field-emission scanning electron microscopy–energy-dispersive X-ray, X-ray photoelectron spectroscopy, potentiometric titration, and Fourier transform infrared were used to characterize the nanocatalysts. The higher activity exhibited by the Zr/Hf-UiO-66 catalyst could be attributed to the lower orbital energy interaction with benzaldehyde, as shown by density functional theory. A synergetic effect is observed for the bimetallic UiO-66 nanocatalyst between Zr and Hf, obtaining a higher reaction rate than the monometallic nanocatalysts. Meanwhile, this antagonistic effect was shown in the bimetallic catalysts between Zr and Ce, which was less active than the monometallic UiO-66 catalyst due to free COOH generated during the synthesis. Finally, the selectivity results showed that incorporating Hf and Ce on Zr-UiO-66 favors benzalacetone formation by cross-coupling condensation of benzaldehyde and acetone at isoconversion conditions.
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    Tuning the sensitization pathway T1→5DJ in Eu-based MOF through modification of the antenna ligand. A theoretical approach via multiconfigurational quantum calculations
    (2023) Hidalgo-Rosa, Yoan; Santoyo-Flores, Julian; Treto-Suarez, Manuel A.; Schott, Eduardo; Paez-Hernandez, Dayan; Zarate, Ximena
    The current study demonstrates the possibility of improving the efficiency of Eu3+ sensitization in an Eu-based MOF, labelled as EuL-R, by modifying the antenna ligand. The electronic structure of seven antenna ligand derivatives with the form R-4-(pyrimidin-5-yl) benzoic acid (L-R) ligand derivates was thoroughly examined in this research. Also, the most likely energy transfer channels for the sensitization pathway of Eu3+ ions in the EuL-R systems (R: CH3, -OH, -SH and -NH2) was studied. The efficiency in the intersystem crossing (ISC) process from S1 to T1 in the antenna make plausible a subsequent energy transfer to the emissive state in the Eu3+. This process was studied via multireference CASSCF/NEVPT2 calculations due to the multiconfigurational character of Eu3+ ions. Based on Latva and Reindhout's empirical rules, the 4-(2-(thiophen-2-yl)pyrimidin-5-yl)benzoic acid (L6) was chosen as efficient antenna for the sensitization process in this system. In conclusion, it was discovered that including the thiophenyl group at the L antenna (L6), increased the energy gaps S1 -> T1 and T1 -> 5DJ (Eu3+) to an optimal range for the ISC and subsequent energy transfer. Finally, a deeply understanding of the sensitization and emission mechanisms was possible from the excited-state dynamics analysis of the L6 antenna, via fluorescence, inter-system crossing (ISC), phosphorescence, and kF, kISC, and kP, rates calculations. This study therefore highlights the importance of a thorough theoretical procedure via a robust quantum me-chanical tool to guide the development of novel luminescent lanthanide-based MOFs.
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    Tuning the visible-NIR absorption of azulenocyanine-based photosensitizers
    (2022) Granados-Tavera, Kevin; Zambrano-Angulo, Michael; Hidalgo-Rosa, Yoan; Zarate, Ximena; Cardenas-Jiron, Gloria
    A new photosensitizer 1-WS55 (dyad) based on two dyes with excellent properties, azulenocyanine (1) and WS55, is proposed at the density functional theory level (M06/def2-SVP). 1 is a dye having a broad NIR absorption (similar to 1000 nm), and WS55 is a metal-free organic dye that presents a huge photoelectric conversion efficiency (PCE) of 9.5%. The dyad presents a panchromatic absorption along the UV-Vis-NIR region. It exhibits two intense Q bands (880, 926 nm) in the NIR region, one strong band (672 nm) in the visible region, and several bands in 300-600 nm. Charge transfer bands in the dyad from 1 to WS55 were found in the visible region, which favors the adsorption on an anatase TiO2 surface. The interaction energies dyad (dye)-TiO2 were calculated as a periodic system and corrected by the basis set superposition error. These show better adsorption for the dyad than fragments 1 and WS55. The electron injection calculated from the dye (dyad) to TiO2 suggests an efficient solar energy conversion because of Delta G(inj) > 0.2 eV. Additionally, calculations performed for the reorganization energy of electrons and holes indicate that the dyad presents the highest charge mobility. In summary, the dyad proposed 1-WS55 constitutes an excellent candidate to be used as a potential photosensitizer for the DSSCs.
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    Tunning the optical properties of a photocatalytic metal-organic framework by means of molecular modelling
    (2023) Treto-Suarez, Manuel A.; Hidalgo-Rosa, Yoan; Ulecia, Karel Mena; Paez-Hernandez, Dayan; Koivisto, Bryan D.; Zarate, Ximena; Schott, Eduardo
    A theoretical study of reported isostructural metal-organic frameworks (MOFs) based on MIL-125-Ti4+ was performed to understand the optical properties and facilitate the rational design of new materials with potentially improved features as photocatalysts. The experimentally tested MOFs (MIL-125-Ti4+ labeled as M) were functionalized with -NH2, -CH3, and -OH substituents on the 1,4-benzene-dicarboxylate (BDC) linker (labeled as M-NH2, M-CH3, and M-OH, respectively), generating a broadened light-harvesting of the MOF and an improvement of the N-2 conversion rate. The M-NH2 showed the highest visible light absorption and N-2 photocatalysis efficiency experimentally. This substituent effect was theoretically studied via Density Functional Theory (DFT) calculations on the ground singlet (S-0) and first excited state (singlet and triplet) using Time-Dependent Density Functional Theory (TD-DFT), the Morokuma-Ziegler energy decomposition scheme, and Natural Orbital of Chemical Valence (NOCV) analysis. These tools allowed for the reproduction of the optical properties and performance in good agreement with the experiment and highlight that the N-2 conversion rate increases as the donor character of the R group improve. This effect is a result of the stabilization of the Occupied Molecular Orbitals (localized on the BDC linker), a decrease in the charge recombination, and by an increase of charge flow to the metal center favoring the photocatalytic Ti4+/Ti3+ reduction (via ligand to metal charge transfer (LMCT) transition). These systems also display a metal-ligand charge transfer (MLCT) process in the excited state favoring the emission localized in the BDC linker, which was confirmed via Complete Active Space Self-Consistent Field (CASSCF) calculation. Finally, through CASSCF, it was possible to propose two new isoreticular structures, with the -SH and -NO2 substituents (labeled as M-SH and M-NO2), with the -SH variant exhibiting optical and photocatalytic properties that could rival M with -NH2 substitution.
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    UiO-66(Zr) as drug delivery system for non-steroidal anti-inflammatory drugs
    (2024) Salazar, Javier; Hidalgo-Rosa, Yoan; Burboa, Pia C.; Wu, Yi-nan; Escalona, Nesor; Leiva, Angel; Zarate, Ximena; Schott, Eduardo
    The toxicity for the human body of non-steroidal anti-inflammatory drugs (NSAIDs) overdoses is a consequence of their low water solubility, high doses, and facile accessibility to the population. New drug delivery systems (DDS) are necessary to overcome the bioavailability and toxicity related to NSAIDs. In this context, UiO-66(Zr) metal-organic framework (MOF) shows high porosity, stability, and load capacity, thus being a promising DDS. However, the adsorption and release capability for different NSAIDs is scarcely described. In this work, the biocompatible UiO-66(Zr) MOF was used to study the adsorption and release conditions of ibuprofen, naproxen, and diclofenac using a theoretical and experimental approximation. DFT results showed that the MOF-drug interaction was due to an intermolecular hydrogen bond between protons of the groups in the defect sites, (mu 3 - OH, and - OH2) and a lone pair of oxygen carboxyl functional group of the NSAIDs. Also, the experimental results suggest that the solvent where the drug is dissolved affects the adsorption process. The adsorption kinetics are similar between the drugs, but the maximum load capacity differs for each drug. The release kinetics assay showed a solvent dependence kinetics whose maximum liberation capacity is affected by the interaction between the drug and the material. Finally, the biological assays show that none of the systems studied are cytotoxic for HMVEC. Additionally, the wound healing assay suggests that the UiO-66(Zr) material has potential application on the wound healing process. However, further studies should be done.