Konposatu metal-organikoen sintesia laborategitik industriako aplikazioetara

Promoted by their promising properties metal-organic frameworks have undergone a huge evolution during the last three decades. Not only the academia but also the industry has payed attention to their possible applications. Motivated for this reason, the scaling up of MOFs from lab to industry has become a priority to the industrial world. In this context, this article wants to give an outlook of the factors that have to be taken into account for the implementation of MOFs in industry as well as some of the first applications of MOFs produced at large scale.; Konposatu metal-organikoen propietate interesgarriak direla eta, azken hiru hamarkadetan material horien ikerketak iraultza handia izan du. Ikerketa-taldeek zein industriak jarri ditu MOFen aplikazio posibleak ikerketaren jomugan. Horregatik, laborategitik industria-mailako ekoizpenera igarotzeko modua ikertzea oso garrantzitsua da ehungintzan eta garraiobideen eta elikagaien industrian. Testuinguru horretan, artikulu honek laborategi-mailako sintesitik industriako ekoizpen handiko sintesira igarotzeko kontuan hartu beharreko faktoreak argitu eta eskala handian produzitutako MOFen lehen aplikazioak aurkeztu nahi ditu

Easy Handling and Cost-Efficient Processing of a Tb3+-MOF: The Emissive Capacity of the Membrane-Immobilized Material, Water Vapour Adsorption and Proton Conductivity

The development of convenient, non-complicated, and cost-efficient processing techniques for packing low-density MOF powders for industry implementation is essential nowadays. To increase MOFs’ availability in industrial settings, we propose the synthesis of a novel 3D Tb-MOF (1) and a simple and non-expensive method for its immobilization in the form of pellets and membranes in polymethacrylate (PMMA) and polysulphone (PSF). The photoluminescent properties of the processed materials were investigated. To simulate industrial conditions, stability towards temperature and humidity have been explored in the pelletized material. Water-adsorption studies have been carried out in bulk and processed materials, and because of the considerable capacity to adsorb water, proton-conduction studies have been investigated for 1.University of the Basque Country GIU 20/028Portuguese Foundation for Science and Technology UIDB/50011/2020 UIDP/50011/2020 LA/P/0006/2020Spanish Government PGC2018-102052-A-C22 PGC2018-102052-B-C21 PID2019-108028GB-C21Basque Government IT1755-22 IT1310-19 IT1291-19Junta de Andalucia B-FQM-734-UGR20 ProyEx-cel_00386 FQM-39

Adsorptive Capacity, Inhibitory Activity and Processing Techniques for a Copper-MOF Based on the 3,4-Dihydroxybenzoate Ligand

Supplementary Materials: The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/molecules27228073/s1Acknowledgments: E.E. is grateful to the Government of the Basque Country for the predoctoral fellowship and R.F.M for the Junior Research Position CEECIND/ 00553/2017. S.R. acknowledges the Juan de la Cierva Incorporación Fellowship (grant agreement no. IJC2019-038894-I). The authors thank for technical and human support provided by SGIker of UPV/EHU and European funding (ERDF and ESF) and also wish to acknowledge the terrific help of all reviewers of the present manuscript, whose comments helped to improve the quality of the work.Funding: This work was developed within the scope of the projects given by the University of the Basque Country (GIU 20/028 Junta de Andalucía (B-FQM-734-UGR20, ProyExcel_00386 and FQM-394), the Spanish Ministry of Science, Innovation and Universities (MCIU/AEI/FEDER, UE) (PGC2018-102052-B-C21) and the CICECO-Aveiro Institute of Materials (UIDB/50011/2020 and UIDP/50011/2020).Due to the fast, emerging development of antibiotic-resistant bacteria, the need for novel, efficient routes to battle these pathogens is crucial; in this scenario, metal-organic frameworks (MOFs) are promising materials for combating them effectively. Herein, a novel Cu-MOF—namely 1—that displays the formula [Cu3L2(DMF)2]n (DMF = N,N-dimethylformamide) is described, synthesized by the combination of copper(II) and 3,4-dihydroxybenzoic acid (H3L)—both having well-known antibacterial properties. The resulting three-dimensional structure motivated us to study the antibacterial activity, adsorptive capacity and processability of the MOF in the form of pellets and membranes as a proof-of-concept to evaluate its future application in devices.Government of the Basque Country for the predoctoral fellowship and R.F.M for the Junior Research Position CEECIND/00553/2017Juan de la Cierva Incorporación Fellowship (grant agreement no. IJC2019-038894-I)SGIker of UPV/EHUEuropean funding (ERDF and ESF)University of the Basque Country (GIU 20/028 Junta de Andalucía (B-FQM-734-UGR20, ProyExcel_00386 and FQM-394)Spanish Ministry of Science, Innovation and Universities (MCIU/AEI/FEDER, UE) (PGC2018-102052-B-C21)CICECO-Aveiro Institute of Materials (UIDB/50011/2020 and UIDP/50011/2020

Synthesis, Structural Features and Physical Properties of a Family of Triply Bridged Dinuclear 3d-4f Complexes

New dinuclear MII-LnIII complexes of general formulas [Cu(µ-L)(µ-OAc)Ln(NO3 )2 ]·CH3CN· H2O (LnIII = Gd (1), Tb (2), Dy (3) and Er (4)), [Ni(CH3CN)(µ-L)(µ-OAc)Ln(NO3 )2 ]·CH3CN (LnIII = Nd (5), Gd (6), Tb (7), Dy (8), Er (9) and Y (10)) and [Co(CH3CN)(µ-L)(µ-OAc)Ln(NO3 )2 ]·CH3CN (LnIII = Gd (11), Tb (12), Dy (13), Er (14) and Y (15)) were prepared from the compartmental ligand N,N0 -dimethyl-N,N0 -bis(2-hydroxy-3-formyl-5-bromo-benzyl)ethylenediamine (H2L). In all these complexes, the transition metal ions occupy the internal N2O2 coordination site of the ligand, whereas the LnIII ions lie in the O4 external site. Both metallic ions are connected by an acetate bridge, giving rise to triple mixed diphenoxido/acetate bridged MIILnIII compounds. Direct current (dc) magnetic measurements allow the study of the magnetic exchange interactions between the 3d and 4f metal ions, which is supported by density functional theory (DFT) theoretical calculations for the GdIII - based counterparts. Due to the weak ferromagnetic exchange coupling constants obtained both experimentally and theoretically, the magneto-thermal properties of the less anisotropic systems (compounds 1 and 6) are also studied. Alternating current (ac)magnetic measurements reveal the occurrence of slight frequency dependency of the out-of-phase signal for complexes 8, 9 and 13, while complex 15 displays well-defined maximums below ~6 K.Junta de Andalucía (FQM-195 and the projects of excellence P11-FQM-7756 and A-FQM-172-UGR18)MINECO of Spain (Projects CTQ2014-56312-P and PGC2018-102052-B-C21)University of GranadaUniversity of The Basque Country UPV/EHU (Project GIU14/01

A Mixed Heterobimetallic Y/Eu-MOF for the Cyanosilylation and Hydroboration of Carbonyls

Supplementary Materials The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/catal12030299/s1. Table S1: Elemental analysis of compounds Y/Eu-MOF. Table S2: ICP-AES results of compound Y/Eu-MOF. Table S3: Crystallographic data and structure refinement details of compound Y/Eu-MOF. Table S4: Selected bond lengths (Å) and angles (°) for compound Y/Eu-MOF. Table S5: Table of the continuous Shape Measurements for the MN3O6 coordination environment. Table S6: Table of the continuous Shape Measurements for the MO8 coordination environment. Table S7: Electrophoretic mobility and ζ-potential dependence, with the pH of the Y/Eu-MOFs particles dispersed in water. Conductivity fixed at 330 µS/cm. Table S8: Optimization of the reaction conditions in the hydroboration reaction. Table S9: Green metrics calculated for Y/Eu-MOF catalyst. Table S10: Catalytic cyanosilylation of benzaldehyde performances of Ln-MOFs, as reported in the literature. Figure S1: Figure of the pattern matching analysis and experimental PXRD for Y/Eu-MOF. Figure S2: Figure of the infrared spectra of the ligand and Y/Eu-MOF. Figure S3: SEM and EDS mapping of bulk material of Y/Eu-MOF. Figure S4: Images and particle size distribution (an overall of 250 particles) in the deposited fraction of Y/Eu-MOF catalyst non-suspended in water (about a 68% of the total amount), determined from optical microscope images. Figure S5: Images and particle size distribution (an overall of 250 particles) of Y/Eu-MOF crystals in the fraction steadily suspended in water (about a 32% of the total amount), determined from optical microscope images. Figure S6: Comparation of the particle size distribution of Y/Eu-MOF in the fraction steadily suspended in water and the non-suspended, determined from optical microscope images. Figure S7: Calibration line of conductivity (µS/cm) vs [NaCl] (mol/L). Figure S8: ζ-potential (mV) dependence with the pH of the Y/Eu-MOF. All the measurements were performed with constant conductivity of 330 µS/cm. Figure S9: Electrophoretic mobility (µm·cm/V·s) dependence with the pH of the Y/Eu-MOF. All the measurements were performed with constant conductivity of 330 µS/cm. Figure S10: Study of the recyclability of Y/Eu-MOF (0.5 mol%) catalyst on the cyanosilylation and hydroboration reaction of acetophenone as carbonyl substrate. Figure S11: Analysis of the TOF (h−1) obtained in the cyanosilylation reaction of acetophenone at different times of reaction with Y/Eu-MOF (0.5 mol%), with the optimized reaction conditions. Figure S12: Analysis of the TOF (h−1) obtained in the hydroboration reaction acetophenone at different times of reaction with Y/Eu-MOF (0.5 mol%), with the optimized reaction conditions. Scheme S1: Reaction conditions used for the study of recyclability of Y/Eu-MOF catalysts in the cyanosilylation reaction. Scheme S2: Reaction conditions used for the study of recyclability of Y/Eu-MOF catalysts in the hydroboration reaction. Scheme S3: Leaching test, carried out after the first and second cycles.Funding: This research has been funded by the State Research Agency (grants CTQ2017-84334-R and PGC2018-102052-B-C21) of the Spanish Ministry of Science, Innovation and Universities, the European Union (European Regional Development Fund—ERDF), Junta de Andalucía (P20_01041, UAL2020-AGR-B1781, B-FQM-734-UGR20 and FQM-394). E.E., S.R., and J.P. acknowledge the Government of the Basque Country, Juan de la Cierva Incorporación (grant no. IJC2019-038894-I) and University of Almeria (grant no. HIPATIA2021_04) for their respective fellowsHerein, to the best of our knowledge, the first heterobimetallic Y/Eu porous metal–organic framework (MOF), based on 3-amino-4-hydroxybenzoic acid (H2L) ligand, with the following formulae {[Y3.5Eu1.5L6(OH)3(H2O)3]·12DMF}n (in advance, namely Y/Eu-MOF), is described. The three-dimensional structure has been synthesized by solvothermal routes and thoroughly characterized, by means of single crystal X-ray diffraction, powder X-ray diffraction, electronic microscopy, ICP-AES, electrophoretic mobility, and FTIR spectra. Intriguingly, the porous nature allows for coordinated solvent molecules displacement, yielding unsaturated metal centers, which can act as a Lewis acid catalyst. This novel supramolecular entity has been tested in cyanosilylation and hydroboration reactions on carbonyl substrates of a diverse nature, exhibiting an extraordinary activity.Cierva Incorporación IJC2019-038894-IState Research Agency CTQ2017-84334-R, PGC2018-102052-B-C21University of Almeria HIPATIA2021_04Ministerio de Ciencia, Innovación y UniversidadesEuropean CommissionEuropean Regional Development FundJunta de Andalucía B-FQM-734-UGR20, FQM-394, IJC2019-038894-I, P20_01041, UAL2020-AGR-B178

Multifunctional Lanthanide-Based Metal−Organic Frameworks Derived from 3‑Amino-4-hydroxybenzoate: Single-Molecule Magnet Behavior, Luminescent Properties for Thermometry, and CO2 Adsorptive Capacity

ACKNOWLEDGMENTS The authors thank SGIker of UPV/EHU and European funding (ERDF and ESF) for technical and human support as well as wish to acknowledge the terrific help of all reviewers of the present manuscript whose comments helped to improve the quality of the work.Supporting Information The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.2c00544.Funding E.E. is grateful to the Government of the Basque Country for the predoctoral fellowship and R.F.M. to the Junior Research Position CEECIND/ 00553/2017. The research contract of FF (REF-168-89-ARH/2018) is funded by national funds (OE), through FCT, in the scope of the framework contract foreseen in nos. 4, 5, and 6 of article 23 of the Decree-Law 57/2016, of 29 August, changed by Law 57/2017, of 19 July. This work was developed within the scope of the projects given by the Spanish Ministry of Science, Innovation and Universities (MCIU/AEI/ FEDER, UE) (PGC2018-102052-A-C22, PGC2018-102052-BC21, and PID2019-108028GB-C21), Gobierno Vasco/Eusko Jaurlaritza (IT1310-19 and IT1291-19), Junta de Andalucía (FQM-394), University of the Basque Country (GIU 20/028), and CICECO-Aveiro Institute of Materials (UIDB/50011/ 2020 and UIDP/50011/2020).Herein, we describe and study a new family of isostructural multifunctional metal–organic frameworks (MOFs) with the formula {[Ln5L6(OH)3(DMF)3]·5H2O}n (where (H2L) is 3-amino-4-hydroxybenzoic acid ligand) for magnetism and photoluminescence. Interestingly, three of the materials (Dy-, Er-, and Yb-based MOFs) present single-molecule magnet (SMM) behavior derived from the magnetic anisotropy of the lanthanide ions as a consequence of the adequate electronic distribution of the coordination environment. Additionally, photoluminescence properties of the ligand in combination with Eu and Tb counterparts were studied, including the heterometallic Eu–Tb mixed MOF that shows potential as ratiometric luminescent thermometers. Finally, the porous nature of the framework allowed showing the CO2 sorption capacity.Government of the Basque CountryJunior Research Position CEECIND/ 00553/2017National funds (OE)Spanish Ministry of Science, Innovation and Universities (MCIU/AEI/ FEDER, UE) (PGC2018-102052-A-C22, PGC2018-102052-BC21, and PID2019-108028GB-C21)Gobierno Vasco/Eusko Jaurlaritza (IT1310-19 and IT1291-19)Junta de Andalucía (FQM-394)University of the Basque Country (GIU 20/028)CICECO-Aveiro Institute of Materials (UIDB/50011/ 2020 and UIDP/50011/2020

Adsorptive Capacity, Inhibitory Activity and Processing Techniques for a Copper-MOF Based on the 3,4-Dihydroxybenzoate Ligand

Due to the fast, emerging development of antibiotic-resistant bacteria, the need for novel, efficient routes to battle these pathogens is crucial; in this scenario, metal-organic frameworks (MOFs) are promising materials for combating them effectively. Herein, a novel Cu-MOF—namely 1—that displays the formula [Cu3L2(DMF)2]n (DMF = N,N-dimethylformamide) is described, synthesized by the combination of copper(II) and 3,4-dihydroxybenzoic acid (H3L)—both having well-known antibacterial properties. The resulting three-dimensional structure motivated us to study the antibacterial activity, adsorptive capacity and processability of the MOF in the form of pellets and membranes as a proof-of-concept to evaluate its future application in devices.This work was developed within the scope of the projects given by the University of the Basque Country (GIU 20/028 Junta de Andalucía (B-FQM-734-UGR20, ProyExcel_00386 and FQM-394), the Spanish Ministry of Science, Innovation and Universities (MCIU/AEI/FEDER, UE) (PGC2018-102052-B-C21) and the CICECO−Aveiro Institute of Materials (UIDB/50011/2020 and UIDP/50011/2020)

Karboxilato estekatzaileetan oinarritutako funtzio anitzeko materialen diseinua, sintesia, karakterizazioa eta aplikazioen garapena.

El capítulo 5 está sujeto a confidencialidad por la autora. En euskera solo están los capítulos 1, 2 y 3. 286 p. (eng.) 179 p. (eusk.)La presente tesis doctoral tiene como objetivo el desarrollo de nuevos compuestos de coordinación y redes metal-orgánicas (MOFs) multifuncionales. Engloba el diseño, la síntesis y caracterización estructural derivada de una apropiada selección de ligandos orgánicos con grupos carboxilato y metales de transición o iones lantánidos. Asimismo, incluye el estudio de diversas aplicaciones perfiladas a las características del material final buscando un óptimo rendimiento. Cabe destacar el empleo de estos materiales con la finalidad del estudio de sus propiedades magnéticas, fotoluminiscentes, quiroópticas (CPL), adsorción de gases, resonancia magnética de imagen (MRI), catálisis heterogénea, actividad biológica y actividad antibacteriana. Adicionalmente, se ha trabajado en técnicas de procesamiento y en el estudio de estabilidad respecto a temperatura y humedad de los materiales procesados simulando condiciones análogas a las que puedan experimentar en procesos industriales; abordando así desde estados iniciales de síntesis hasta requerimientos derivados de implementación del material relativa en una particular aplicación

Diseño, síntesis y caracterización de nuevos complejos de coordinación basados en principios activos con actividad biológica conocida

[ES]El presente trabajo tiene como objetivo la síntesis y caracterización de nuevos complejos de coordinación partiendo de ligandos con actividad biológica conocida. El principio activo elegido es el diclofenaco sódico, fármaco que pertenece al grupo de medicamentos Antiinflamatorio No Esteroideos (AINES) y se emplea, entre otras cosas, para tratar artritis reumatoide y osteoartritis. Una vez sintetizados, los complejos se caracterizarán empleando diferentes técnicas experimentales como son el análisis elemental, espectroscopía infrarroja (FT-IR) y difracción de rayos X en polvo y en monocristal. Además, se analizarán las propiedades magnéticas y luminiscentes de los complejos obtenidos. El interés en medir las propiedades magnéticas viene motivado por que los complejos podrían presentar propiedades de molécula imán (o Single Molecule Magnets “SMMs”) los cuales, hoy en día, atraen gran interés debido a que son la base de nuevos materiales magnéticos con múltiples aplicaciones industriales como puede ser el almacenamiento de información, el procesamiento cuántico de información y la refrigeración magnética. El estudio de la emisión luminiscente de los iones de lantánidos es también un campo con diferentes aplicaciones tecnológicas de gran interés. Entre las posibles aplicaciones, cabe destacar el creciente interés del estudio de los complejos que emiten en el NIR –[Pr(III), Nd(III), Er(III) e Yb(III)]–, debido a que presentan aplicaciones en dispositivos ópticos y electrónicos . Además, los complejos formados con los iones metálicos Eu(III) y Tb(III) se emplean en análisis biomédicos. Por lo descrito anteriormente, en el presente trabajo se recoge la síntesis y caracterización de nuevos complejos de coordinación basados en el ligando diclofenaco sódico, el cual presenta propiedades biológicas conocidas, y un análisis de las propiedades magnéticas y luminiscentes.[EN]The principal goal of this work is the synthesis and characterization of new coordination complexes using ligands that present known biological properties. Diclofenac sodium salt will be used as ligand in this work. It belongs to Nonsteroidal Anti-Inflammatory drugs and is employed to treat rheumatic arthritis and osteoporosis among other diseases. Once the complexes are synthesised several characterization techniques will be applied to determine their structures; such as, infrared spectroscopy (FT-IR), elemental analysis, and X ray diffraction in powder and in monocrystal. Analysis of magnetic properties and photoluminiscence measurements will be carried out in order to enrich and extend information about these complexes. Due to the fact that molecules could behave as Single Molecule Magnets (SMMs), the measurements of their magnetic properties present an important role in this work. These materials are nowadays becoming more and more famous as they present several possible industrial applications such as information storage, quantum processing or magnetic cooling.1 In addition, photoluminiscence emission analysis in lanthanide ions is another powerful field that is being developed and today offers interesting technological applications. The study of complexes that emit in NIR –[Pr(III), Nd(III), Er(III) and Yb(III)]–, must be highlighted occasioned by their application in optic devices. Also, Eu(III) and Tb(III) coplexes are used in biomedical analysis.2 In summary, the present study describes the synthesis and characterization of new coordination complexes that are based on ligands with known biological properties, so as diclofenac sodium salt, with the final goal of studying and measuring magnetic and photoluminescence properties in the complexes

A Mixed Heterobimetallic Y/Eu-MOF for the Cyanosilylation and Hydroboration of Carbonyls

Herein, to the best of our knowledge, the first heterobimetallic Y/Eu porous metal–organic framework (MOF), based on 3-amino-4-hydroxybenzoic acid (H2L) ligand, with the following formulae {[Y3.5Eu1.5L6(OH)3(H2O)3]·12DMF}n (in advance, namely Y/Eu-MOF), is described. The three-dimensional structure has been synthesized by solvothermal routes and thoroughly characterized, by means of single crystal X-ray diffraction, powder X-ray diffraction, electronic microscopy, ICP-AES, electrophoretic mobility, and FTIR spectra. Intriguingly, the porous nature allows for coordinated solvent molecules displacement, yielding unsaturated metal centers, which can act as a Lewis acid catalyst. This novel supramolecular entity has been tested in cyanosilylation and hydroboration reactions on carbonyl substrates of a diverse nature, exhibiting an extraordinary activity