Síntesis de nuevos materiales magnéticos multifuncionales con ligandos aromáticos polioxamato

The main goal of this Ph.D thesis concerns the synthesis of multifunctional magnetic coordination polymers with oxamato ligands, which is one of the most challenging topics for chemists and physicists working together in the multidisciplinary field of materials chemistry. In order to do so, we have taken advantage of the new developments of metallosupramolecular chemistry, in particular the molecular-programmed self-assembly methods that exploit the coordination preferences of metal ions and specifically tailored ligands. In this sense, the judicious choice of the appropriate oxamato-based metal building block (substitution pattern and steric requirements of the bridging ligand, as well as the electronic configuration and magnetic anisotropy of the metal ion) allowed us to control the different structural topologies as well as the interesting and predictable magnetic properties in the final compounds. Interestingly, most of the synthesized coordination polymers are anionic. Thus, we can, tentatively, insert an additional physical property (to the magnetic ones) by using the appropriate countercation. The results obtained along this Ph.D thesis are divided in three different chapters according to the dimensionality of the coordination polymer. Furthermore, each chapter is subdivided in two parts (A and B) depending on the properties exhibited by the compounds (Chapter I) and the nature of the precursor used to synthesized the coordination polymers (Chapters II and III). Chapter I has been divided in two parts in accordance with the properties of the one-dimensional compounds. Thus, in the first part we present the synthesis of a new family of neutral oxamato-bridged heterobimetallic chains MIICuII (M = Mn and Co) prepared by treating the corresponding anionic oxamatocopper(II) complexes with 3d cations using DMF or DMSO as solvents. Interestingly, this family of heterobimetallic chains provides several examples of Single Chain Magnets (SCMs), where the nature of the corresponding transition metal as well as the substitution pattern of the bridging ligand on the SCM behaviour were studied. In the second part of this chapter we prepared a new series of neutral oxamato-bridged heterobimetallic chiral chains MIICuII (M = Mn and Co), where only the enantiopure CoIICuII chains showed slow magnetic relaxation at low temperatures, which is characteristic of SCMs. Furthermore, solid circular dichroism (CD) spectra of the bimetallic chain compounds were recorded in order to establish their chiral and enantiomeric nature. As each couple of enantiomeric chains are non superimposable mirror images, they exhibit maximum positive and negative Cotton effects, constituting the first examples of enantiopure SCMs. In the second chapter, we present several two- (2D) and three-dimensional (3D) coordination polymers exhibiting different architectures and magnetic properties, that can somehow be controlled by means of the appropriate choice of the precursor and the metal ion used to build them. Furthermore, we present for the first time in oxamato-based compounds the porous properties of some of them. At this respect, in the first part of this chapter we explain the influence of the metal ions and the monooxamatocopper(II) complexes on the topology and the magnetic properties of the synthesized coordination polymers. In the second part we describe a family of heterobimetallic MIICuII (M = Mn and Co) bidimensional coordination polymers obtained by reaction of the corresponding dinuclear bis-oxamatocopper(II) complexes with the metal ions. Additionally, in this family we studied the influence of the substitution pattern of the bridging ligand on the magnetic properties. The last chapter is devoted to the introduction of multifunctionality in oxamato-based systems. It has been divided again in two parts in accordance with the nature of the precursor used to synthesize the multifunctional coordination polymer. Anyway both parts have a common background consisting on the use of the complex as ligand strategy in order to build the anionic inorganic network, the other physical property being brought by the organic countercation. At this respect, in the first part we focus on the use the monooxamatocopper(II) precursor complexes with different functional countercations, which added the new property, toward manganese(II) ions to obtain the corresponding bi- and tridimensional compounds that encapsulate the non-innocent counteractions. Similarly, in the second part we describe the synthesis of the same kind of multifunctional 2D and 3D polymers by using dinuclear oxamato-copper(II) precursors instead of the mononuclear ones. For example, herein we report the first oxamato-based examples of: (i) chiral magnets, (ii) luminescent magnets, (iii) porous magnets showing sorption properties and (iv) a porous magnet showing a solvatomagnetic switching

Supramolecular coordination chemistry of aromatic polyoxalamide ligands: A metallosupramolecular approach toward functional magnetic materials

The impressive potential of the metallosupramolecular approach in designing new functional magnetic materials constitutes a great scientific challenge for the chemical research community that requires an interdisciplinary collaboration. New fundamental concepts and future applications in nanoscience and nanotechnology will emerge from the study of magnetism as a supramolecular function in metallosupramolecular chemistry. Our recent work on the rich supramolecular coordination chemistry of a novel family of aromatic polyoxalamide (APOXA) ligands with first-row transition metal ions has allowed us to move one step further in the rational design of metallosupramolecular assemblies of increasing structural and magnetic complexity. Thus, we have taken advantage of the new developments of metallosupramolecular chemistry and, in particular, the molecular-programmed self-assembly methods that exploit the coordination preferences of paramagnetic metal ions and suitable designed polytopic ligands. The resulting self-assembled di- and trinuclear metallacyclic complexes with APOXA ligands, either metallacyclophanes or metallacryptands, are indeed ideal model systems for the study of the electron exchange mechanism between paramagnetic metal centers through extended π-conjugated aromatic bridges. So, the influence of different factors such as the topology and conformation of the bridging ligand or the electronic configuration and magnetic anisotropy of the metal ion have been investigated in a systematic way. These oligonuclear metallacyclic complexes can be important in the development of a new class of molecular magnetic devices, such as molecular magnetic wires (MMWs) and switches (MMSs), which are major goals in the field of molecular electronics and spintronics. On the other hand, because of their metal binding capacity through the outer carbonyl-oxygen atoms of the oxamato groups, they can further be used as ligands, referred to as metal–organic ligands (MOLs), toward either coordinatively unsaturated metal complexes or fully solvated metal ions. This well-known “complex-as-ligand” approach affords a wide variety of high-nuclearity metal–organic clusters (MOCs) and high-dimensionality metal–organic polymers (MOPs). The judicious choice of the oligonuclear MOL, ranging from mono- to di- and trinuclear species, has allowed us to control the overall structure and magnetic properties of the final oxamato-bridged multidimensional (nD, n = 0–3) MOCs and MOPs. The intercrossing between short- (nanoscopic) and long-range (macroscopic) magnetic behavior has been investigated in this unique family of oxamato-bridged metallosupramolecular magnetic materials expanding the examples of low-dimensional, single-molecule (SMMs) and single-chain (SCMs) magnets and high-dimensional, open-framework magnets (OFMs), which are brand-new targets in the field of molecular magnetism and materials science

Measuring Spin⋅⋅⋅Spin Interactions between Heterospins in a Hybrid [2]Rotaxane.

Use of molecular electron spins as qubits for quantum computing will depend on the ability to produce molecules with weak but measurable interactions between the qubits. Here we demonstrate use of pulsed EPR spectroscopy to measure the interaction between two inequivalent spins in a hybrid rotaxane molecule

Toward Engineering Chiral Rodlike Metal-Organic Frameworks with Rare Topologies

The establishment of novel design strategies to target chiral rodlike MOFs, elusively faced until now, is one of the most straightforward manners to widen the scope of MOFs. Here we describe our last advances on the application of the metalloligand design strategy toward the development of efficient routes to obtain chiral rodlike MOFs. To this end, we have used as precursor an enantiopure homochiral hexanuclear wheel (1), derived from the amino acid d-valine, which, after a supramolecular reorganization into a one-dimensional homochiral chain-with the same configuration as 1-led to the formation of a homochiral rodlike MOF (2) exhibiting rare etd topology

OMA -AMO - Casa de la música de Oporto

La investigación de un “objeto arquitectónico” enlaza con los principios teóricos desde los que en ARKRIT-LAB se entiende la crítica la arquitectura: la obra antes que el autor y su descripción antes que su interpretación. Consecuentemente, se propuso estudiar un edificio relevante y considerado de gran impacto teórico y mediático, entrando primero de manera precisa en su respuesta al medio, al material, a la medida, a la morfología y a la misión -metodo M3- y proponiendo después, entre los investigadores del laboratorio diversas actividades: re exionar de manera abierta sobre las condiciones de su “arquitectura”, experimentar el edi cio, rastrear sus antecedentes e investigar en la materia concreta y en las formas utilizadas; actividades que buscaban nuevas realidades que pudieran mostrar otras visiones. En el laboratorio consideramos que como arquitectos y como críticos, no resulta super uo aprender a ver más, a oír más, a sentir más y a pensar más4. El edificio elegido para el curso 2010-2011 fue la “Casa da Musica” de Oporto, proyecto de OMA-Rem Koolhaas, siendo el texto que se convirtió en referencia para la primera aproximación el titulado “Otra Modernidad” de Rafael Moneo. Texto en el que se describe el proyecto como encarnación de los nuevos atributos de la arquitectura contemporánea5. “Otra Modernidad” entendida desde la Modernidad, como frontera considerada por Antonio Miranda como referente de progreso y faro de toda acción arquitectónica. Modernidad como anhelo de una sociedad nueva más justa

Metal-organic frameworks as chemical nanoreactors for the preparation of catalytically active metal compounds

[EN] Since the emergence of metal¿organic frameworks (MOFs), a myriad of thrilling properties and applications, in a wide range of fields, have been reported for these materials, which mainly arise from their porous nature and rich host¿guest chemistry. However, other important features of MOFs that offer great potential rewards have been only barely explored. For instance, despite the fact that MOFs are suitable candidates to be used as chemical nanoreactors for the preparation, stabilization and characterization of unique functional species, that would be hardly accessible outside the functional constrained space offered by MOF channels, only very few examples have been reported so far. In particular, we outline in this feature recent advances in the use of highly robust and crystalline oxamato- and oxamidato-based MOFs as reactors for the in situ preparation of well-defined catalytically active single atom catalysts (SACS), subnanometer metal nanoclusters (SNMCs) and supramolecular coordination complexes (SCCs). The robustness of selected MOFs permits the post-synthetic (PS) in situ preparation of the desired catalytically active metal species, which can be characterised by single-crystal X-ray diffraction (SC-XRD) taking advantage of its high crystallinity. The strategy highlighted here permits the always challenging large-scale preparation of stable and well-defined SACs, SNMCs and SCCs, exhibiting outstanding catalytic activities.This work was supported by the MICINN (Spain) (Projects PID2019-104778GB-I00, PID2020-115100GB-I00, and Excellence Unit Maria de Maeztu CEX2019-000919-M) and the Ministero dell Istruzione, dell Universita` e della Ricerca (Italy). The work has also been funded by Generalitat Valenciana, Prometeo Grupos de Investigacio¿n de Excelencia (PROMETEU/2021/ 054). D. A. acknowledges the financial support of the Fondazione CARIPLO/ Economia Circolare: ricerca per un futuro sostenibile 2019, Project code: 2019 2090, MOCA. Thanks are also extended to the 2019 Post-doctoral Junior LeaderRetaining Fellowship, la Caixa Foundation (ID100010434 and fellowship code LCF/BQ/PR19/11700011), the Generalitat Valenciana (SEJI/2020/034) and the Ramo¿n y Cajal program (J. F.-S.). E. P. acknowledges the financial support of the European Research Council under the European Union s Horizon 2020 research and innovation programme/ERC Grant Agreement No 814804, MOF-reactors. This study forms part of the Advanced Materials programme and was supported by MCIN with funding from European Union NextGenerationEU (PRTR-C17.I1) and by Generalitat Valenciana (MFA/2022/048).Escamilla, P.; Guerra, WD.; Leyva Perez, A.; Armentano, D.; Ferrando-Soria, J.; Pardo, E. (2023). Metal-organic frameworks as chemical nanoreactors for the preparation of catalytically active metal compounds. Chemical Communications. 59. https://doi.org/10.1039/d2cc05686k5

Crystallographic Visualization of a Double Water Molecule Addition on a Pt-1-MOF during the Low-temperature Water-Gas Shift Reaction

This is the peer reviewed version of the following article: C. Bilanin, E. Tiburcio, J. Ferrando-Soria, D. Armentano, A. Leyva-Pérez, E. Pardo, ChemCatChem 2021, 13, 1195, which has been published in final form at https://doi.org/10.1002/cctc.202001492. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.[EN] The low-temperature water-gas shift reaction (WGSR, CO+H2O H-2+CO2) is considered a very promising reaction -candidate for fuel cells- despite an efficient and robust catalyst is still desirable. One of the more prominent catalysts for this reaction is based on single Pt atoms (Pt-1) on different supports, which are supposed to manifold the reaction by the accepted mechanism for the general WGSR, i. e. by addition of one H2O molecule to CO, with generation of CO2 and H-2. Here we show, experimentally, that not one but two H2O molecules are added to CO on the Pt-1 catalyst, as assessed by a combination of reactivity experiments with soluble Pt catalysts, kinetic and spectroscopic measurements, and finally by in-operando single crystal X-ray diffraction on a Pt-1-MOF, to visualize the formation of the hemiacetal intermediate on the solid catalytic site. These results confirm our previous DFT predictions and provide a paradigmatic shift in the assumed mechanism of the WGSR, which may open the debate if two H2O molecules are recurrently added during the WGSR, not only for Pt-1 catalysts but also for other metal catalysts.This work was supported by the Ministero dell'Istruzione, dell'Universita e della Ricerca (Italy) and the Ministerio de Ciencia e Innovacion (Spain) (Projects PID2019-104778GB-I00 and CTQ2017-86735-P and the excellence units "Severo Ochoa" SEV-2016-0683 and "Maria de Maeztu" CEX2019-000919-M). C. B. and E. T. thank ITQ and MINECO for the concession of fellowships. Thanks are extended to the "2019 Post-doctoral Junior Leader-Retaining Fellowship, la Caixa Foundation (ID100010434 and fellowship code LCF/BQ/PR19/11700011" (J. F.-S.). D.A. acknowledges the financial support of the Fondazione CARIPLO / "Economia Circolare: ricerca per un futuro sostenibile" 2019, Grant number: 2019-2090, MOCA. We thank to Dr. R. Adam, Dr. J. Oliver-Meseguer and J. C. Arango for their help. E.P. acknowledges the financial support of the European Research Council under the European Union's Horizon 2020 research and innovation programme / ERC Grant Agreement No 814804, MOF-reactors. We acknowledge Diamond Light Source for awarded beamtime and provision of synchrotron radiation facilities with dosing gas cell and thank Dr Mark Warren for his assistance at I19 beamline (Proposal number MT18768-2).Bilanin-Artigado, C.; Tiburcio, E.; Ferrando-Soria, J.; Armentano, D.; Leyva Perez, A.; Pardo, E. (2021). Crystallographic Visualization of a Double Water Molecule Addition on a Pt-1-MOF during the Low-temperature Water-Gas Shift Reaction. ChemCatChem. 13(4):1195-1200. https://doi.org/10.1002/cctc.202001492S1195120013

Design of Multivariate Biological Metal-Organic Frameworks: Toward Mimicking Active Sites of Enzymes

[EN] Mimicking enzymatic processes carried out by natural enzymes, which are highly efficient biocatalysts with key roles in living organisms, attracts much interest but constitutes a synthetic challenge. Biological metal-organic frameworks (bioMOFs) are potential candidates to be enzyme catalysis mimics, as they offer the possibility to combine biometals and biomolecules into open-framework porous structures capable of simulating the catalytic pockets of enzymes. In this work, we first study the catalase activity of a previously reported bioMOF, derived from the amino acid L-serine, with formula {(CaCu6II)-Cu-II[(S,S)-serimox](3)(OH)(2)(H2O)} 39H(2)O (1) (serimox = bis[(S)-serine]oxalyl diamide), which is indeed capable to mimic catalase enzymes, in charge of preventing cell oxidative damage by decomposing, efficiently, hydrogen peroxide to water and oxygen (2H(2)O(2) -> 2 H2O + O-2). With these results in hand, we then prepared a new multivariate bioMOF (MTV-bioMOF) that combines two different types of bioligands derived from L-serine and L-histidine amino acids with formula (CaCu6II)-Cu-II[(S,S)-serimox](2)[(S,S)-hismox](1)(OH)(2)(H2O)}27H(2)O (2) (hismox = bis[(S)-histidine]oxalyl diamide ligand). MTV-bioMOF 2 outperforms 1 degrading hydrogen peroxide, confirming the importance of the amino acid residue from the histidine amino acid acting as a nucleophile in the catalase degradation mechanism. Despite displaying a more modest catalytic behavior than other reported MOF composites, in which the catalase enzyme is immobilized inside the MOF, this work represents the first example of a MOF in which an attempt is made to replicate the active center of the catalase enzyme with its constituent elements and is capable of moderate catalytic activity.This work was supported by the Ministero dell'Istruzione, dell'Universita e della Ricerca (Italy) and the MINECO (Spain) (Projects PID2019-104778GB-I00, PID2021-123856OBI00 PID2022-136349OB-I00 and Excellence Unit "Maria de Maeztu" CEX2019-000919-M). D.A. acknowledges the financial support of the Fondazione CARIPLO/"Economia Circolare: Ricerca per un futuro sostenibile" 2019, Project code: 2019-2090. Thanks are also extended to the "Generalitat Valenciana" (Project PROMETEO/2021/054). E.P. acknowledges the financial support of the European Research Council under the European Union's Horizon 2020 research and innovation programme/ERC Grant Agreement No 814804, MOF-reactors. Thanks are also extended to the Ramon y Cajal Program, RYC2019-027940-I (J.F.-S.). D.A. acknowledges Diamond Light Source (I-19, CY28808-1) for the access to Synchrotron beamtime. This study forms part of the Advanced Materials programme (MFA/2022/048) and was supported by MCIN with funding from European Union NextGenerationEU (PRTR-C17.I1) and by Generalitat Valenciana. A.D. is beneficiary of a grant Maria Zambrano in Universitat Politecnica de Valencia within the framework of the grants for retraining in the Spanish university system (Spanish Ministry of Universities, financed by the European Union, NextGeneration EU). S.N. thanks the support of grant PID2021-123856OBI00 funded by MICIU/AEI/10.13039/501100011033 and by ERDF A way of making Europe.Navarro-Alapont, J.; Negro, C.; Navalón, S.; Amarajothi, DM.; Armentano, D.; Ferrando-Soria, J.; Pardo, E. (2024). Design of Multivariate Biological Metal-Organic Frameworks: Toward Mimicking Active Sites of Enzymes. Inorganic Chemistry. 63(29):13681-13688. https://doi.org/10.1021/acs.inorgchem.4c019881368113688632

Magnetic order in a CuII-DyIII oxamato-based two-dimensional coordination polymer

We report the synthesis, crystal structure and magnetic characterization of a novel two-dimensional copper(II)-dysprosium(III) coordination polymer of formula [LiI(OH2)4]2[DyIIICuII2(Me2pma)4Cl(H2O)] . 4H2O (1) [Me2pma = N-2,6-dimethylphenyloxamate]. Compound 1 was obtained by using the mononuclear anionic complex, [CuII(Me2pma)2]2-, as a bis(bidentate) metalloligand toward solvated dysprosium(III) cations and shows a square [DyIIICuII2] layered structure of (44.62) net topology. Interestingly, the combination of two factors, the well-known efficiency of oxamato ligands to transmit strong magnetic couplings between neighboring atoms and such structural topology, is responsible for the observation of a ferromagnetic interaction between copper(II) and dysprosium(III) cations and a magnetic ordering (TC = 7.5 K), paving the way for the obtention of novel future examples of the still very scarce magnetically ordered lanthanide-based coordination polymers

Stabilized Ru[(H2O)(6)](3+) in Confined Spaces (MOFs and Zeolites) Catalyzes the lmination of Primary Alcohols under Atmospheric Conditions with Wide Scope

[EN] Imines are ubiquitous intermediates in organic synthesis, and the metal-mediated imination of alcohols is one of the most direct and simple methods for their synthesis. However, reported protocols lack compatibility with many other functional groups since basic supports/media, pure oxygen atmospheres, and/or released hydrogen gas are required during reaction. Here we show that, in contrast to previous metal-catalyzed methods, hexa-aqueous Ru(III) catalyzes the imination of primary alcohols with very wide functional group tolerance, at slightly acid pH and under low oxygen atmospheres. The inorganic metal complex can be supported and stabilized, integrally, within either faujasite-type zeolites (Y and X) or a metal organic framework (MOF), to give a reusable heterogeneous catalyst which provides an industrially viable process well below the flammability limit of alcohols and amines.This work was supported by the MINECO (Spain) (Projects CTQ2017-86735-P, CTQ2016-75671-P, CTQ2014-56312-P, CTQ2014-55178-R, and MAT2013-40823-R and Excellence Units "Severo Ochoa" SEV2016-0683 and "Maria de Maeztu" and MDM-2015-0538) and the European Union through ERC-AdG-2014-671093 (SynCatMatch) and the Ministero dell'Istruzione, dell'Universita e della Ricerca (Italy) (FFABR 2017). M.M. thanks the MINECO for a predoctoral contract. RA. thanks UPV for a postdoctoral contract. J.F.-S. acknowledges financial support from the Subprograma Atraccio de Talent - Contractes Postdoctorals de la Universitat de Valencia. We also acknowledge SOLEIL for provision of the synchrotron radiation facility and thank Pierre Fertey for his assistance.Mon, M.; Adam-Ortiz, R.; Ferrando-Soria, J.; Corma Canós, A.; Pardo, E.; Armentano, D.; Leyva Perez, A. (2018). Stabilized Ru[(H2O)(6)](3+) in Confined Spaces (MOFs and Zeolites) Catalyzes the lmination of Primary Alcohols under Atmospheric Conditions with Wide Scope. ACS Catalysis. 8(11):10401-10406. https://doi.org/10.1021/acscatal.8b03228S104011040681