Efficient Gas Separation and Transport Mechanism in Rare Hemilabile Metal–Organic Framework

Understanding/visualizing the established interactions between gases and adsorbents is mandatory to implement better performance materials in adsorption/separation processes. Here we report the unique behavior of a rare example of a hemilabile chiral three-dimensional metal–organic framework (MOF) with an unprecedented qtz-e-type topology, with formula CuII2(S,S)-hismox·5H2O (1) (hismox = bis[(S)-histidine]oxalyl diamide). 1 exhibits a continuous and reversible breathing behavior, based on the hemilability of carboxylate groups from l-histidine. In situ powder (PXRD) and single crystal X-ray diffraction (SCXRD) using synchrotron radiation allowed us to unveil the crystal structures of four …

Soluble/MOF-Supported Palladium Single Atoms Catalyze the Ligand-, Additive-, and Solvent-Free Aerobic Oxidation of Benzyl Alcohols to Benzoic Acids.

Metal single-atom catalysts (SACs) promise great rewards in terms of metal atom efficiency. However, the requirement of particular conditions and supports for their synthesis, together with the need of solvents and additives for catalytic implementation, often precludes their use under industrially viable conditions. Here, we show that palladium single atoms are spontaneously formed after dissolving tiny amounts of palladium salts in neat benzyl alcohols, to catalyze their direct aerobic oxidation to benzoic acids without ligands, additives, or solvents. With this result in hand, the gram-scale preparation and stabilization of Pd SACs within the functional channels of a novel methyl-cystein…

Multivariate Metal-Organic Frameworks for the Simultaneous Capture of Organic and Inorganic Contaminants from Water

We report a new water-stable multivariate (MTV) Metal-Organic Framework (MOF) prepared by combining two different oxamide-based metalloligands derived from the natural amino acids L-serine and L-methionine. This unique material features hexagonal channels decorated with two types of flexible and functional 'arms' (-CH2OH and -CH2CH2SCH3) capable to act, synergistically, for the simultaneous and efficient removal of both inorganic (heavy metals like Hg2+, Pb2+ and Tl+) and organic (dyes such as Pyronin Y, Auramine O, Brilliant Green and Methylene Blue) contaminants and, in addition, this MTV-MOF is completely reusable. Single-crystal X-ray diffraction (SCXRD) measurements allowed to solve th…

Highly Efficient MOF-Driven Silver Subnanometer Clusters for the Catalytic Buchner Ring Expansion Reaction

The preparation of novel efficient catalysts-that could be applicable in industrially important chemical processes-has attracted great interest. Small subnanometer metal clusters can exhibit outstanding catalytic capabilities, and thus, research efforts have been devoted, recently, to synthesize novel catalysts bearing such active sites. Here, we report the gram-scale preparation of Ag2subnanometer clusters within the channels of a highly crystalline three-dimensional anionic metal-organic framework, with the formula [Ag2]@AgNa{Ni[Cu(Mempba)]}·48HO [Mempba= N,N′-2,4,6-trimethyl-1,3-phenylenebis(oxamate)]. The resulting crystalline solid catalyst-fully characterized with the help of single-c…

Cover Feature: Crystallographic Visualization of a Double Water Molecule Addition on a Pt 1 ‐MOF during the Low‐temperature Water‐Gas Shift Reaction (ChemCatChem 4/2021)

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

[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 measur…

Efficient Capture of Organic Dyes and Crystallographic Snapshots by a Highly Crystalline Amino-Acid-Derived Metal-Organic Framework

The presence of residual organic dyes in water resources or wastewater treatment systems, derived mainly from effluents of different industries, is a major environmental problem with no easy solution. Herein, an ecofriendly, water-stable metal-organic framework was prepared from a derivative of the natural amino acid l-serine. Its functional channels are densely decorated with highly flexible l-serine residues bearing hydroxyl groups. The presence of such a flexible and functional environment within the confined environment of the MOF leads to efficient removal of different organic dyes from water: Pyronin Y, Auramine O, Methylene Blue and Brilliant Green, as unveiled by unprecedented snaps…

A post-synthetic approach triggers selective and reversible sulphur dioxide adsorption on a metal-organic framework.

We report the application of a post-synthetic solid-state cation-exchange process to afford a novel 3D MOF with hydrated barium cations hosted at pores able to trigger selective and reversible SO2 adsorption. Computational modelling supports the full reversibility of the adsorption process on the basis of weak supramolecular interactions between SO2 and coordinated water molecules.

Front Cover: Efficient Capture of Organic Dyes and Crystallographic Snapshots by a Highly Crystalline Amino-Acid-Derived Metal-Organic Framework (Chem. Eur. J. 67/2018)

Polímeros de coordinación porosos como reactores químicos para nuevos materiales avanzados: química en espacios confinados

The central aim of this PhD thesis is to develop synthetic procedures to construct metal organic-frameworks (MOFs) able to host/build up molecular-based species, such as metal ions with particular coordination environments, single atom catalysts (SACs), sub-nanometric metal clusters (SNMCs) and supramolecular coordination complexes (SCCs), otherwise hardly accessible, with high catalytic reactivity and in a multigram scale. The nature of the final assemblies has been characterised with a myriad of physical techniques, where taking advantage of the high crystallinity and structural robustness of the MOFs used as platforms, single-crsytal X-ray crystallography play a promienet role and provid…

Preparation and Characterization of Aminoglycoside-Loaded Chitosan/Tripolyphosphate/Alginate Microspheres against E. coli

Although aminoglycosides are one of the common classes of antibiotics that have been widely used for treating infections caused by pathogenic bacteria, the evolution of bacterial resistance mechanisms and their inherent toxicity have diminished their applicability. Biocompatible carrier systems can help sustain and control the delivery of antibacterial compounds while reducing the chances of antibacterial resistance or accumulation in unwanted tissues. In this study, novel chitosan gel beads were synthesized by a double ionic co-crosslinking mechanism. Tripolyphosphate and alginate, a polysaccharide obtained from marine brown algae, were employed as ionic cross-linkers to prepare the chitos…

Metal–Organic Frameworks as Playgrounds for Reticulate Single-Molecule Magnets

Achieving an accurate control on the final structure of Metal-Organic Frameworks (MOFs) is mandatory to obtain target physical properties. Here we describe how the combination of a metalloligand design strategy and a post-synthetic method is a versatile and powerful approach to success on this extremely difficult task. In a first stage, a novel oxamato-based tetranuclear cobalt(III) complex with a tetrahedron-shape geometry is used, for the first time, as metalloligand toward cal-cium(II) cations to lead a diamagnetic Ca(II)-Co(III) three-dimensional (3D) MOF (1). In a second stage, in a single-crystal to single-crystal manner the calcium(II) ions are replaced by terbium (III), dysprosium(I…

MOF-Triggered Synthesis of Subnanometer Ag02 Clusters and Fe3+ Single Atoms: Heterogenization Led to Efficient and Synergetic One-Pot Catalytic Reactions

Click amidations, esterifications and one–pot reactions catalyzed by Cu salts and multimetal–organic frameworks (M–MOFs)

Amides and esters are prevalent chemicals in Nature, industry and academic laboratories. Thus, it is not surprising that a plethora of synthetic methods for these compounds has been developed along the years. However, these methods are not 100% atom economical and generally require harsh reagents or reaction conditions. Here we show a “spring–loaded”, 100% atom–efficient amidation and esterification protocol which consists in the ring opening of cyclopropenones with amines or alcohols. Some alkyl amines react spontaneously at room temperature in a variety of solvents and reaction conditions, including water at different pHs, while other alkyl amines, aromatic amines and alcohols react in th…

CCDC 1891588: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Aida Grau-Atienza, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Alessio Fuoco, Elisa Esposito, Marcello Monteleone, Johannes C. Jansen, Joan Cano, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2019|Chem.Mater.|31|5856|doi:10.1021/acs.chemmater.9b01995

CCDC 1843114: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Pierre‐Edouard Casteran, Jesús Ferrando‐Soria, Donatella Armentano, Emilio Pardo|2018|Chem.-Eur.J.|24|17712|doi:10.1002/chem.201803547

CCDC 2090411: Experimental Crystal Structure Determination

Related Article: Rossella Greco, Estefanía Tiburcio, Brenda Palomar-De Lucas, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo, Antonio Leyva-Pérez|2022|Mol.Catal.|522|112228|doi:10.1016/j.mcat.2022.112228

CCDC 1891577: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Aida Grau-Atienza, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Alessio Fuoco, Elisa Esposito, Marcello Monteleone, Johannes C. Jansen, Joan Cano, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2019|Chem.Mater.|31|5856|doi:10.1021/acs.chemmater.9b01995

CCDC 1843112: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Pierre‐Edouard Casteran, Jesús Ferrando‐Soria, Donatella Armentano, Emilio Pardo|2018|Chem.-Eur.J.|24|17712|doi:10.1002/chem.201803547

CCDC 2155456: Experimental Crystal Structure Determination

Related Article: Estefanía Tiburcio, Yongkun Zheng, Marta Mon, Nuria Martín, Jesús Ferrando−Soria, Donatella Armentano, Antonio Leyva−Pérez, Emilio Pardo|2022|Inorg.Chem.|61|11796|doi:10.1021/acs.inorgchem.2c01508

CCDC 1891583: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Aida Grau-Atienza, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Alessio Fuoco, Elisa Esposito, Marcello Monteleone, Johannes C. Jansen, Joan Cano, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2019|Chem.Mater.|31|5856|doi:10.1021/acs.chemmater.9b01995

CCDC 2155455: Experimental Crystal Structure Determination

Related Article: Estefanía Tiburcio, Yongkun Zheng, Marta Mon, Nuria Martín, Jesús Ferrando−Soria, Donatella Armentano, Antonio Leyva−Pérez, Emilio Pardo|2022|Inorg.Chem.|61|11796|doi:10.1021/acs.inorgchem.2c01508

CCDC 1891594: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Aida Grau-Atienza, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Alessio Fuoco, Elisa Esposito, Marcello Monteleone, Johannes C. Jansen, Joan Cano, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2019|Chem.Mater.|31|5856|doi:10.1021/acs.chemmater.9b01995

CCDC 1891591: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Aida Grau-Atienza, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Alessio Fuoco, Elisa Esposito, Marcello Monteleone, Johannes C. Jansen, Joan Cano, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2019|Chem.Mater.|31|5856|doi:10.1021/acs.chemmater.9b01995

CCDC 1891582: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Aida Grau-Atienza, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Alessio Fuoco, Elisa Esposito, Marcello Monteleone, Johannes C. Jansen, Joan Cano, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2019|Chem.Mater.|31|5856|doi:10.1021/acs.chemmater.9b01995

CCDC 1891587: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Aida Grau-Atienza, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Alessio Fuoco, Elisa Esposito, Marcello Monteleone, Johannes C. Jansen, Joan Cano, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2019|Chem.Mater.|31|5856|doi:10.1021/acs.chemmater.9b01995

CCDC 1891590: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Aida Grau-Atienza, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Alessio Fuoco, Elisa Esposito, Marcello Monteleone, Johannes C. Jansen, Joan Cano, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2019|Chem.Mater.|31|5856|doi:10.1021/acs.chemmater.9b01995

CCDC 1891593: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Aida Grau-Atienza, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Alessio Fuoco, Elisa Esposito, Marcello Monteleone, Johannes C. Jansen, Joan Cano, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2019|Chem.Mater.|31|5856|doi:10.1021/acs.chemmater.9b01995

CCDC 1891579: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Aida Grau-Atienza, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Alessio Fuoco, Elisa Esposito, Marcello Monteleone, Johannes C. Jansen, Joan Cano, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2019|Chem.Mater.|31|5856|doi:10.1021/acs.chemmater.9b01995

CCDC 1891584: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Aida Grau-Atienza, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Alessio Fuoco, Elisa Esposito, Marcello Monteleone, Johannes C. Jansen, Joan Cano, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2019|Chem.Mater.|31|5856|doi:10.1021/acs.chemmater.9b01995

CCDC 1846740: Experimental Crystal Structure Determination

Related Article: Marta Mon, Estefanía Tiburcio, Jesús Ferrando-Soria, Rodrigo Gil San Millán, Jorge A. R. Navarro, Donatella Armentano, Emilio Pardo|2018|Chem.Commun.|54|9063|doi:10.1039/C8CC04482A

CCDC 1891576: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Aida Grau-Atienza, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Alessio Fuoco, Elisa Esposito, Marcello Monteleone, Johannes C. Jansen, Joan Cano, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2019|Chem.Mater.|31|5856|doi:10.1021/acs.chemmater.9b01995

CCDC 1891580: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Aida Grau-Atienza, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Alessio Fuoco, Elisa Esposito, Marcello Monteleone, Johannes C. Jansen, Joan Cano, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2019|Chem.Mater.|31|5856|doi:10.1021/acs.chemmater.9b01995

CCDC 1891586: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Aida Grau-Atienza, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Alessio Fuoco, Elisa Esposito, Marcello Monteleone, Johannes C. Jansen, Joan Cano, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2019|Chem.Mater.|31|5856|doi:10.1021/acs.chemmater.9b01995

CCDC 1891581: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Aida Grau-Atienza, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Alessio Fuoco, Elisa Esposito, Marcello Monteleone, Johannes C. Jansen, Joan Cano, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2019|Chem.Mater.|31|5856|doi:10.1021/acs.chemmater.9b01995

CCDC 1891592: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Aida Grau-Atienza, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Alessio Fuoco, Elisa Esposito, Marcello Monteleone, Johannes C. Jansen, Joan Cano, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2019|Chem.Mater.|31|5856|doi:10.1021/acs.chemmater.9b01995

CCDC 1843113: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Pierre‐Edouard Casteran, Jesús Ferrando‐Soria, Donatella Armentano, Emilio Pardo|2018|Chem.-Eur.J.|24|17712|doi:10.1002/chem.201803547

CCDC 1891585: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Aida Grau-Atienza, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Alessio Fuoco, Elisa Esposito, Marcello Monteleone, Johannes C. Jansen, Joan Cano, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2019|Chem.Mater.|31|5856|doi:10.1021/acs.chemmater.9b01995

CCDC 1843115: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Pierre‐Edouard Casteran, Jesús Ferrando‐Soria, Donatella Armentano, Emilio Pardo|2018|Chem.-Eur.J.|24|17712|doi:10.1002/chem.201803547

CCDC 1891578: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Aida Grau-Atienza, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Alessio Fuoco, Elisa Esposito, Marcello Monteleone, Johannes C. Jansen, Joan Cano, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2019|Chem.Mater.|31|5856|doi:10.1021/acs.chemmater.9b01995

CCDC 1891589: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Aida Grau-Atienza, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Alessio Fuoco, Elisa Esposito, Marcello Monteleone, Johannes C. Jansen, Joan Cano, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2019|Chem.Mater.|31|5856|doi:10.1021/acs.chemmater.9b01995

CCDC 1891595: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Aida Grau-Atienza, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Alessio Fuoco, Elisa Esposito, Marcello Monteleone, Johannes C. Jansen, Joan Cano, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2019|Chem.Mater.|31|5856|doi:10.1021/acs.chemmater.9b01995

CCDC 1891596: Experimental Crystal Structure Determination

Related Article: Marta Mon, Rosaria Bruno, Estefanía Tiburcio, Aida Grau-Atienza, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Alessio Fuoco, Elisa Esposito, Marcello Monteleone, Johannes C. Jansen, Joan Cano, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2019|Chem.Mater.|31|5856|doi:10.1021/acs.chemmater.9b01995