Emilio Pardo

Emilio Pardo
University of Valencia | UV · Instituto de Ciencia Molecular (ICMol)

PhD in Chemistry

About

168
Publications
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7,094
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Additional affiliations
January 2010 - December 2012
January 2008 - December 2012
Sorbonne Université
January 2003 - December 2013
University of Valencia

Publications

Publications (168)
Article
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 r...
Article
Based on a β-diketiminate ligand, an iron(III) tetrahedral high-spin complex, [LFeIII(Cl)2] (1), and an iron(II) high-spin triangular planar complex, [LFeIICl] (2), have been synthesized and structurally characterized. Also, complex 1 can be considered as a precursor to produce 2via a reduction process, with a concomitant change in its magnetic ani...
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Allylic alcohol epoxidation and dehydrogenation reactivity is distinguished when VO(acac)2 is used in solution or anchored in a metal organic framework (MOF). The chemical mechanism depends on the electronic profile...
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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–loade...
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The search for efficient technologies empowering the selective capture of environmentally harmful heavy metals from wastewater treatment plants, at affordable prices, attracts wide interest but constitutes an important technological challenge. We report here an eco-friendly single-walled carbon nanotube buckypaper (SWCNT-BP) enriched with a multiva...
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The combination of high crystallinity and rich host‐guest chemistry in metal‐organic frameworks (MOFs), have situated them in an advantageous position, with respect to traditional porous materials, to gain insight on specific weak noncovalent supramolecular interactions. In particular, sulfur s‐hole interactions are known to play a key role in the...
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The synthesis of mixed-component metal-organic frameworks (MOFs) –including multivariate MOFs (MTV-MOFs), multicomponent MOFs, mixed-metals MOFs and mixed-ligands and metals MOFs– is becoming a very active research field. This is mainly based on the unique possibilities these materials offer to incorporate multiple functionalities and in how this h...
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Extremely high electrophilic metal complexes, composed by a metal cation and very electron poor σ-donor ancillary ligands, are expected to be privileged catalysts for oxidation reactions in organic chemistry. However, their low lifetime prevents any use in catalysis. Here we show the synthesis of fluorinated pyridine-Pd 2+ coordinate cages within t...
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Developing efficient adsorbent materials is crucial for adsorption and separation to realize the purification of energy source and raw chemicals. Here, we report a novel and robust 3D In‐based MOF built up with fluorine‐functionalized ligands, QMOF‐2F , with improved separation properties of C2‐light hydrocarbons over methane at room temperature re...
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Achieving a precise control of the final structure of metal–organic frameworks (MOFs) is necessary to obtain desired physical properties. Here, we describe how the use of a metalloligand design strategy and a judicious choice of ligands inspired from nature is a versatile approach to succeed in this challenging task. We report a new porous chiral M...
Chapter
Herein, experimental developments in the construction of various well defined small aggregations of metal atoms, close to or within the sub-nanometric regime, so-called metal nanoclusters (MNCs), are summarized. In particular, the discussion is focussed on the use of metal–organic frameworks (MOFs) – an emerging type of porous functional materials...
Article
Composite Material for Lanthanides Recovery from Water In article number 2100730, Fiore Nicoletta, Giovanni De Filpo, Emilio Pardo, Donatella Armentano, and co-workers report the preparation of a novel bioMOF-based single-walled carbon nanotube buckypaper (MOF = metal–organic–framework) as a new and performant composite material for lanthanides rec...
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Human society is facing—among other environmental threats—an enormous challenge due to human activities. The extensive use of high-tech devices and electronics equipment in the daily life makes, among others, rare-earth elements (REEs) recovery from secondary sources highly required. Here, a novel bioMOF-based single-walled carbon nanotube buckypap...
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We present a novel bio-friendly water-stable Zn-based MOF (1), derived from the natural amino acid L-serine, which was able to efficiently photodegrade water solutions of brilliant green dye in only 120 min. The total degradation was followed by UV-Vis spectroscopy and further confirmed by single-crystal X-ray crystallography, revealing the presenc...
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Today, it is extremely urgent to face the increasing shortage of clean and safe water resources, determined by the exponential growth of both world population and its consumerism, climate change...
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The Cover Feature shows the presence of Pt1 single atoms, within the channels of a metal‐organic framework (MOF), which are capable of catalyzing, at low temperature, the water‐gas‐shift reaction (WGSR). In their Full Paper, C. Bilanin et al. show evidence that a double water attack occurs in the Pt‐catalyzed low‐temperature WGSR by a combination o...
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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 si...
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The mercury removal efficiency of a novel metal‐organic framework (MOF) derived from the amino acid S‐methyl‐L‐cysteine is presented and the process is characterized by single‐crystal X‐ray crystallography. A feasibility study is further presented on the performance of this MOF—and also that of another MOF derived from the amino acid L‐methionine—w...
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Ecuadorian black mineral sands were used as starting material for the production of iron-titanium oxide nanostructures. For this purpose, two types of mineral processing were carried out, one incorporating a pre-treatment before conducting an alkaline hydrothermal synthesis (NaOH 10 M at 180 °C for 72 h), and the other prescinding this first step....
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We report the two-step synthesis of a novel chiral rod-based porous coordination polymer (PCP). The chemical approach consists of the use of a previously prepared bis(ethylenediamine) copper monomer [Cu(en)]2(NO3)2 [where en = ethylenediamine] reacting with the cytidine 5′-monophosphate (CMP) nucleotide. The bis(ethylenediamine) copper compound—sta...
Chapter
Herein, experimental developments in the construction of various well defined small aggregations of metal atoms, close to or within the sub-nanometric regime, so-called metal nanoclusters (MNCs), are summarized. In particular, the discussion is focussed on the use of metal-organic frameworks (MOFs) - an emerging type of porous functional materials...
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Full-text available
A tetranuclear cubane-type complex [Co4(ntfa)4(CH3O)4(CH3OH)4] (1) with a {Co4O4} core, and a mononuclear complex [Co(ntfa)2(CH3OH)2] (2) have been rationally obtained by adjusting the ratio of the β-diketonate and Co(II) ions,...
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The low‐temperature water‐gas shift reaction (WGSR, CO + H 2 O ⇔ H 2 + CO 2 ) 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...
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The reactions of LnIII ions with a versatile pyridyl-decorated dicarboxylic acid ligand lead to the formation of a series of novel three-dimensional (3D) Ln-MOFs, [Ln3(pta)4(Hpta)(H2O)]·xH2O (Ln = Dy (1), Eu (2), Gd (3), Tb (4), H2pta = 2-(4-pyridyl)-terephthalic acid, x = 6 for 1, 2.5 for 2, 1.5 for 3 and 2 for 4). The Ln3+ ions act as nine-coordi...
Chapter
This chapter describes the different approaches that have been developed to synthesize metal organic frameworks (MOFs) with catalytic centres. In general, MOFs are materials composed of an organic and inorganic part, giving them great potential for catalysis. However, many of the stable MOF structures do not have active centres, and these have to b...
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Data revealing the phase and chemical compositions of natural black sands from “El Ostional” beach, located in the northern Ecuadorian Pacific coast have been presented. The samples were collected from six points over the shore area of approximately 500 × 40 m². The data on crystalline phases (iron titanium oxide, orthoclase feldspar and zircon) we...
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An amendment to this paper has been published and can be accessed via a link at the top of the paper.
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The Pt-catalysed addition of silanes to functional groups such alkenes, alkynes, carbonyls and alcohols, i.e. the hydrosilylation reaction, is a fundamental transformation in industrial and academic chemistry, often claimed as the most important application of Pt catalysts in solution. However, the exact nature of the Pt active species and its mech...
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The exact chemical structure of non–crystallising natural products is still one of the main challenges in Natural Sciences. Despite tremendous advances in total synthesis, the absolute structural determination of a myriad of natural products with very sensitive chemical functionalities remains undone. Here, we show that a metal–organic framework (M...
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The most widely used method to measure the transport properties of dense polymeric membranes is the time lag method in a constant volume/pressure increase instrument. Although simple and quick, this method provides only relatively superficial, averaged data of the permeability, diffusivity, and solubility of gas or vapor species in the membrane. Th...
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Structural insight into reactive species can be achieved via strategies such as matrix isolation in frozen glasses, whereby species are kinetically trapped, or by confinement within the cavities of host molecules. More recently, Metal-organic Frameworks (MOFs) have been used as molecular scaffolds to isolate reactive metal-based species within thei...
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A bio-metal-organic framework (bio-MOF) derived from the amino acid L-serine has been prepared in bulk form and evaluated as sorbent for the molecular recognition and extraction of B-vitamins. The functional pores of bio-MOF exhibit high amounts of hydroxyl groups jointly directing other supramolecular host-guest interactions thus providing the rec...
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Mixed matrix membranes (MMMs) are seen as promising candidates to overcome the fundamental limit of polymeric membranes, known as the so-called Robeson upper bound, which defines the best compromise between permeability and selectivity of neat polymeric membranes. To overcome this limit, the permeability of the filler particles in the MMM must be c...
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Since the advent of the first metal-organic frameworks (MOFs), we have witnessed an explosion of captivating architectures with exciting physicochemical properties and applications in a wide range of fields. This, in part, can be understood under the light of their rich host-guest chemistry and the possibility to use single-crystal X-ray diffractio...
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Complexation of dysprosium(iii) ions with a multidentate hydrazone ligand, N-[(E)-pyridin-2-ylmethylideneamino]pyridine-2-carboxamide (L), in the presence of different β-diketonate coligands, leads to the formation of two novel DyIII dimers, with formulas Dy2(BTFA)4(L)2 (1) and Dy2(TTA)4(L)2 (2) (BTFA = 3-benzoyl-1,1,1-trifluoroacetone and TTA = 4,...
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Achieving fine control on the structure of metal-organic frameworks (MOFs) is mandatory to obtain target physical properties. Herein, we present how the combination of a metalloligand approach and a postsynthetic method is a suitable and highly useful synthetic strategy to success on this extremely difficult task. First, a novel oxamato-based tetra...
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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) capa-ble t...
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Understand/visualize the established interactions between gases and adsorbents is mandatory to implement better per-formant materials in adsorption/separation processes. Here we report the unique behavior of a rare example of a hemila-bile chiral three-dimensional metal-organic framework (MOF) with an unprecedented qtz-e-type topology, with formula...
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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 using the mononuclear anionic complex [CuII(Me2pma)2]2–, as a bis(bidentat...
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By means of solvent effect, three new azido-copper 1D coordination polymers, [Cu(4-aba)(N3)] (1), [Cu(4-aba)(N3)(CH3OH)] (2), and [Cu(4-aba)(N3)(C2H5OH)] (3) (4-aba = 4-azidobenzoic acid), were successfully prepared in the presence of Cu2+ ion, NaN3 and 4-azidobenzoic acid. Interestingly, 1 can be employed as a precursor and transformed to 2 and 3...
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Supramolecular Coordination Compounds (SCCs) represent the power of Coordination Chemistry methodologies to self-assemble discrete architectures with targeted properties. SCCs are generally synthesised in solution, with isolat-ed fully-coordinated metal atoms as structural nodes, thus severely limited as metal-based catalysts. Metal-Organic Framewo...
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The efficient organization of discrete functional molecules into extended frameworks, while retaining its physical properties, is a mandatory requisite to move towards applications. Here we describe the validity of the metalloligand design strategy as a versatile and powerful approach to build up a two-dimensional (2D) magnetic Metal-Organic Framew...
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Metal‐Organic Frameworks can be used as porous templates to exert control over polymerization reactions. Here we show the possibilities offered by these crystalline, porous nanoreactors to capture highly‐reactive intermediates for a better understanding of the mechanism of polymerization reactions. By using a cyclodextrin framework we are capable o...
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Metal‐Organic Frameworks can be used as porous templates to exert control over polymerization reactions. Here we show the possibilities offered by these crystalline, porous nanoreactors to capture highly‐reactive intermediates for a better understanding of the mechanism of polymerization reactions. By using a cyclodextrin framework we are capable o...
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Two mononuclear cobalt(II) complexes, with formulas: [Co(2,6-dfba)2(bpp)2(H2O)2]n (1) and [Co(2,6-dfba)2(bpe)2(H2O)2]n (2) (2,6-Hdfba = 2,6-difluorobenzoic acid, bpp = 1,3-bis(4-pyridyl)propane, bpe = 1,2-bis(4-pyridyl)ethylene), have been synthesized by combing Co(II) ion with benzoate derivatives and two homogeneous N-donor ligands, respectively....
Article
We report the two-step synthesis of a chiral rod-like metal-organic framework (MOF). The chemical approach consists on the use of a previously prepared oxamato-based homochiral hexanuclear wheel, the ligand being a derivative of the natural amino acid L-alanine, with formula (Me4N)6{CuII6[(S)-alama])6}·10H2O (1) [where (S)-alama = (S)-N-(ethyl oxoa...
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A family of four mononuclear β-diketonate-DyIII complexes, with formulas Dy(tmhd)3(Br2-bpy) (1), Dy(tmhd)3(Br-bpy) (2), Dy(tmhd)3(dppz) (3) and Dy(tmhd)3(mcdpq) (4) (tmhd = 2,2,6,6- tetramethyl-3,5-heptanedione, Br2-bpy = 5,5'-dibromo-2,2'-bipyridine, Br-bpy = 5-bromo-2,2'-bipyridine, dppz = dipyrido [3,2-a:2',3'- c]phenazine and mcdpq = 2-methoxyl...
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Invited for the cover of this issue are the groups of Emilio Pardo at Universitat de València, and Donatella Armentano at Università della Calabria. The image depicts both water contamination by industry and decontamination by metal–organic frameworks. Read the full text of the article at 10.1002/chem.201803547. “The high crystallinity of these mat...
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By means of the facile chemistry, structural assembly, and transformation of four mononuclear Dy(III) complexes, Dy(bpad)3·CH3OH·H2O (1), Dy(bpad)2(H2O)2·NO3 (2), [Dy(bpad)2(tmhd)] (3), and [Dy(bpad)2(btfa)] (4) (Hbpad = N3-benzoylpyridine-2-carboxamidrazone, tmhd = 2,2,6,6-tetramethylheptane-3,5-dione, btfa = 3-benzoyl-1,1,1-trifluoroacetone), wit...
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The synthesis and reactivity of single metal atoms in low–valence state bound to just water, rather than to organic ligands or surfaces, is a major experimental challenge. Here, we show a gram–scale wet synthesis of Pt11+ stabilized in a confined space by a well–defined crystallographic first water sphere, and with a second coordination sphere link...
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The synthesis and reactivity of single metal atoms in low–valence state bound to just water, rather than to organic ligands or surfaces, is a major experimental challenge. Here, we show a gram–scale wet synthesis of Pt11+ stabilized in a confined space by a well–defined crystallographic first water sphere, and with a second coordination sphere link...
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We report two new highly crystalline metal-organic frameworks (MOFs), derived from the natural amino acids serine (1) and threonine (2), featuring hexagonal channels densely decorated with hydroxyl groups belonging to the amino acid residues. Both 1 and 2 are capable of discriminating, via solid-phase extraction, a mixture of selected chloride salt...
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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...
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Imines are ubiquitous intermediates in organic synthesis and the metal–mediated imination of alcohols is one of the most direct and simple method 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 r...
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A novel eco‐friendly water‐stable metal–organic framework, prepared from a derivative of the natural amino acid L‐serine and featuring functional channels, efficiently captures different organic dyes at very low concentrations, similar to those observed in industrial discharges. In addition, single‐crystal X‐ray diffraction offers unprecedented sna...
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The residual presence of organic dyes in water resources or wastewater treatment systems, derived mainly from dumping of different industries, constitutes a major environmental problem with no easy answer. Here we report an eco‐friendly water‐stable metal‐organic framework ‐prepared from a derivative of the natural amino acid L‐serine‐ featuring fu...
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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 a selective and reversible...
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The search for simple, earth–abundant, cheap and non–toxic metal catalysts able to perform industrial hydrogenations is a topic of interest, transversal to many catalytic processes. Here, we show that isolated FeIII–O sites on solids are able to dissociate and chemoselectively transfer H2 to acetylene in an industrial process. For that, a novel, ro...
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We report a new chiral coordination polymer, prepared from the cytidine 5’-monophosphate (CMP) nucleotide, capable to separate efficiently (enantiomeric excess of ca. 100 %) racemic mixtures of L- and D-...
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We report a novel metal-organic framework (MOF) featuring functional pores decorated with hydroxyl groups derived from the natural amino acid L-serine, which is able to establish specific interactions of different nature, strength and directionality with organic molecules of technological interest, i.e. ascorbic acid, pyridoxine, bupropion and 17-b...