Self-assembly of a chiral three-dimensional manganese(II)-copper(II) coordination polymer with a double helical architecture

2013

The use of the anionic dicopper(ii) complex, [CuII(mpba) 2]4- [mpba = N,N′-1,3-phenylenebis(oxamate)], as tetrakis(bidentate) metalloligand toward MnII ions in the presence of oxalate and the chiral (S)-trimethyl-(1-phenylethyl)ammonium cation affords the first example of a mixed oxalato/oxamato-based chiral 3D metal-organic polymer. © 2013 The Royal Society of Chemistry.

Glassy PEEK‐WC vs Rubbery Pebax®1657 Polymers: Effect on the Gas Transport in CuNi‐MOF Based Mixed Matrix Membranes

2020

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 carefully matched with that of the polymer matrix. The present work shows that it is not sufficient to match only the permeability of the polymer and the dispersed phase, but that one should consider also the individual contributions of the diffusivity and the solubility of the gas in both components. Here we compare the gas transport performance o…

Bio-metal-organic frameworks for molecular recognition and sorbent extraction of hydrophilic vitamins followed by their determination using HPLC-UV

2020

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 recognition of B-vitamins in fruit juices and energy drinks. Single-crystal X-ray diffraction studies reveal the specific B-vitamin binding sites and the existence of multiple hydrogen bonds between these target molecules and the framework. It offered unique snapshots to accomplish an efficient capture of these solutes in complex aqueous matrices. Fo…

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

2023

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 par…

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

2019

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.

2021

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…

Selective and Efficient Removal of Mercury from Aqueous Media with the Highly Flexible Arms of a BioMOF

2016

A robust and water-stable metal-organic framework (MOF), featuring hexagonal channels decorated with methionine residues (1), selectively captures toxic species such as CH3 Hg(+) and Hg(2+) from water. 1 exhibits the largest Hg(2+) uptake capacity ever reported for a MOF, decreasing the [Hg(2+) ] and [CH3 Hg(+) ] concentrations in potable water from highly hazardous 10 ppm to the much safer values of 6 and 27 ppb, respectively. Just like with biological systems, the high-performance metal capture also involves a molecular recognition process. Both CH3 Hg(+) and Hg(2+) are efficiently immobilized by specific conformations adopted by the flexible thioether "claws" decorating the pores of 1. T…

Enantioselective self-assembly of antiferromagnetic hexacopper(ii) wheels with chiral amino acid oxamates

2013

The Cu(2+)-mediated self-assembly of oxamato-based ligands derived from either the (S)- or (R)-enantiomers of the amino acid valine leads to the formation of two antiferromagnetically coupled homochiral anionic hexacopper(II) wheels in the presence of templating tetramethylammonium countercations.

ChemInform Abstract: Oxamato-Based Coordination Polymers: Recent Advances in Multifunctional Magnetic Materials

2014

The design and synthesis of novel examples of multifunctional magnetic materials based on the so-called coordination polymers (CPs) have become very attractive for chemists and physicists due to their potential applications in nanoscience and nanotechnology. However, their preparation is still an experimental challenge, which requires a deep knowledge of coordination chemistry and large skills in organic chemistry. The recent advances in this field using a molecular-programmed approach based on rational self-assembly methods which fully exploit the versatility of the coordination chemistry of the barely explored and evergreen family of N-substituted aromatic oligo(oxamato) ligands are prese…

Multivariate Metal-Organic Framework/Single-Walled Carbon Nanotube Buckypaper for Selective Lead Decontamination.

2022

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 multivariate amino acid-based metal-organic framework (MTV-MOF) for the efficient and selective removal of Pb

Synthesis and Enhanced Capture Properties of a New BioMOF@SWCNT‐BP: Recovery of the Endangered Rare‐Earth Elements from Aqueous Systems (Adv. Mater. …

2021

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

2019

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…

Synthesis of a chiral rod-like metal–organic framework from a preformed amino acid-based hexanuclear wheel

2019

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 oxoacetate)alanine]. The anionic hexacopper(II) wheels, stabilized by the presence of templating tetramethylammonium counter-cations, disassemble in the presence of cationic square-planar [Ni(cyclam)]2+ complexes to yield, after a supramolecular reorganization process that involves axial coordination of the [Ni(cyclam)]2+ cations through the free carbon…

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

2021

Multielectron oxidation in a ferromagnetically coupled dinickel(ii) triple mesocate.

2015

Triple-stranded dinuclear nickel(ii) complexes of the meso-helicate type have been obtained from the new N,N'-1,3-phenylenebis(pyrazine-2-carboxamidate) ligand; they possess a multielectron redox behaviour featuring up to four stepwise, one-electron oxidation reactions of the two ferromagnetically coupled Ni(II) ions to afford the putative high-valent dinickel(iii) and dinickel(iv) species, as supported by theoretical calculations.

MOF-Stabilized Perfluorinated Palladium Cages Catalyze the Additive-Free Aerobic Oxidation of Aliphatic Alcohols to Acids

2021

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 coordinate cages within the channels of an anionic tridimensional metal-organic framework (MOF), and their use as efficient metal catalysts for the aerobic oxidation of aliphatic alcohols to carboxylic acids without any additive. Mechanistic studies strongly support that the MOF-stabilized coordination cage with perfluorinated ligands unleashes the full electrophilic potenti…

Dicopper(II) Metallacyclophanes with Electroswitchable Polymethyl-Substitutedpara-Phenylene Spacers

2013

Double-stranded anionic dinuclear copper(II) metallacyclic complexes of the paracyclophane type [Cu2L2]4- have been prepared by the CuII-mediated self-assembly of different para-phenylenebis(oxamato) bridging ligands with either zero-, one-, or four-electron-donating methyl substituents (L=N,N′-para- phenylenebis(oxamate) (ppba; 1), 2-methyl- N,N′-para-phenylenebis(oxamate) (Meppba; 2), and 2,3,5,6-tetramethyl- N,N′-para-phenylenebis(oxamate) (Me4ppba; 3)). These complexes have been isolated as their tetra-n-butylammonium (1 a-3 a), lithium(I) (1 b-3 b), and tetraphenylphosphonium salts (1 c-3 c). The X-ray crystal structures of 1 a and 3 c show a parallel-displaced π-stacked conformation w…

Coordinating and hydrogen bonding ability of a bifunctional 2D paddle-wheel copper(II) coordination polymer

2015

abstract A new copper(II) complex of formula {[Cu 2 (H 2 btc) 2 (dmf) 2 ] 4dmf} n (1)[H 4 btc = 1,2,4,5-benzenetetracarb-oxylic acid, dmf = dimethylformamide] has been synthesised and its structure determined by X-raydiffraction. The structure displays a new square grid of ‘‘paddle-wheel’’ tetracarboxylate-bridgeddicopper(II) units with an intradimer copper–copper separation of 2.619(2) A. The dmf molecules areretained through weak axial coordinative bonds and hydrogen bonding interactions with the carboxylicgroups of the porous neutral network of 4 4 net topology. The magnetic behaviour of 1 corresponds to astrong antiferromagnetic coupling within each dicopper(II) unit (J = 343 cm 1 with …

Copper(II) complexes with 2,5-bis(2-pyridyl)pyrazine and oxalate and croconate: Synthesis, crystal structure and magnetic properties

2012

Abstract Two new copper(II) complexes of formula [Cu2(2,5-dpp)(C2O4)2(H2O)4] (1) and [Cu2(2,5-dpp)(C5O5)2(H2O)4]·3H2O (2) [2,5-dpp = 2,5-bis(2-pyridyl)pyrazine, C2O42− = oxalate and C5O52− = croconate (dianion of 4,5-dihydroxycyclopent-4-ene-1,2,3-trione)] have been prepared and their structures determined by X-ray crystallographic methods. Compounds 1 and 2 are dinuclear complexes where the 2,5-dpp molecule acts as a bis-bidentate bridge between the two copper(II) ions, the electroneutrality being achieved by the presence of bidentate oxalate (1) and croconate (2) ligands. Each copper(II) ion exhibits an elongated octahedral CuN2O4 environment with two nitrogen atoms from 2,5-dpp and two o…

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

2010

Abstract 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 …

Spin control in oxamato-based manganese(II)-copper(II) coordination polymers with brick-wall layer architectures.

2011

Two new heterobimetallic manganese(II)-copper(II) coordination polymers of formulas [Mn(2)Cu(2)(Me(3)mpba)(2)(H(2)O)(6)]·8H(2)O (1) and [Mn(2)Cu(2)(Me(4)ppba)(2)(H(2)O)(6)]·8H(2)O (2) [Me(3)mpba = 2,4,6-trimethyl-N,N'-1,3-phenylenebis(oxamate) and Me(4)ppba = 2,3,5,6-tetramethyl-N,N'-1,4-phenylenebis(oxamate)] have been synthesized following a molecular-programmed self-assembly method from the corresponding dicopper(II) complexes acting as metalloligands toward Mn(II) ions. 1 and 2 consist of neutral Mn(II)(2)Cu(II)(2) layers with a brick-wall structure made up of oxamato-bridged Mn(II)Cu(II) chains connected through double meta- (1) and para-substituted (2) permethylated phenylene spacers.…

Oligo-m-phenyleneoxalamide Copper(II) Mesocates as Electro-Switchable Ferromagnetic Metal–Organic Wires

2010

Double-stranded copper(II) string complexes of varying nuclearity, from di- to tetranuclear species, have been prepared by the CuII-mediated self-assembly of a novel family of linear homo- and heteropolytopic ligands that contain two outer oxamato and either zero (1 b), one (2 b), or two (3 b) inner oxamidato donor groups separated by rigid 2-methyl-1,3-phenylene spacers. The X-ray crystal structures of these CuIIn complexes (n=2 (1 d), 3 (2 d), and 4 (3 d)) show a linear array of metal atoms with an overall twisted coordination geometry for both the outer CuN2O2 and inner CuN4 chromophores. Two such nonplanar all-syn bridging ligands 1 b–3 b in an anti arrangement clamp around the metal ce…

Formation of an interlocked double-chain from an organic-inorganic [2]rotaxane.

2019

Here we show that a structure containing a polymeric interlocking daisy chain is obtained from the reaction of an inorganic–organic [2]rotaxane [HB{CrIII7NiII(μ-F)8(O2CtBu)16}], where B is an organic thread terminated with a bi-pyridyl unit, with an oxo-centered metal carboxylate triangle [FeIII2CoII(μ3-O)(O2CtBu)6(HO2CtBu)3].

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

2018

[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 …

Self-assembly of catalytically-active supramolecular coordination compounds within metal-organic frameworks

2019

[EN] Supramolecular coordination compounds (SCCs) represent the power of coordination chemistry methodologies to self-assemble discrete architectures with targeted properties. SCCs are generally synthesized in solution, with isolated fully coordinated metal atoms as structural nodes, thus severely limited as metal-based catalysts. Metal-organic frameworks (MOFs) show unique features to act as chemical nanoreactors for the in situ synthesis and stabilization of otherwise not accessible functional species. Here, we present the self-assembly of Pd-II SCCs within the confined space of a pre-formed MOF (SCCs@MOF) and its post-assembly metalation to give a Pd-II-Au-III supra molecular assembly, c…

Reversible Solvatomagnetic Switching in a Spongelike Manganese(II)-Copper(II) 3D Open Framework with a Pillared Square/Octagonal Layer Architecture

2012

The concept of "molecular magnetic sponges" was introduced for the first time in 1999 by the creative imagination of the late Olivier Kahn. It refers to the exotic spongelike behavior of certain molecule-based materials that undergo a dramatic change of their magnetic properties upon reversible dehydration/rehydration processes. Here we report a unique example of a manganese(II)-copper(II) mixed-metal-organic framework of formula [Na(H(2)O)(4)](4)[Mn(4){Cu(2)(mpba)(2)(H(2)O)(4)}(3)]·56.5H(2)O (1) (mpba=N,N'-1,3-phenylenebis(oxamate)). Compound 1 possesses a 3D Mn(II)(4)Cu(II)(6) pillared layer structure with mixed square and octagonal pores of approximate dimensions 1.2×1.2 nm and 2.1×3.0 n…

The oxamate route, a versatile post-functionalization for metal incorporation in MIL-101(Cr): Catalytic applications of Cu, Pd, and Au

2013

Abstract A new consecutive post-functionalization method has been developed for the inclusion of additional metal functionalities in Metal Organic Frameworks (MOFs) through oxamate as chelating agent. This may result in catalytic centers of metal–organic complexes or in controlled formation of metal nanoparticles, demonstrated for Cu, Pd and Au, in the highly stable MIL-101(Cr) framework. In a first post-synthesis step, reduction of the NO 2 -MIL-101(Cr) leads to the formation of NH 2 -MIL-101(Cr). The second functionalization consists of a straightforward condensation of the amino groups of the ligand with ethyl chloro-oxoacetate resulting in the formation of free oxamates attached to the …

Gas Transport in Mixed Matrix Membranes: Two Methods for Time Lag Determination

2020

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. The present manuscript discusses a more sophisticated computational method to determine the transport properties on the basis of a fit of the entire permeation curve, including the transient period. The traditional tangent method and the fitting procedure were compared for the transport of six light gases (H2, He, O2, N2, CH4, and CO2) and ethane an…

Rational enantioselective design of chiral heterobimetallic single-chain magnets: synthesis, crystal structures and magnetic properties of oxamato-br…

2011

A new series of neutral oxamato-bridged M(II)Cu(II) chiral chains of general formula [MCuL(x)(S)(m)(H(2)O)(n)]·aS·bH(2)O [L(1)=(M)-1,1'-binaphthalene-2,2'-bis(oxamate) with M=Mn (1a) and Co (1b); L(2)=(P)-1,1'-binaphthalene-2,2'-bis(oxamate) with M=Mn (2a) and Co (2b)] and the analogous racemic chains of formula [MCuL(3)(S)(m)(H(2)O)(n)]·aS·bH(2)O [L(3)=1,1'-binaphthalene-2,2'-bis(oxamate) with M=Mn (3a) and Co (3b)] have been prepared by reaction of the corresponding dianionic oxamatocopper(II) complex [Cu(L(x))](2-) with Mn(2+) or Co(2+) cations in either dimethylformamide (DMF) or dimethyl sulfoxide (DMSO). Solid circular dichroism (CD) spectra of the bimetallic chain compounds were reco…

Capping N‐Donor Ligands Modulate the Magnetic Dynamics of Dy III β‐Diketonate Single‐Ion Magnets with D 4 d Symmetry

2019

A family of four mononuclear DyIII β-diketonate 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, mcdpq=2-methoxyl-3-cyanodipyrido[3,2-f:2,3'-h]quinoxaline) were prepared by modifying the capping N-donor coligands. DyIII centers in these complexes feature an N2 O6 octacoordinate environment with distorted square-antiprismatic D4d symmetry. Magnetic investigations evidenced single-ion magnet behavior in all complexes with energy barriers Ueff of 42.10 (1), 61.47…

Synthesis, crystal structures and magnetic properties of M(II)Cu(II) chains (M = Mn and Co) with sterically hindered alkyl-substituted phenyloxamate …

2011

A series of neutral oxamato-bridged heterobimetallic chains of general formula [MCu(L(x)2 (S)2] · p S · q H2O [p = 0-1, q = 0-2.5; L1 = N-2,6-dimethylphenyloxamate, S = DMF with M = Mn (1a) and Co (1b); L2 = N-2,6-diethylphenyloxamate, S = DMF with M = Mn (2a) and Co (2b) or S = DMSO with M = Mn (2c) and Co (2 d); L3 = N-2,6-diisopropylphenyloxamate, S = DMF with M = Mn (3a) and Co (3b) or S = DMSO with M = Mn (3c) and Co (3d)] were prepared by treating the corresponding anionic oxamatocopper(II) complexes [Cu(L(x))(2)]2- (x = 1-3) with M(2+) cations (M = Mn and Co) in DMF or DMSO as the solvent. The single-crystal X-ray structures of 2a and 3a reveal the occurrence of well-isolated, zigzag…

Ferromagnetic coupling and magnetic anisotropy in oxalato-bridged trinuclear chromium(iii)-cobalt(ii) complexes with aromatic diimine ligands

2010

Two novel heterotrinuclear chromium(III)-cobalt(II) complexes of formula {[Cr(III)(bpy)(ox)(2)](2)Co(II)(Me(2)bpy)}.2H(2)O (1) and {[Cr(III)(phen)(ox)(2)](2)Co(II)(Me(2)bpy)}.1.5H(2)O (2) [ox = oxalato, bpy = 2,2'-bipyridine, Me(2)bpy = 6,6'-dimethyl-2,2'-bipyridine, and phen = 1,10-phenanthroline] have been synthesized using the "complex-as-ligand/complex-as-metal" strategy. The X-ray crystal structure of 2 consists of neutral oxalato-bridged Cr(III)(2)Co(II) bent entities formed by the coordination of two anionic [Cr(III)(phen)(ox)(2)](-) complexes through one of their oxalato groups toward a cationic cis-[Co(II)(Me(2)bpy)](2+) complex. The three tris(chelated), six-coordinated metal atom…

Switching of easy-axis to easy-plane anisotropy in cobalt(ii) complexes

2021

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, with the synthetic processes being monitored by in situ microcalorimetry. Then, following synthetic conditions to obtain 2, but using three distinct N-donor coligands - 2,2'-bipyridyl (bpy), 6,6'-dimethyl-2,2'-bipyridyl (6,6-(CH3)2-bpy) and 5,5'-dimethyl-2,2'-bipyridyl (5,5-(CH3)2-bpy) - three novel mononuclear complexes have been obtained, [Co(ntfa)2(bpy)2] (3), [Co(ntfa)2(6,6-(CH3)2- bpy)2] (4) and [Co(ntfa)2(5,5-(CH3)2-bpy)2] (5). The introduction of different cap…

Highly Efficient Removal of Neonicotinoid Insecticides by Thioether-Based (Multivariate) Metal–Organic Frameworks

2021

Circumventing the impact of agrochemicals on aquatic environments has become a necessity for health and ecological reasons. Herein, we report the use of a family of five eco-friendly water-stable isoreticular metal-organic frameworks (MOFs), prepared from amino acids, as adsorbents for the removal of neonicotinoid insecticides (thiamethoxam, clothianidin, imidacloprid, acetamiprid, and thiacloprid) from water. Among them, the three MOFs containing thioether-based residues show remarkable removal efficiency. In particular, the novel multivariate MOF {SrIICuII6[(S,S)-methox]1.5[(S,S)-Mecysmox]1.50(OH)2(H2O)}·36H2O (5), featuring narrow functional channels decorated with both -CH2SCH3 and -CH2…

Topological control of the spin coupling in dinuclear copper(II) complexes with meta- and para-phenylenediamine bridging ligands

2010

Abstract A novel series of copper(II) complexes of formula [Cu(tren)(mpda)](ClO4)2 · 1/2H2O (1), [Cu2(tren)2(mpda)](ClO4)4 · 2H2O (2), and [Cu2(tren)2(ppda)](ClO4)4 · 2H2O (3) containing the tetradentate tris(2-aminoethyl)amine (tren) terminal ligand and the potentially bridging 1,n-phenylenediamine [n = 3 (mpda) and 4 (ppda)] ligand have been prepared and spectroscopically characterized. X-ray diffraction on single crystals of 1 and 3 show the presence of mono- (1) and dinuclear (3) copper(II) units where the mpda (1) and ppda (3) ligands adopt terminal monodentate (1) and bridging bis(monodentate) (3) coordination modes toward [Cu(tren)]2+ cations with an overall non-planar, orthogonal di…

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

2021

[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…

Synthesis, structural analysis, and magnetic properties of ethylmalonate-manganese(II) complexes

2011

12 páginas, 10 figuras, 6 tablas.-- et al.

Solid-State Aggregation of Metallacyclophane-Based MnIICuII One-Dimensional Ladders

2012

Two distinct one-dimensional (1) and two-dimensional (2) mixed-metal-organic polymers have been synthesized by using the "complex-as-ligand" strategy. The structure of 1 consists of isolated ladderlike Mn(II)(2)Cu(II)(2) chains separated from each other by neutral Mn(II)(2) dimers, whereas 2 possesses an overall corrugated layer structure built from additional coordinative interactions between adjacent Mn(II)(2)Cu(II)(2) ladders. Interestingly, 1 and 2 show overall ferri- and antiferromagnetic behavior, respectively, as a result of their distinct crystalline aggregation in the solid state.

A Metalloligand Approach for the Self-Assembly of a Magnetic Two-Dimensional Grid-of-Grids

2019

The efficient organization of discrete functional molecules into extended frameworks, while retaining their physical properties, is a mandatory requisite to move toward applications. Here we descri...

Spin-crossover complex encapsulation within a magnetic metal-organic framework.

2016

The solid-state incorporation of a mononuclear iron(III) complex within the pores of a magnetic 3D metal–organic framework (MOF) in a single crystal to single crystal process leads to the formation of a new hybrid material showing both a guest-dependent long-range magnetic ordering and a spin-crossover (SCO) behaviour.

Intermolecular binding modes in a novel [1 + 1] condensation 1H-pyrazole azamacrocycle: a solution and solid state study with evidence for CO2 fixati…

2013

The synthesis of a novel cyclophane (L1) consisting of a 1H-pyrazole moiety linked through methylene groups to a 1,5,9,13-tetraazadecane chain is described. As far as we know, this is one of the first reported syntheses of a [1 + 1] condensation 1H-pyrazole azamacrocyclic ligand. The crystal structures of the complexes [Cu2(H(H(-1)L1))(H(-1)L1)](ClO4)3·3.75H2O (1) and ([Cu2(H(H(-1)L1))(0.5)(H(-1)L1)(1.5)]2(ClO4)3Br2·4.2H2O (2) show that Cu(2+) coordination leads to formation of 2:2 Cu(2+):L dinuclear dimeric complexes in which the 1H-pyrazole units lose a proton behaving as bis(monodentate) bridging ligands. Unlike previously reported complexes of [2 + 2] pyrazole azamacrocycles, the pyrazo…

The MOF-driven synthesis of supported palladium clusters with catalytic activity for carbene-mediated chemistry

2016

The development of catalysts able to assist industrially important chemical processes is a topic of high importance. In view of the catalytic capabilities of small metal clusters, research efforts are being focused on the synthesis of novel catalysts bearing such active sites. Here we report a heterogeneous catalyst consisting of Pd4 clusters with mixed-valence 0/+1 oxidation states, stabilized and homogeneously organized within the walls of a metal-organic framework (MOF). The resulting solid catalyst outperforms state-of-the-art metal catalysts in carbene-mediated reactions of diazoacetates, with high yields (>90%) and turnover numbers (up to 100,000). In addition, the MOF-supported Pd4 c…

Insights into the Dynamics of Grotthuss Mechanism in a Proton-Conducting Chiral bioMOF

2016

Proton conduction in solids attracts great interest, not only because of possible applications in fuel cell technologies, but also because of the main role of this process in many biological mechanisms. Metal–organic frameworks (MOFs) can exhibit exceptional proton-conduction performances, because of the large number of hydrogen-bonded water molecules embedded in their pores. However, further work remains to be done to elucidate the real conducting mechanism. Among the different MOF subfamilies, bioMOFs, which have been constructed using biomolecule derivatives as building blocks and often affording water-stable materials, emerge as valuable systems to study the transport mechanisms involve…

Copper(II) assembling with bis(2-pyridylcarbonyl)amidate and N,N'-2,2-phenylenebis(oxamate).

2013

We herein present the synthesis and X-ray structures of five copper(II) complexes of formulae [Cu(bpca)(CF3SO3)(H2O)]·H2O (1), [Cu(bpca)(Phpr)(H2O)]·3/2H2O (2), {[Cu(bpca)]2[Cu(opba)(H2O)]}·H2O (3), {[Cu(bpca)]2(H2opba)}2·6H2O (4) and [Cu(bpca)(EtH2opba)]n (5), where bpca = bis(2-pyridylcarbonyl)amidate, Phpr = 3-phenylpropionate, CF3SO3(−) = triflate (anion of the trifluoromethanesulphonic acid), H4opba = N,N′-1,2-phenylenebis(oxamic acid), and EtH3opba = monoethyl ester derivative of the H4opba. 1 and 2 are mononuclear copper(II) complexes where the copper atom is five-coordinate in distorted square pyramidal surroundings with a tridentate bpca and a water molecule (1)/carboxylate oxygen …

Highly selective chemical sensing in a luminescent nanoporous magnet.

2012

Among the wide variety of properties of interest that a given material can exhibit, luminescence is attracting an increasing attention due to its potential application in optical devices for lighting equipment and optical storage, [ 1a − c] optical switching, [ 1d ,e] and sensing. [ 1f − i ] At this respect, many scientists, working in the multidisciplinary fi eld of the materials science, have directed their efforts to the obtention of luminescent materials with potential sensing applications. For instance, sensitive and selective detection of gas and vapor phase analytes can result specially interesting because of the variety of applications that can be found in many different fi elds. A …

Photoswitching of the antiferromagnetic coupling in an oxamato-based dicopper(ii) anthracenophane

2011

Thermally reversible photomagnetic (ON/OFF) switching behavior has been observed in a dinuclear oxamatocopper(ii) anthracenophane upon UV light irradiation and heating; the two CuII ions (SCu = 1/2) that are antiferromagnetically coupled in the dicopper(ii) metallacyclic precursor (ON state) become uncoupled in the corresponding [4+4] photocycloaddition product (OFF state), as substantiated from both experimental and theoretical studies. © 2011 The Royal Society of Chemistry.

Postsynthetic Improvement of the Physical Properties in a Metal-Organic Framework through a Single Crystal to Single Crystal Transmetallation

2015

As ingle crystal to single crystal transmetallation process takes place in the three-dimensional (3D) metal- organic framework (MOF) of formula Mg II 2{Mg II 4(Cu II 2- (Me3mpba)2)3}·45 H2 O( 1 ;M e 3mpba 4¢ = N,N'-2,4,6-trimethyl- 1,3-phenylenebis(oxamate)). After complete replacement of the Mg II ions within the coordination network and those hosted in the channels by either Co II or Ni II ions, 1 is transmetallated to yield two novel MOFs of formulae Co2 II {Co II 4(Cu II 2(Me3- mpba)2)3}·56 H2 O( 2 )a nd Ni2 II {Ni II 4(Cu II 2(Me3mpba)2)3}· 54 H2 O( 3). This unique postsynthetic metal substitution affords materials with higher structural stability leading to enhanced gas sorption and m…

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

2018

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…

Cover Picture: Solid-State Molecular Nanomagnet Inclusion into a Magnetic Metal-Organic Framework: Interplay of the Magnetic Properties (Chem. Eur. J…

2015

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

2018

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.

Ligand effects on the dimensionality of oxamato-bridged mixed-metal open-framework magnets

2012

Increasing dimensionality [from 2D (1) to 3D (2)] and T(C) [from 10 (1) to 20 K (2)] in two new oxamato-bridged heterobimetallic Mn(II)(2)Cu(II)(3) open-frameworks result from the steric hindrance provided by the different alkyl substituents of the N-phenyloxamate bridging ligands.

Rational Synthesis of Chiral Metal-Organic Frameworks from Preformed Rodlike Secondary Building Units.

2017

The lack of rational design methodologies to obtain chiral rod-based MOFs is a current synthetic limitation that hampers further expansion of MOF chemistry. Here we report a metalloligand design strategy consisting of the use, for the first time, of preformed 1D rodlike SBUs (1) for the rational preparation of a chiral 3D MOF (2) exhibiting a rare eta net topology. The encoded chiral information on the enantiopure ligand is efficiently transmitted first to the preformed helical 1D building block and, in a second stage, to the resulting chiral 3D MOF. These results open new routes for the rational design of chiral rod-based MOFs, expanding the scope of these unique porous materials.

Growth of thin films of single-chain magnets on functionalized silicon surfaces

2018

A one-pot strategy for the direct growth of continuous and regular thin films of a neutral oxamato-bridged heterobimetallic chain, synthesized from Co2+ nitrate and the tetramethylammonium salt of the anionic copper(II) complex (Me4N)2[Cu(2,6-Et2pa)2]·6H2O (1) (2,6-Etpa = N-2,6-diethylphenyloxamate) over Si(111) surfaces functionalized with carboxylic acid terminating groups has been developed. Variation of the growth conditions can provide important differences in the morphology of the obtained films when working in H2O at 20 °C. An anisotropic growth of 1-D fibers is observed under stoichiometric conditions (Co2+/1 = 1:1), while an isotropic growth of 3-D particles occurs for an excess of…

Metal–organic framework technologies for water remediation: towards a sustainable ecosystem

2018

Having access to clean water is a mandatory requirement for the proper development of living beings. So, addressing the removal of contaminants from aquatic systems should be a priority research topic in order to restore ecosystem balance and secure a more sustainable future. The fascinating structures and striking physical properties of metal–organic frameworks (MOFs) have revealed them as excellent platforms for the removal of harmful species from water. In this review, we have focused our attention on critically highlighting the latest developments achieved in the adsorptive removal of inorganic – metal cations, inorganic acids, oxyanions/cations, nuclear wastes and other inorganic anion…

Bioinspired Metal-Organic Frameworks in Mixed Matrix Membranes for Efficient Static/Dynamic Removal of Mercury from Water

2020

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 when used as the sorbent in mixed matrix membranes (MMMs). These MOF-based MMMs exhibit high efficiency and selectivity in both static and dynamic regimes in the removal of Hg2+ from aqueous environments, due to the high density of thioalkyl groups decorating MOF channels. Both MMMs are capable to reduce different concentration of the pollutant to …

Chromium(III) complexes with 2-(2′-pyridyl)imidazole: Synthesis, crystal structure and magnetic properties

2011

Abstract The preparation, crystal structure and variable temperature-magnetic investigation of three 2-(2′-pyridyl)imidazole-containing chromium(III) complexes of formula PPh4[Cr(pyim)(C2O4)2]·H2O (1), AsPh4[Cr(pyim)(C2O4)2]·H2O (2) and [Cr2(pyim)2(C2O4)2(OH2)2]·2pyim · 6H2O (3) [pyim = 2-(2′-pyridyl)imidazole, C 2 O 4 2 - = dianion of oxalic acid , PPh 4 + = tetraphenylphosphonium cation and AsPh 4 + = tetraphenylarsonium cation ] are reported herein. The isomorphous compounds are made up of discrete [Cr(pyim)(C2O4)2]− anions, XPh 4 + cations [X = P (1) and As (2)] and uncoordinated water molecules. The chromium environment in 1 and 2 is distorted octahedral with Cr–N and Cr–O bond distanc…

A Biocompatible Aspartic-Decorated Metal–Organic Framework with Tubular Motif Degradable under Physiological Conditions

2021

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 MOF, with the formula Ca5II{CuII10[(S,S)-aspartamox]5}·160H2O (1), constructed from Cu2+ and Ca2+ ions and aspartic acid-decorated ligands, where biometal Cu2+ ions are bridged by the carboxylate groups of aspartic acid moieties. The structure of MOF 1 reveals an infinite network of basket-like cages, built by 10 crystallographically distinct Cu(II…

Postsynthetic Approach for the Rational Design of Chiral Ferroelectric Metal–Organic Frameworks

2017

International audience; Ferroelectrics (FEs) are materials of paramount importance with a wide diversity of applications. Herein, we propose a postsynthetic methodology for the smart implementation of ferroelectricity in chiral metal−organic frameworks (MOFs): following a single-crystal to single-crystal cation metathesis, the Ca2+ counterions of a preformed chiral MOF of formula Ca6II{CuII24[(S,S)-hismox]12(OH2)3}·212H2O (1), where hismox is a chiral ligand derived from the natural amino acid l-histidine, are replaced by CH3NH3+. The resulting compound, (CH3NH3)12{CuII24[(S,S)-hismox]12(OH2)3}·178H2O (2), retains the polar space group of 1 and is ferroelectric below 260 K. These results op…

Front Cover: Efficient Capture of Organic Dyes and Crystallographic Snapshots by a Highly Crystalline Amino-Acid-Derived Metal-Organic Framework (Che…

2018

(Multivariate)-Metal–Organic Framework for Highly Efficient Antibiotic Capture from Aquatic Environmental Matrices

2023

Contamination of aquatic environments by pharmaceuticals used by modern societies has become a serious threat to human beings. Among them, antibiotics are of particular concern due to the risk of creating drug-resistant bacteria and, thus, developing efficient protocols for the capture of this particular type of drug is mandatory. Herein, we report a family of three isoreticular MOFs, derived from natural amino acids, that exhibit high efficiency in the removal of a mixture of four distinct families of antibiotics, such as fluoroquinolones, penicillins, lincomycins, and cephalosporins, as solid-phase extraction (SPE) sorbents. In particular, a multivariate (MTV)-MOF, prepared using equal pe…

Selective Gas and Vapor Sorption and Magnetic Sensing by an Isoreticular Mixed-Metal–Organic Framework

2012

A novel isoreticular oxamato-based manganese(II)-copper(II) open metal-organic framework H(2)O@iso1 featuring a pillared square/octagonal layer structure with alternating open and closed octagonal pores has been rationally prepared. The open-framework topology is responsible for a large selectivity in the separation of small gas (CO(2) over CH(4)) and vapor molecules (CH(3)OH over CH(3)CN and CH(3)CH(2)OH). H(2)O@iso1 displays a long-range three-dimensional ferromagnetic ordering with a drastic variation of the critical temperature as a function of the guest molecule [T(C)2.0 K (CO(2)@iso1 and CH(4)@iso1) and T(C) = 6.5 (CH(3)OH@iso1) and 21.0 K (H(2)O@iso1)].

Redox switching of the antiferromagnetic coupling in permethylated dicopper(ii) paracyclophanes

2012

A unique magnetic electroswitching behavior has been observed in an oxamato-based permethylated dicopper(II) paracyclophane; upon reversible one-electron oxidation of the double tetramethyl-substituted p-phenylenediamidate bridging skeleton, the spin alignment of the two Cu(II) ions (S(Cu) = ½) changes from antiparallel (OFF) to parallel (ON) in the resulting dicopper(II) π-radical cation species.

Fine-tuning of the confined space in microporous metal–organic frameworks for efficient mercury removal

2017

Offsetting the impact of human activities on the biogeochemical cycle of mercury has become necessary for a sustainable planet. Herein, we report the development of a water-stable and eco-friendly metal–organic framework, which has the formula {Cu4II[(S,S)-methox]2}·5H2O (1), where methox is bis[(S)-methionine]oxalyl diamide. Its features include narrow functional channels decorated with thioalkyl chains, which are able to capture HgCl2 from aqueous media in an efficient, selective, and rapid manner. The conscious design effort in terms of size, shape, and reactivity of the channels results in extremely efficient immobilization of HgCl2 guest species in a very stable conformation, similar t…

Modulating magnetic dynamics through tailoring the terminal ligands in Dy2 single-molecule magnets

2020

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 = 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionate). They exhibit slightly different coordination geometries around DyIII centers and discrepant binuclear motifs – as a result of altering the β-diketonate coligands – which has an impact on the magnetic interactions between metal centers, the local tensor of anisotropy on each DyIII site and their relat…

A [13]rotaxane assembled via a palladium molecular capsule

2019

Molecules that are the size of small proteins are difficult to make. The most frequently examined route is via self-assembly, and one particular approach involves molecular nanocapsules, where ligands are designed that will enforce the formation of specific polyhedra of metals within the core of the structure. Here we show that this approach can be combined with mechanically interlocking molecules to produce nanocapsules that are decorated on their exterior. This could be a general route to very large molecules, and is exemplified here by the synthesis and structural characterization of a [13]rotaxane, containing 150 metal centres. Small angle X-ray scattering combined with atomistic molecu…

Dicopper(II) Metallacyclophanes as Multifunctional Magnetic Devices: A Joint Experimental and Computational Study

2015

Metallosupramolecular complexes constitute an important advance in the emerging fields of molecular spintronics and quantum computation and a useful platform in the development of active components of spintronic circuits and quantum computers for applications in information processing and storage. The external control of chemical reactivity (electro- and photochemical) and physical properties (electronic and magnetic) in metallosupramolecular complexes is a current challenge in supramolecular coordination chemistry, which lies at the interface of several other supramolecular disciplines, including electro-, photo-, and magnetochemistry. The specific control of current flow or spin delocaliz…

Solid-State Molecular Nanomagnet Inclusion into a Magnetic Metal-Organic Framework: Interplay of the Magnetic Properties.

2015

Single-ion magnets (SIMs) are the smallest possible magnetic devices and are a controllable, bottom-up approach to nanoscale magnetism with potential applications in quantum computing and high-density information storage. In this work, we take advantage of the promising, but yet insufficiently explored, solid-state chemistry of metal-organic frameworks (MOFs) to report the single-crystal to single-crystal inclusion of such molecular nanomagnets within the pores of a magnetic MOF. The resulting host-guest supramolecular aggregate is used as a playground in the first in-depth study on the interplay between the internal magnetic field created by the long-range magnetic ordering of the structur…

Synthesis of Densely Packaged, Ultrasmall Pt02Clusters within a Thioether-Functionalized MOF: Catalytic Activity in Industrial Reactions at Low Tempe…

2018

The gram-scale synthesis, stabilization, and characterization of well-defined ultrasmall subnanometric catalytic clusters on solids is a challenge. The chemical synthesis and X-ray snapshots of Pt02 clusters, homogenously distributed and densely packaged within the channels of a metal-organic framework, is presented. This hybrid material catalyzes efficiently, and even more importantly from an economic and environmental viewpoint, at low temperature (25 to 140 °C), energetically costly industrial reactions in the gas phase such as HCN production, CO2 methanation, and alkene hydrogenations. These results open the way for the design of precisely defined catalytically active ultrasmall metal c…

Dicopper(II) metallacyclophanes with photoswitchable oligoacene spacers: a joint experimental and computational study on molecular magnetic photoswit…

2018

Dinuclear copper(II) complexes of the metallacyclophane-type, (nBu4N)4[Cu2(2,6-anba)2] (1) and (nBu4N)4[Cu2(1,5-naba)2]·4H2O (2) with photoactive 2,6-anthracene-(2,6-anba) and 1,5-naphthalenebis(oxamate) (1,5-naba) bridging ligands, are reported. They undergo a thermally reversible, solid-state photomagnetic (ON/OFF) switching between the moderately strong antiferromagnetically coupled dicopper(II) species and the corresponding magnetically uncoupled [4+4] photocycloaddition product. Density functional calculations give further insights on the intramolecular (“pseudo-bimolecular”) photocycloaddition reaction of the two facing 2,6-anthracene or 1,5-naphthalene spacers in this novel family of…

Synthesis and Enhanced Capture Properties of a New BioMOF@SWCNT‐BP: Recovery of the Endangered Rare‐Earth Elements from Aqueous Systems

2021

Solid-state dinuclear-to-trinuclear conversion in an oxalato-bridged chromium(III)-cobalt(II) complex as a new route toward single-molecule magnets.

2011

A novel bis(oxalato)chromium(III) salt of a ferromagnetically coupled, oxalato-bridged dinuclear chromium(III)-cobalt(II) complex of formula [CrL(ox)(2)CoL'(H(2)O)(2)][CrL(ox)(2)]·4H(2)O (1) has been self-assembled in solution using different aromatic α,α'-diimines as blocking ligands, such as 2,2'-bipyridine (L = bpy) and 2,9-dimethyl-1,10-phenanthroline (L' = Me(2)phen). Thermal dehydration of 1 leads to an intriguing solid-state reaction between the S = 3/2 Cr(III) anions and the S = 3 Cr(III)Co(II) cations to give a ferromagnetically coupled, oxalato-bridged trinuclear chromium(III)-cobalt(II) complex of formula {[CrL(ox)(2)](2)CoL'} (2). Complex 2 possesses a moderately anisotropic S =…

Toward Engineering Chiral Rodlike Metal-Organic Frameworks with Rare Topologies.

2018

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.

Molecular magnetism, quo vadis? A historical perspective from a coordination chemist viewpoint☆

2017

Abstract Molecular magnetism has travelled a long way from the pioneering studies on electron exchange and double exchange or spin crossover and valence tautomerism in small oligonuclear complexes, from mono- to di- and tetranuclear species, to the current investigations about magnetic anisotropy and spin dynamics or quantum coherence of simple mono- or large polynuclear complexes, behaving as switchable bistable molecular nanomagnets for potential applications in information data storage and processing. In this review, we focus on the origin and development of the research in the field of molecular magnetism from a coordination chemistry viewpoint, which dates back to the establishment of …

Tuning the Spin Ground State in Heterononanuclear Nickel(II)−Copper(II) Cylinders with a Triangular Metallacyclophane Core

2010

3 páginas, 2 figuras, 1 gráfico.-- et al.

Double Interpenetration in a Chiral Three-Dimensional Magnet with a (10,3)-a Structure

2015

A unique chiral three-dimensional magnet with an overall racemic double-interpenetrated (10,3)-a structure of the formula [(S)-(1-PhEt)Me3N]4[Mn4Cu6(Et2pma)12](DMSO)3]·3DMSO·5H2O (1; Et2pma = N-2,6-diethylphenyloxamate) has been synthesized by the self-assembly of a mononuclear copper(II) complex acting as a metalloligand toward Mn(II) ions in the presence of a chiral cationic auxiliary, constituting the first oxamato-based chiral coordination polymer exhibiting long-range magnetic ordering.

Metallosupramolecular approach toward multifunctional magnetic devices for molecular spintronics

2015

Abstract The work presented in this review constitutes a successful extension of our group's research on the chemistry and physics of dinuclear copper(II) metallacyclophanes with aromatic polyoxalamide ligands. The design and synthesis of metallacyclic complexes that contain multiple electro- and photoactive (either metal- or ligand-based) spin carriers and the study of their spectroscopic and magnetic properties as well as their redox and photochemical activity are of large interest in the multidisciplinary field of metallosupramolecular chemistry. In doing this, a ligand design approach has been followed which is based on the copper(II)-mediated self-assembly of bis(oxamato) bridging liga…

Inside Cover: Oligo-m-phenyleneoxalamide Copper(II) Mesocates as Electro-Switchable Ferromagnetic Metal-Organic Wires (Chem. Eur. J. 43/2010)

2010

Photodegradation of Brilliant Green Dye by a Zinc bioMOF and Crystallographic Visualization of Resulting CO2

2021

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 presence of CO2 within its channels. Reusability studies further demonstrate the structural and performance robustness of 1.

Mixed component metal-organic frameworks: Heterogeneity andcomplexity at the service of application performances

2022

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 heterogenity and complexity is translated in unexpected properties, which are not just the sum of each component. This review critically encompasses the progress made in this field, covering the synthetic approaches, and specially focusing on the current reported applications –such as gas storage and separation, catalysis, luminescence, conductivit…

Concise Chemistry Modulation of the SMM Behavior within a Family of Mononuclear Dy(III) Complexes.

2018

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), with distinct architectures and local symmetries were established. The disparity of the coordination geometries around the Dy(III) ion among these complexes impacts the strength of the crystal field and the local tensor of anisotropy ( D) of each Dy site and their relative orientations, therefore giving rise to diverse SIM behaviors with distinguishi…

Enhanced Sieving of C2‐Hydrocarbon from Methane by Fluoro‐Functionalization of In‐MOF with Robust Stability

2021

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 respect isoreticular non-fluorinated MOF. QMOF-2F shows a remarkable chemical stability in different solvents, including water, and pH (2-12). DFT calculations support the key role of fluorine-functionalization on the improved performance of QMOF-2F.

Tuning the selectivity of light hydrocarbons in natural gas in a family of isoreticular MOFs

2017

Purification of methane from other light hydrocarbons in natural gas is a topic of intense research due to its fundamental importance in the utilization of natural gas fields. Porous materials have emerged as excellent alternative platforms to conventional cryogenic methodologies to perform this task in a cost- and energy-efficient manner. Here we report a new family of isoreticular chiral MOFs, prepared from oxamidato ligands derived from natural amino acids L-alanine, L-valine and L-leucine, where, by increasing the length of the alkyl residue of the amino acid, the charge density of the MOF's channels can be tuned (1 > 2 > 3), decreasing the adsorption preference towards methane over lig…

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

2019

Abstract 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(bidentate) metalloligand toward solvated dysprosium(III) cations, and it 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…

Selective Gold Recovery and Catalysis in a Highly Flexible Methionine-Decorated Metal–Organic Framework

2016

A novel chiral 3D bioMOF exhibiting functional channels with thio-alkyl chains derived from the natural amino acid l-methionine (1) has been rationally prepared. The well-known strong affinity of gold for sulfur derivatives, together with the extremely high flexibility of the thioether "arms" decorating the channels, account for a selective capture of gold(III) and gold(I) salts in the presence of other metal cations typically found in electronic wastes. The X-ray single-crystal structures of the different gold adsorbates Au(III)@1 and Au(I)@1 suggest that the selective metal capture occurs in a metal ion recognition process somehow mimicking what happens in biological systems and protein r…

Cover Feature: Design of Magnetic Coordination Polymers Built from Polyoxalamide Ligands: A Thirty Year Story (Eur. J. Inorg. Chem. 3‐4/2018)

2018

Oxamato-based coordination polymers: recent advances in multifunctional magnetic materials

2014

The design and synthesis of novel examples of multifunctional magnetic materials based on the so-called coordination polymers (CPs) have become very attractive for chemists and physicists due to their potential applications in nanoscience and nanotechnology. However, their preparation is still an experimental challenge, which requires a deep knowledge of coordination chemistry and large skills in organic chemistry. The recent advances in this field using a molecular-programmed approach based on rational self-assembly methods which fully exploit the versatility of the coordination chemistry of the barely explored and evergreen family of N-substituted aromatic oligo(oxamato) ligands are prese…

Confined Pt-1(1+) Water Clusters in a MOF Catalyze the Low-Temperature Water-Gas Shift Reaction with both CO2 Oxygen Atoms Coming from Water

2018

[EN] The synthesis and reactivity of single metal atoms in a low-valence state bound to just water, rather than to organic ligands or surfaces, is a major experimental challenge. Herein, we show a gram-scale wet synthesis of Pt-1(1+) stabilized in a confined space by a crystallographically well-defined first water sphere, and with a second coordination sphere linked to a metal-organic framework (MOF) through electrostatic and H-bonding interactions. The role of the water cluster is not only isolating and stabilizing the Pt atoms, but also regulating the charge of the metal and the adsorption of reactants. This is shown for the low-temperature water-gas shift reaction (WGSR: CO + H2O CO2 + H…

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

2019

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…

>3 + 1 = 6 + 2> In Cu(ii) coordination chemistry of 1H-pyrazole aza cryptands

2015

A polyazamacrocycle formed from two tris(2-aminoethyl)amine units connected by 1H-pyrazole units shows unique hexanuclear Cu(ii) complexes by combination of two binuclear Cu(ii) cryptand complexes through pyrazolate moieties belonging to both cryptands. The formation of these dimeric entities has been proven both in solution by potentiometric studies and mass spectroscopy and in the solid state by X-ray diffraction of crystals of three different batches of formulae [Cu6(H-3L)2(H2O)2](TsO)6·22H2O (2), [Cu6(H-3L)2(NO3)2](NO3)4·2H2O (3) and [Cu6(H-3L)2Cl2]Cl4·(C4H5N3O2)2·14.35H2O (4). The hexanuclear unit in 2 and 4 can be viewed like three magnetically independent binuclear complexes with J =…

Slow relaxation of the magnetization in Oximato-bridged heterobimetallic Copper(II)-Manganese(III) chains

2011

The use of the oximato-containing copper(II) complexes, [Cu(Hdeg)2] (H2deg = diethylglyoxime), [Cu(Hmeg)2] (H2meg = methylethylglyoxime) and [Cu(Hdmg)2] (H2dmg = dimethylglyoxime), as ligands toward manganese(II) acetate in methanol afforded the heterobimetallic compounds of formula [MnCu(deg)2(CH3COO)(H2O)2] (1), [MnCu(meg)2(CH3COO)(H2O)2] (2) and [MnCu(dmg)2(CH3COO)(H2O)2] (3) where the starting manganese(II) ion was oxidized to manganese(III) by air. In the lack of single crystals suitable for X-ray diffraction analysis, X-ray absorption techniques (EXAFS and XANES) at 40 K were used for the structural characterization of 1-3. The analysis of the X-ray absorption data reveals that 1-3 ar…

Lanthanide Discrimination with Hydroxyl-Decorated Flexible Metal–Organic Frameworks

2018

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 salts of lanthanides on the basis of their size, chemical affinity, and/or the flexibility of the network. In addition, this discrimination follows a completely different trend for 1 and 2 because of the different locations of the hydroxyl groups in each compound, which is evocative of steric complementarity between the substrate and receptor. Last bu…

Design of Magnetic Coordination Polymers Built from Polyoxalamide Ligands: A Thirty Year Story

2018

International audience; The aim of this review is to pay tribute to the legacy of O. Kahn. Kahn's credo was to synthesize magnetic compounds with predictable structure and magnetic properties. This is illustrated herein with results obtained by Kahn's group during his Orsay period thirty years ago, but also on the basis of our recent results on the synthesis of coordination polymers with oxamate ligands. The first part of this review is devoted to a short description of the necessary knowledge in physics and theoretical chemistry that Kahn and his group have used to select oxamate ligands, the complex‐as‐ligand strategy and the synthesis of heterobimetallic systems. Then, we describe the st…

Slow magnetic relaxation in a trigonal-planar mononuclear Fe(II) complex.

2022

A trigonal planar Fe(ii) complex exhibits slow magnetic relaxation and a significant butterfly-like hysteresis loop.

Crystallographic snapshots of host–guest interactions in drugs@metal–organic frameworks: towards mimicking molecular recognition processes

2018

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 natures, strengths and directionalities with organic molecules of technological interest, i.e. ascorbic acid, pyridoxine, bupropion and 17-β-estradiol, based on their different sizes and chemical natures. The ability of 1 to distinctly organize guest molecules within its channels, through the concomitant effect of different directing supramolecular host–guest interactions, enables gaining unique insights, by means of single-crystal X-ray crystallography, into the host–guest intera…

Modulation of the magnetic anisotropy of octahedral cobalt(ii) single-ion magnets by fine-tuning the axial coordination microenvironment

2019

Two mononuclear cobalt(II) complexes, with the 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 combining Co(II) ions with benzoate derivatives and two homogeneous N-donor ligands, respectively. Constrained by the analogous CoN2O4 coordination spheres, the discretely hexa-coordinated Co(II) cores in both complexes display stretched octahedral geometries. The equatorial environments in both complexes are identical, whereas the axial sites are finely modulated by the different chemical natures of the terminal N-donor ligands. The com…

Metal-Organic Frameworks as Unique Platforms to Gain Insight of σ-Hole Interactions for the Removal of Organic Dyes from Aquatic Ecosystems.

2022

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 σ-hole interactions are known to play a key role in the biological activity of living beings as well as on relevant molecular recognitions processes. However, so far, they have been barely explored. Here, we describe both how the combination of the intrinsic features of MOFs, especially the possibility of using single-crystal X-ray crystallography (SCXRD), can be an extremely valuable tool to gain insi…

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

2023

Isolated Fe(III)-O Sites Catalyze the Hydrogenation of Acetylene in Ethylene Flows under Front-End Industrial Conditions

2018

[EN] The search for simple, earth-abundant, cheap, and nontoxic 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, robust, and highly crystalline metal¿organic framework (MOF), embedding FeIII¿OH2 single sites within its pores, was prepared in multigram scale and used as an efficient catalyst for the hydrogenation of 1% acetylene in ethylene streams under front-end conditions. Cutting-edge X-ray crystallography allowed the resolution of the crystal structur…

Structural Studies on a New Family of Chiral BioMOFs

2016

The use of a family of dinuclear copper(II) complexes, prepared from enantiopure disubstituted oxamidato ligands derived from the natural amino acids l-alanine, l-valine, and l-leucine, as metalloligands toward barium(II) cations leads to the formation of three novel three-dimensional (3D) chiral metal–organic frameworks (MOFs). They exhibit different architectures, which serve as playground to study both how the chiral information contained in the starting enantiopure ligands is ultimately transmitted to the 3D structure and the effect of the size of the aliphatic residue of the amino acid on the final architecture.

Long-distance magnetic coupling in dinuclear copper(II) complexes with oligo-para-phenylenediamine bridging ligands

2010

Abstract Two novel dinuclear copper(II) complexes of formulae [Cu2(tren)2(bpda)](ClO4)4 (2) and [Cu2(tren)2(tpda)](ClO4)4 (3) containing the tripodal tris(2-aminoethyl)amine (tren) terminal ligand and the 4,4′-biphenylenediamine (bpda) and 4,4″-p-terphenylenediamine (tpda) bridging ligands have been synthesized and structurally, spectroscopically, and magnetically characterized. Their experimentally available electronic spectroscopic and magnetic properties have been reasonably reproduced by DFT and TDDFT calculations. Single crystal X-ray diffraction analysis of 2 shows the presence of dicopper(II) cations where the bpda bridging ligand adopts a bismonodentate coordination mode toward two …

Solvent-induced single-crystal-to-single-crystal transformation and tunable magnetic properties of 1D azido-Cu(ii) chains with a carboxylate bridge

2019

By means of the 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 3via the coordination of methanol or ethanol, respectively. Meanwhile, the identical products of 1, namely 1a and 1b, could be obtained from both 2 and 3 by a dealcoholized process. As a result, the geometric configurations of Cu(II) ions vary from the tetracoordinated square-planar in 1 to the hexacoordinated octahedron in 2 or 3. Compound 1 di…

Exploring the Role of Amino Acid-Derived Multivariate Metal–Organic Frameworks as Catalysts in Hemiketalization Reactions

2023

A series of lanthanide(iii) metal-organic frameworks derived from a pyridyl-dicarboxylate ligand: single-molecule magnet behaviour and luminescence p…

2020

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-coordinated muffin spheres, linking to each other to generate trinuclear {Ln3(OOC)6N2} SBUs, which are further extended to be interesting 3D topological architectures. To the best of our knowledge, the Dy-MOF exhibits zero-field single-molecule magnet (SMM) behaviour with the largest effective energy barrier among the previously reported 3D MOF-based Dy…

Influence of the alkaline earth cations on the topology of MII/CuII mixed-metal-organic frameworks (M = Ca, Sr and Ba)

2012

The use of the mononuclear copper(ii) complex, [Cu II(Me 2pma) 2] 2- (Me 2pma = N-2,6-dimethylphenyloxamate), as a bis(bidentate) metalloligand toward solvated alkaline earth metal cations affords a new series of oxamato-bridged heterobimetallic two-dimensional compounds with mixed square-octagonal [Ca II 2Cu II 3] or square [M II 2Cu II 3] (M = Sr and Ba) layered structures of (4·82) and (44·62) net topologies, respectively. © 2012 The Royal Society of Chemistry.

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

2022

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…

Epoxidation vs. dehydrogenation of allylic alcohols: heterogenization of the VO(acac)2 catalyst in a metal–organic framework

2022

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 of alkene substituents when the vanadyl complex is used in the homogenous phase. However, confinement effects imparted by MOF channels allow gaining control of the chemoselectivity toward the dehydrogenation product.

Metal-Organic Frameworks as Chemical Nanoreactors: Synthesis and Stabilization of Catalytically Active Metal Species in Confined Spaces

2020

ConspectusSince 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 diffraction (SC-XRD) as a basic characterization tool. Moreover, chemistry on preformed MOFs, applying recent developments in template-directed synthesis and postsynthetic methodologies (PSMs), has shown to be a powerful synthetic tool to (i) tailor MOFs channels of known topology via single-crystal to single-crystal (SC-SC) processes, (ii) impart…

Hydrolase–like catalysis and structural resolution of natural products by a metal–organic framework

2020

[EN] 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 (MOF) with alcohol-containing arms and adsorbed water, enables selective hydrolysis of glycosyl bonds, supramolecular order with the so-formed chiral fragments and absolute determination of the organic structure by single-crystal X-ray crystallography in a single operation. This combined strategy based on a biomimetic, cheap, robust and multigr…

CCDC 1891588: Experimental Crystal Structure Determination

2019

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 1451174: Experimental Crystal Structure Determination

2017

Related Article: Thais Grancha, Jesús Ferrando-Soria, Joan Cano, Pedro Amoros , Beatriz Seoane, Jorge Gascon, Montse Bazaga-García, Enrique R. Losilla, Aurelio Cabeza, Donatella Armentano, Emilio Pardo|2016|Chem.Mater.|28|4608|doi:10.1021/acs.chemmater.6b01286

CCDC 973978: Experimental Crystal Structure Determination

2013

Related Article: Raquel Belda, Javier Pitarch-Jarque, Conxa Soriano, José M. Llinares, Salvador Blasco, Jesús Ferrando-Soria, and Enrique García-España|2013|Inorg.Chem.|52|10795|doi:10.1021/ic400645t

CCDC 1823995: Experimental Crystal Structure Determination

2018

Related Article: Marta Mon, Rosaria Bruno, Jesús Ferrando-Soria, Lucia Bartella, Leonardo Di Donna, Marianna Talia, Rosamaria Lappano, Marcello Maggiolini, Donatella Armentano, Emilio Pardo|2018|Materials Horizons|5|683|doi:10.1039/C8MH00302E

CCDC 1558089: Experimental Crystal Structure Determination

2017

Related Article: Marta Mon, Xiaoni Qu, Jesús Ferrando-Soria, Isaac Pellicer-Carreño, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Johannes C. Jansen, Donatella Armentano, Emilio Pardo|2017|J.Mater.Chem.A|5|20120|doi:10.1039/C7TA06199D

CCDC 1530550: Experimental Crystal Structure Determination

2017

Related Article: Thais Grancha, Marta Mon, Jesús Ferrando-Soria, Jorge Gascon, Beatriz Seoane, Enrique V. Ramos-Fernandez, Donatella Armentano, Emilio Pardo|2017|J.Mater.Chem.A|5|11032|doi:10.1039/C7TA01179B

CCDC 1558090: Experimental Crystal Structure Determination

2017

Related Article: Marta Mon, Xiaoni Qu, Jesús Ferrando-Soria, Isaac Pellicer-Carreño, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Johannes C. Jansen, Donatella Armentano, Emilio Pardo|2017|J.Mater.Chem.A|5|20120|doi:10.1039/C7TA06199D

CCDC 1432054: Experimental Crystal Structure Determination

2016

Related Article: Thais Grancha, Jesús Ferrando-Soria, Joan Cano, Pedro Amoros , Beatriz Seoane, Jorge Gascon, Montse Bazaga-García, Enrique R. Losilla, Aurelio Cabeza, Donatella Armentano, Emilio Pardo|2016|Chem.Mater.|28|4608|doi:10.1021/acs.chemmater.6b01286

CCDC 2019863: Experimental Crystal Structure Determination

2020

Related Article: Chengcheng Zhang, Xiufang Ma, Peipei Cen, Xiaoyong Jin, Jinhui Yang, Yi-Quan Zhang, Jesús Ferrando-Soria, Emilio Pardo, Xiangyu Liu|2020|Dalton Trans.|49|14123|doi:10.1039/D0DT02736G

CCDC 1030505: Experimental Crystal Structure Determination

2015

Related Article: Thais Grancha, Jesús Ferrando-Soria, Hong-Cai Zhou, Jorge Gascon, Beatriz Seoane, Jorge Pasán, Oscar Fabelo, Miguel Julve and Emilio Pardo|2015|Angew.Chem.,Int.Ed.|54|6521|doi:10.1002/anie.201501691

CCDC 2128259: Experimental Crystal Structure Determination

2022

Related Article: Mariafrancesca Baratta, Teresa Fina Mastropietro, Rosaria Bruno, Antonio Tursi, Cristina Negro, Jesús Ferrando-Soria, Alexander I. Mashin, Aleksey Nezhdanov, Fiore P. Nicoletta, Giovanni De Filpo, Emilio Pardo, Donatella Armentano|2022|ACS Appl. Nano Mater.|5|5223|doi:10.1021/acsanm.2c00280

CCDC 1826456: Experimental Crystal Structure Determination

2018

Related Article: Marta Mon, Rosaria Bruno, Rosangela Elliani, Antonio Tagarelli, Xiaoni Qu, Sanping Chen, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2018|Inorg.Chem.|57|13895|doi:10.1021/acs.inorgchem.8b02409

CCDC 1873718: Experimental Crystal Structure Determination

2019

Related Article: Peipei Cen, Xiangyu Liu, Jesús Ferrando-Soria, Yi-Quan Zhang, Gang Xie, Sanping Chen, Emilio Pardo|2018|Chem.-Eur.J.|25|3884|doi:10.1002/chem.201805608

CCDC 1860913: Experimental Crystal Structure Determination

2019

Related Article: Xiangyu Liu, Xiufang Ma, Jinhui Yang, Shuchang Luo, Zheng Wang, Jesús Ferrando-Soria, Yulong Ma, Quan Shi, Emilio Pardo|2019|Dalton Trans.|48|11268|doi:10.1039/C9DT02031D

CCDC 1416018: Experimental Crystal Structure Determination

2015

Related Article: Thais Grancha, Marta Mon, Francesc Lloret, Jesús Ferrando-Soria, Yves Journaux, Jorge Pasán, and Emilio Pardo|2015|Inorg.Chem.|54|8890|doi:10.1021/acs.inorgchem.5b01738

CCDC 1878502: Experimental Crystal Structure Determination

2019

Related Article: Yuewei Wu, Danian Tian, Jesús Ferrando-Soria, Joan Cano, Lei Yin, Zhongwen Ouyang, Zhenxing Wang, Shuchang Luo, Xiangyu Liu, Emilio Pardo|2019|Inorg.Chem.Front.|6|848|doi:10.1039/C8QI01373J

CCDC 941373: Experimental Crystal Structure Determination

2013

Related Article: Thais Grancha, Clarisse Tourbillon, Jesús Ferrando-Soria, Miguel Julve, Francesc Lloret, Jorge Pasán, Catalina Ruiz-Pérez, Oscar Fabelo, Emilio Pardo|2013|CrystEngComm|15|9312|doi:10.1039/C3CE41022F

CCDC 1826450: Experimental Crystal Structure Determination

2018

Related Article: Marta Mon, Rosaria Bruno, Rosangela Elliani, Antonio Tagarelli, Xiaoni Qu, Sanping Chen, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2018|Inorg.Chem.|57|13895|doi:10.1021/acs.inorgchem.8b02409

CCDC 1873720: Experimental Crystal Structure Determination

2019

Related Article: Peipei Cen, Xiangyu Liu, Jesús Ferrando-Soria, Yi-Quan Zhang, Gang Xie, Sanping Chen, Emilio Pardo|2018|Chem.-Eur.J.|25|3884|doi:10.1002/chem.201805608

CCDC 973974: Experimental Crystal Structure Determination

2013

Related Article: Raquel Belda, Javier Pitarch-Jarque, Conxa Soriano, José M. Llinares, Salvador Blasco, Jesús Ferrando-Soria, and Enrique García-España|2013|Inorg.Chem.|52|10795|doi:10.1021/ic400645t

CCDC 1826452: Experimental Crystal Structure Determination

2018

Related Article: Marta Mon, Rosaria Bruno, Rosangela Elliani, Antonio Tagarelli, Xiaoni Qu, Sanping Chen, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2018|Inorg.Chem.|57|13895|doi:10.1021/acs.inorgchem.8b02409

CCDC 1486650: Experimental Crystal Structure Determination

2016

Related Article: Marta Mon, Francesc Lloret, Jesús Ferrando-Soria, Carlos Martí-Gastaldo, Donatella Armentano, Emilio Pardo|2016|Angew.Chem.,Int.Ed.|55|1167|doi:10.1002/anie.201606015

CCDC 2090411: Experimental Crystal Structure Determination

2022

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 1530549: Experimental Crystal Structure Determination

2017

Related Article: Thais Grancha, Marta Mon, Jesús Ferrando-Soria, Jorge Gascon, Beatriz Seoane, Enrique V. Ramos-Fernandez, Donatella Armentano, Emilio Pardo|2017|J.Mater.Chem.A|5|11032|doi:10.1039/C7TA01179B

CCDC 1891577: Experimental Crystal Structure Determination

2019

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 1478222: Experimental Crystal Structure Determination

2016

Related Article: Marta Mon, Jesús Ferrando-Soria, Thais Grancha, Francisco R. Fortea-Pérez, Jorge Gascon, Antonio Leyva-Pérez, Donatella Armentano, and Emilio Pardo|2016|J.Am.Chem.Soc.|138|7864|doi:10.1021/jacs.6b04635

CCDC 1030506: Experimental Crystal Structure Determination

2015

Related Article: Thais Grancha, Jesús Ferrando-Soria, Hong-Cai Zhou, Jorge Gascon, Beatriz Seoane, Jorge Pasán, Oscar Fabelo, Miguel Julve and Emilio Pardo|2015|Angew.Chem.,Int.Ed.|54|6521|doi:10.1002/anie.201501691

CCDC 973976: Experimental Crystal Structure Determination

2013

Related Article: Raquel Belda, Javier Pitarch-Jarque, Conxa Soriano, José M. Llinares, Salvador Blasco, Jesús Ferrando-Soria, and Enrique García-España|2013|Inorg.Chem.|52|10795|doi:10.1021/ic400645t

CCDC 1826453: Experimental Crystal Structure Determination

2018

Related Article: Marta Mon, Rosaria Bruno, Rosangela Elliani, Antonio Tagarelli, Xiaoni Qu, Sanping Chen, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2018|Inorg.Chem.|57|13895|doi:10.1021/acs.inorgchem.8b02409

CCDC 1541852: Experimental Crystal Structure Determination

2017

Related Article: Marta Mon, Jesús Ferrando-Soria, Michel Verdaguer, Cyrille Train, Charles Paillard, Brahim Dkhil, Carlo Versace, Rosaria Bruno, Donatella Armentano, Emilio Pardo|2017|J.Am.Chem.Soc.|139|8098|doi:10.1021/jacs.7b03633

CCDC 1860912: Experimental Crystal Structure Determination

2019

Related Article: Xiangyu Liu, Xiufang Ma, Jinhui Yang, Shuchang Luo, Zheng Wang, Jesús Ferrando-Soria, Yulong Ma, Quan Shi, Emilio Pardo|2019|Dalton Trans.|48|11268|doi:10.1039/C9DT02031D

CCDC 1486651: Experimental Crystal Structure Determination

2016

Related Article: Marta Mon, Francesc Lloret, Jesús Ferrando-Soria, Carlos Martí-Gastaldo, Donatella Armentano, Emilio Pardo|2016|Angew.Chem.,Int.Ed.|55|1167|doi:10.1002/anie.201606015

CCDC 1875514: Experimental Crystal Structure Determination

2019

Related Article: Peipei Cen, Xiangyu Liu, Yi-Quan Zhang, Jesús Ferrando-Soria, Gang Xie, Sanping Chen, Emilio Pardo|2020|Dalton Trans.|49|808|doi:10.1039/C9DT03993G

CCDC 1891583: Experimental Crystal Structure Determination

2019

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 1520974: Experimental Crystal Structure Determination

2017

Related Article: Thais Grancha, Xiaoni Qu, Miguel Julve, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2017|Inorg.Chem.|56|6551|doi:10.1021/acs.inorgchem.7b00681

CCDC 1558088: Experimental Crystal Structure Determination

2017

Related Article: Marta Mon, Xiaoni Qu, Jesús Ferrando-Soria, Isaac Pellicer-Carreño, Antonio Sepúlveda-Escribano, Enrique V. Ramos-Fernandez, Johannes C. Jansen, Donatella Armentano, Emilio Pardo|2017|J.Mater.Chem.A|5|20120|doi:10.1039/C7TA06199D

CCDC 2062290: Experimental Crystal Structure Determination

2022

Related Article: Paula Escamilla, Marta Viciano-Chumillas, Rosaria Bruno, Donatella Armentano, Emilio Pardo, Jesús Ferrando-Soria|2021|Molecules|26|4098|doi:10.3390/molecules26134098

CCDC 1826458: Experimental Crystal Structure Determination

2018

Related Article: Marta Mon, Rosaria Bruno, Rosangela Elliani, Antonio Tagarelli, Xiaoni Qu, Sanping Chen, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2018|Inorg.Chem.|57|13895|doi:10.1021/acs.inorgchem.8b02409

CCDC 1823991: Experimental Crystal Structure Determination

2018

Related Article: Marta Mon, Rosaria Bruno, Jesús Ferrando-Soria, Lucia Bartella, Leonardo Di Donna, Marianna Talia, Rosamaria Lappano, Marcello Maggiolini, Donatella Armentano, Emilio Pardo|2018|Materials Horizons|5|683|doi:10.1039/C8MH00302E

CCDC 1826454: Experimental Crystal Structure Determination

2018

Related Article: Marta Mon, Rosaria Bruno, Rosangela Elliani, Antonio Tagarelli, Xiaoni Qu, Sanping Chen, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2018|Inorg.Chem.|57|13895|doi:10.1021/acs.inorgchem.8b02409

CCDC 1826455: Experimental Crystal Structure Determination

2018

Related Article: Marta Mon, Rosaria Bruno, Rosangela Elliani, Antonio Tagarelli, Xiaoni Qu, Sanping Chen, Jesús Ferrando-Soria, Donatella Armentano, Emilio Pardo|2018|Inorg.Chem.|57|13895|doi:10.1021/acs.inorgchem.8b02409

CCDC 2120156: Experimental Crystal Structure Determination

2022

Related Article: Yuzhu Li, Jing Xi, Jesús Ferrando-Soria, Yi-Quan Zhang, Wenyuan Wang, You Song, Yan Guo, Emilio Pardo, Xiangyu Liu|2022|Dalton Trans.|||doi:10.1039/D2DT00899H

CCDC 1891594: Experimental Crystal Structure Determination

2019

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 2215543: Experimental Crystal Structure Determination

2023

Related Article: Cristina Negro, Héctor Martínez Pérez-Cejuela, Ernesto Francisco Simó-Alfonso, Waseem Iqbal, José Manuel Herrero-Martínez, Donatella Armentano, Jesús Ferrando-Soria, Emilio Pardo|2023|ACS Applied Materials and Interfaces|15|3069|doi:10.1021/acsami.2c20458

CCDC 1961611: Experimental Crystal Structure Determination

2020

Related Article: Chengcheng Zhang, Xiufang Ma, Peipei Cen, Xiaoyong Jin, Jinhui Yang, Yi-Quan Zhang, Jesús Ferrando-Soria, Emilio Pardo, Xiangyu Liu|2020|Dalton Trans.|49|14123|doi:10.1039/D0DT02736G

CCDC 2122007: Experimental Crystal Structure Determination

2022

Related Article: Cristina Negro, Cristina Bilanin, Xiaoni Qu, Judit Oliver-Meseguer, Jesús Ferrando-Soria, Antonio Leyva-Pérez, Donatella Armentano, Emilio Pardo|2022|Chem.Commun.|58|5578|doi:10.1039/D2CC01137A

CCDC 1823993: Experimental Crystal Structure Determination

2018

Related Article: Marta Mon, Rosaria Bruno, Jesús Ferrando-Soria, Lucia Bartella, Leonardo Di Donna, Marianna Talia, Rosamaria Lappano, Marcello Maggiolini, Donatella Armentano, Emilio Pardo|2018|Materials Horizons|5|683|doi:10.1039/C8MH00302E

CCDC 1891591: Experimental Crystal Structure Determination

2019

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CCDC 1045153: Experimental Crystal Structure Determination

2015

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CCDC 1478221: Experimental Crystal Structure Determination

2016

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CCDC 2062289: Experimental Crystal Structure Determination

2022

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CCDC 1891582: Experimental Crystal Structure Determination

2019

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CCDC 1486649: Experimental Crystal Structure Determination

2016

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CCDC 1891587: Experimental Crystal Structure Determination

2019

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CCDC 2215542: Experimental Crystal Structure Determination

2023

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CCDC 1891590: Experimental Crystal Structure Determination

2019

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CCDC 2107391: Experimental Crystal Structure Determination

2022

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CCDC 1985884: Experimental Crystal Structure Determination

2020

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CCDC 1891593: Experimental Crystal Structure Determination

2019

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CCDC 949613: Experimental Crystal Structure Determination

2018

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CCDC 983272: Experimental Crystal Structure Determination

2015

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CCDC 1823992: Experimental Crystal Structure Determination

2018

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CCDC 1891579: Experimental Crystal Structure Determination

2019

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CCDC 983271: Experimental Crystal Structure Determination

2015

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CCDC 2019858: Experimental Crystal Structure Determination

2020

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CCDC 1030504: Experimental Crystal Structure Determination

2015

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CCDC 1891584: Experimental Crystal Structure Determination

2019

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CCDC 1846740: Experimental Crystal Structure Determination

2018

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CCDC 1891576: Experimental Crystal Structure Determination

2019

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CCDC 983274: Experimental Crystal Structure Determination

2015

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CCDC 1860914: Experimental Crystal Structure Determination

2019

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CCDC 1572780: Experimental Crystal Structure Determination

2019

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CCDC 1891580: Experimental Crystal Structure Determination

2019

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CCDC 1478223: Experimental Crystal Structure Determination

2016

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CCDC 1414395: Experimental Crystal Structure Determination

2016

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CCDC 1826457: Experimental Crystal Structure Determination

2018

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CCDC 1873719: Experimental Crystal Structure Determination

2019

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CCDC 1891586: Experimental Crystal Structure Determination

2019

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CCDC 1826449: Experimental Crystal Structure Determination

2018

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CCDC 1520975: Experimental Crystal Structure Determination

2017

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CCDC 1878500: Experimental Crystal Structure Determination

2019

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CCDC 1891581: Experimental Crystal Structure Determination

2019

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CCDC 983273: Experimental Crystal Structure Determination

2015

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CCDC 1891550: Experimental Crystal Structure Determination

2019

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CCDC 1875515: Experimental Crystal Structure Determination

2019

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CCDC 1841391: Experimental Crystal Structure Determination

2018

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CCDC 2120154: Experimental Crystal Structure Determination

2022

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CCDC 891353: Experimental Crystal Structure Determination

2014

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CCDC 1921930: Experimental Crystal Structure Determination

2020

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CCDC 1517224: Experimental Crystal Structure Determination

2017

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CCDC 1891592: Experimental Crystal Structure Determination

2019

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CCDC 1520973: Experimental Crystal Structure Determination

2017

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CCDC 1541853: Experimental Crystal Structure Determination

2017

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CCDC 2019861: Experimental Crystal Structure Determination

2020

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CCDC 2128260: Experimental Crystal Structure Determination

2022

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CCDC 1826451: Experimental Crystal Structure Determination

2018

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CCDC 973975: Experimental Crystal Structure Determination

2013

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CCDC 1891585: Experimental Crystal Structure Determination

2019

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CCDC 1823994: Experimental Crystal Structure Determination

2018

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CCDC 1841392: Experimental Crystal Structure Determination

2018

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CCDC 1572781: Experimental Crystal Structure Determination

2019

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CCDC 1921928: Experimental Crystal Structure Determination

2020

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CCDC 911161: Experimental Crystal Structure Determination

2013

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CCDC 1891578: Experimental Crystal Structure Determination

2019

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CCDC 1849587: Experimental Crystal Structure Determination

2018

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CCDC 1985885: Experimental Crystal Structure Determination

2020

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CCDC 1873721: Experimental Crystal Structure Determination

2019

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CCDC 1891589: Experimental Crystal Structure Determination

2019

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CCDC 973977: Experimental Crystal Structure Determination

2013

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CCDC 1891595: Experimental Crystal Structure Determination

2019

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CCDC 1891596: Experimental Crystal Structure Determination

2019

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CCDC 1921929: Experimental Crystal Structure Determination

2020

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CCDC 1517225: Experimental Crystal Structure Determination

2017

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