Self-assembly mechanism of nanoparticles of Ni-based Prussian Blue analogues at the air/liquid interface: a synchrotron X-ray reflectivity study.

Prussian Blue analogue (PBA) nanoparticles can be self-assembled at air/liquid interfaces to build novel materials with interesting magnetic features. Herein, we study the influence of the size of PBA Cs0.4 Ni[Cr(CN)6 ]0.9 and K0.25 Ni[Fe(CN)6 ]0.75 nanoparticles on the self-assembly behavior by synchrotron X-ray reflectivity. Both nanoparticles show similar Z-potential values. The phospholipid dipalmitoylphosphatidylcholine and the amino surfactant dimethyldioctadecylammonium have been used as Langmuir monolayers to anchor the PBA nanoparticles and study the interplay of forces directing the self-assembly of the nanoparticles at the surfactant/liquid interface. Whereas Cs0.4 Ni[Cr(CN)6 ]0.…

Design of molecular materials combining magnetic, electrical and optical properties †

The possibilities offered by hybrid functional materials formed by two molecular networks in the context of crystal engineering are illustrated with two different examples: (i) hybrid magnets constructed from combination of an extended ferromagnetic or ferrimagnetic inorganic network, with a molecular paramagnetic metal complex acting as template. (ii) Hybrid organic–inorganic compounds combining an organic π-electron donor network that furnishes the pathway for electronic conductivity, with inorganic metal complexes that act as structural and/or magnetic components. These examples illustrate how this hybrid approach allows the design of molecular materials combining non-conventional magnet…

A spin-crossover complex based on a 2,6-bis(pyrazol-1-yl)pyridine (1-bpp) ligand functionalized with a carboxylate group

Combining Fe(ii) with the carboxylate-functionalized 2,6-bis(pyrazol-1-yl)pyridine (bppCOOH) ligand results in the spin-crossover compound [Fe(bppCOOH)2](ClO4)2 which shows an abrupt spin transition with a T1/2 of ca. 380 K and a TLIESST of 60 K due to the presence of a hydrogen-bonded linear network of complexes.

Insertion of FeII complexes with Schiff base ligands derived from imidazole or pyridine into 3D bimetallic oxalate-based ferromagnets

Abstract The syntheses, structures and magnetic properties of the compounds [FeII(imid2-trien)][MnII(CH3OH)CrIII(ox)3]2·(CH3OH)4(CH3CN)(H2O) (1), [FeII(tren(6-Me-py)3)][MnIICrIII(ox)3][MnII(CH3OH)0.58(H2O)0.42CrIII(ox)3]·(CH3OH)2(CH3CN)0.5(H2O)0.42 (2) and [FeII(tren(imid)3)]2[Mn2.5(CH3OH)3Cr3(ox)9]·(CH3OH)4.75·(H2O)4.25 (3) are reported. They are prepared by the insertion of FeII-Schiff base complexes derived from imidazole and pyridine into bimetallic oxalate networks. Different types of 3D oxalate networks are obtained for each templating cation. Thus, [FeII(imid2-trien)]2+ and [FeII(tren(6-Me-py)3)]2+ give rise to unusual 3D achiral bimetallic oxalate networks with heptacoordinated MnII…

Tuning the nuclearity of iron(iii) polynuclear clusters by using tetradentate Schiff-base ligands

Three novel octanuclear, hexanuclear and tetranuclear complexes of high-spin Fe(III) ions were obtained by the reaction of the N,N′-bis-(1R-imidazol-4-ylmethylene)-ethane-1,2-diamine ligand (R = H, CH3) and its derivatives with Fe(ClO4)3·6H2O and KSCN. The tetradentate Schiff-base ligand acts as a bis(bidentate) chelating bridge between two adjacent high-spin Fe(III) centers. The presence of a methyl group in the imidazolyl substituent, the change of counterions or the replacement of imidazole by pyridine has a drastic effect on the nuclearity of the cluster. The magnetic properties of all compounds exhibit antiferromagnetic interactions via μ-oxo or μ-hydroxo pathways in Fe(III) dimers.

Unusual Magnetic Behavior in the Layered Ferromagnet [Ni(C6H14N2)2]3[Fe(CN)6]2·2H2O

The cyano-bridged molecular complex [Ni(C6H14N2)2]3[Fe(CN)6]2·2H2O, with a rectangular 2D structure, displays long-range ferromagnetic ordering at 14 K, and exhibits unusual magnetic properties for this type of material, as confirmed by the appearance of two different peaks in the AC magnetic susceptibility plot, and a high coercive field (2.3 kOe) and remnant magnetization (6.8 μB). (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

Towards Organization of Molecular Machines at Interfaces. Langmuir Films and Langmuir-Blodgett Multilayers of an Acid-Base Switchable Rotaxane

In this context we investigated, for the first time, the organi-zation of a non-amphiphilic tricationic switchable rotaxaneand its dumbbell-shaped component into Langmuir films andLangmuir–Blodgett (LB) multilayers by using a cospreadingstrategy. The Langmuir films have been characterized by sur-face pressure–area (

Iron(ii) complexes of tris(2-pyridylmethyl)amine (TPMA) and neutral bidentate ligands showing thermal- and photo-induced spin crossover

Three new mononuclear Fe(ii) complexes have been prepared and characterized by the combination of tetradentate tris(2-pyridylmethyl)amine (TPMA) with three neutral bidentate ligands, such as ethylenediamine (en), 1,2-diaminopropane (pn) and 2-picolylamine (2-pic), in compounds [FeII(TPMA)(en)](ClO4)2 (1), [FeII(TPMA)(2-pic)](ClO4)2 (2) and [FeII(TPMA)(pn)](ClO4)2 (3). Structural and magnetic characterization demonstrates that the three compounds present a complete SCO behavior. The absence of strong intermolecular interactions and solvent molecules leads to reversible and gradual spin transitions. The different ligands allow tuning T1/2 from 130 K (2) to 325 K (3). The compound with the low…

Polyoxometalates: From Magnetic Models to Multifunctional Materials

In this article we have presented some recent achievements of the polyoxometalates in the fields of molecular magnetism and functional molecular materials. In the context of the molecular magnetism we have shown that POMs provide ideal examples of magnetic clusters with coexisting ferro and antiferromagnetic exchange interactions which can be investigated using a variety of magnetic techniques, including the Inelastic Neutron Scattering spectroscopy, to get a thorough characterization of the magnetic levels in these large clusters, and to test the validity of the spin hamiltonians commonly used in magnetism.

Manipulation and Orientation of Zeolite L by Using a Magnetic Field

A simple approach for the functionalization of cylindrically shaped zeolite L crystals with iron oxide magnetic nanoparticles is reported. These functionalized zeolites can be aligned very easily by applying a magnetic field in solution, on different substrates, and in a polymeric matrix. The aligned zeolite loaded with fluorescent dyes are anisotropic in both absorption and fluorescence owing to the linear arrangement of the channels and the restricted rotation of the molecules inside the channels. These findings can be applied on polymeric matrices, such as poly[3-3′(vinylcarbazole)].

Langmuir monolayers and Langmuir–Blodgett films of ferritin prepared by using a surfactant mixture of eicosylamine (EA) and methyl stearate (SME)

Abstract Magnetic Langmuir–Blodgett films of ferritin have been prepared by using the adsorption properties of a 1/4 mixed monolayer of eicosylamine (EA) and methyl stearate (SME). BAM images show that a more homogeneous distribution of ferritin at the air–water interface is achieved by using this mixture of surfactants instead of the DODA/SME mixed matrix of a previous work. Transfer of the monolayer onto different substrates allowed the preparation of multilayer LB films. Infrared and UV–Vis spectroscopies indicate that ferritin molecules are incorporated within the LB films. Furthermore, UV–Vis spectroscopy measurements reveal that the amount of ferritin incorporated into these LB film h…

Multifunctional magnetic materials obtained by insertion of spin-crossover Fe(III) complexes into chiral 3D bimetallic oxalate-based ferromagnets.

The syntheses, structures, and magnetic properties of compounds of formula [Fe(III)(5-Clsal(2)-trien)][Mn(II)Cr(III)(ox)(3)]·0.5(CH(3)NO(2)) (1), [Fe(III)(5-Brsal(2)-trien)][Mn(II)Cr(III)(ox)(3)] (2), and [In(III)(5-Clsal(2)-trien)][Mn(II)Cr(III)(ox)(3)] (3) are reported. The structure of the three compounds, which crystallize in the orthorhombic P2(1)2(1)2(1) chiral space group, presents a 3D chiral anionic network formed by Mn(II) and Cr(III) ions linked through oxalate ligands with inserted [Fe(III)(5-Clsal(2)-trien)](+), [Fe(III)(5-Brsal(2)-trien)](+), and [In(III)(5-Clsal(2)-trien)](+) cations. The magnetic properties indicate that the three compounds undergo long-range ferromagnetic o…

Nonanuclear Spin-Crossover Complex Containing Iron(II) and Iron(III) Based on a 2,6-Bis(pyrazol-1-yl)pyridine Ligand Functionalized with a Carboxylate Group.

The synthesis and magnetostructural characterization of [Fe(III)3(μ3-O)(H2O)3[Fe(II)(bppCOOH)(bppCOO)]6](ClO4)13·(CH3)2CO)6·(solvate) (2) are reported. This compound is obtained as a secondary product during synthesis of the mononuclear complex [Fe(II)(bppCOOH)2](ClO4)2 (1). The single-crystal X-ray diffraction structure of 2 shows that it contains the nonanuclear cluster of the formula [Fe(III)3(μ3-O)(H2O)3[Fe(II)(bppCOOH)(bppCOO)]6](13+), which is formed by a central Fe(III)3O core coordinated to six partially deprotonated [Fe(II)(bppCOOH)(bppCOO)](+) complexes. Raman spectroscopy studies on single crystals of 1 and 2 have been performed to elucidate the spin and oxidation states of iron …

Magnetic Langmuir–Blodgett films of ferritin with different iron loadings

Abstract Magnetic Langmuir–Blodgett multilayers of two ferritin molecules 1 and 2 , containing, respectively, 4220 and 3062 Fe atoms have been prepared by using the adsorption properties of a 6/1 mixed monolayer of dioctadecyldimethylammonium bromide (DODABr) and methyl stearate (SME). Transfer ratios close to unity were reached giving rise to LB films with a strong red colour. Infrared and UV–vis spectroscopy indicates that ferritin molecules are incorporated within the LB films. Magnetic measurements show that the superparamagnetic properties of these molecules are preserved. Thus, a marked hysteresis loop of magnetisation is obtained for LB films of 1 and 2 with a coercive field of 3400 …

Magneto-optical Investigations of Nanostructured Materials Based on Single Molecule Magnets Monitor Strong Environmental Effects

The determination of the magnetic properties of molecular magnets in environments similar to those used in spintronic devices is fundamental for the development of applications. Single-molecule magnets (SMMs) are molecular cluster systems that display magnetic hysteresis of dynamical origin at low temperature. As they behave like perfectly monodisperse nanomagnets and show clear macroscopic quantum effects in their magnetic properties, they are extremely appealing candidates for the forthcoming generation of molecular devices: they have been proposed as efficient systems for quantum computation, ultra-high-density magnetic recording media, and molecular spintronic systems. These attractive …

Insertion of a single-molecule magnet inside a ferromagnetic lattice based on a 3D bimetallic oxalate network: Towards molecular analogues of permanent magnets

The insertion of the single-molecule magnet (SMM) [MnIII(salen) (H2O)]2 2+ (salen2-=N,N-ethylenebis- (salicylideneiminate)) into a ferromagnetic bimetallic oxalate network affords the hybrid compound [MnIII(salen)(H2O)] 2[MnIICrIII(ox)3] 2×(CH3OH)×(CH3CN)2 (1). This cationic Mn2 cluster templates the growth of crystals formed by an unusual achiral 3D oxalate network. The magnetic properties of this hybrid magnet are compared with those of the analogous compounds [Mn III(salen)(H2O)]2[ZnIICr III(ox)3]2×(CH3OH) ×(CH3CN)2 (2) and [InIII(sal 2-trien)][MnIICrIII(ox)3] ×(H2O)0.25×(CH3OH) 0.25×(CH3CN)0.25 (3), which are used as reference compounds. In 2 it has been shown that the magnetic isolatio…

Polyoxometalates in Langmuir–Blodgett films: toward new magnetic materials

Abstract Polyoxometalates having various structures and properties can be organized by the Langmuir–Blodgett (LB) technique. The adsorption of such polyanions along a positively charged monolayer of DODA (dimethyldioctadecylammonium) induces large changes in the compression isotherm and enables the transfer of the Langmuir film onto solid substrate. X-ray diffraction and infrared dichroism experiments demonstrate that the polyoxometalates are organized in monolayers within the LB films. Furthermore, these magnetic multilayers were characterized by their paramagnetic susceptibility measured by a SQUID magnetometer.

Organic/inorganic molecular conductors based upon perylene and Lindquist-type polyoxometalates

The preparation, structures and physical properties of the organic/inorganic radical salts based upon perylene (per) and Lindquist type polyoxometalates (POMs) are reported. Three new hybrid salts have been prepared: (per)5[Mo6O19] (1), (per)5[W6O19] (2), and (per)5[VW5O19] (3). Only structures 1 (P, Z = 2) and 3 (P, Z = 2) were fully determined as compound 2 was found to have unit cell parameters practically identical to 1 and, therefore, is considered isostructural with the latter. The structures consist of interpenetrated organic and mixed organic/inorganic layers in the ac plane alternating along the a direction. The organic layers present a novel packing mode of the perylene molecules …

Hybrid Materials Based on Polyoxometalates with Solid State Properties

Molecular materials with cooperative physical properties constitute one of the most active focus of interest in contemporary materials science. An attractive chemical feature of these materials derives from the possibility of building them from molecular bricks using the advantages provided by molecular chemistry and the knowledge achieved over the last 20 years in the so-called molecular engineering. From the point of view of the physical properties, it is well known that molecular materials can exhibit the properties typically associated with the inorganic network solids, as for example metallic conductivity and superconductivity [1], ferromagnetism [2] and non-linear optics [3].

Ion-Pairing Effects in the Self-Assembly of a Fluorescent Pseudorotaxane

Herein we report on the self-assembly, in a low polarity solvent, of a pseudorotaxane species comprising binaphthyl-26-crown-8 (BN26C8) as the macrocyclic host and anthracenyl-benzylammonium as the threadlike positively charged guest (ABH+). Absorption and luminescence data reveal a very efficient energy transfer process occurring from the binaphthyl to the anthracene singlet excited states. The self-assembly is highly dependent on the nature of the counteranion confirming the crucial role played by it in the competition between the self-assembly process and the formation of ion pairs (ABH+X-). This behavior can be readily evidenced in dilute solutions from the analysis of the luminescence …

Photomagnetic properties of an Fe(ii) spin-crossover complex of 6-(3,5-diamino-2,4,6-triazinyl)-2,2'-bipyridine and its insertion into 2D and 3D bimetallic oxalate-based networks.

International audience; The Fe(ii) complex of the L1 ligand (L1 = 6-(3,5-diamino-2,4,6-triazinyl)-2,2'-bipyridine) has been used as a templating cation for the growth of oxalate-based networks. The magnetic characterization of the [Fe(II)(L1)2](ClO4)2·CH3CN (1) precursor in the solid state has been performed for the first time showing that the low-spin (LS) state is predominating from 2 to 400 K with 10% of Fe(ii), which undergoes a gradual and irreversible spin-crossover above 350 K. 1 presents the LIESST effect with a photo-conversion close to 25% and a T(LIESST) of 49 K. During the preparation of 1, a secondary product of the formula [Fe(II)(L1)(CH3CN)2(H2O)](ClO4)2·CH3CN (2) has been ob…

Electrochromic polyoxometalate material as a sensor of bacterial activity

L. fermentum, a bacterium of human microbiota, acts as an electron donor to the electrochromic [P2MoVI18O62]6. Since, the reductive capacity of L. fermentum correlates with its metabolic activity, the reaction with [P2MoVI18O62]6- affords a means of evaluating its activity. Following this logic, we have concluded that vancomycin severely affects the activity of L. fermentum whereas omeprazole does not.

Hybrid Molecular Materials Based upon Organic π-Electron Donors and Metal Complexes. Radical Salts of Bis(ethylenethia)tetrathiafulvalene (BET-TTF) with the Octahedral Anions Hexacyanoferrate(III) and Nitroprusside. The First Kappa Phase in the BET-TTF Family

The synthesis, structure, and physical characterization of two new radical salts formed with the organic donor bis(ethylenethia)tetrathiafulvalene (BET-TTF) and the octahedral anions hexacyanoferrate(III), [Fe(CN)(6)](3-), and nitroprusside, [Fe(CN)(5)NO](2-), are reported. These salts are (BET-TTF)(4)(NEt(4))(2)[Fe(CN)(6)] (1) (monoclinic space group C2/c with a = 38.867(7) A, b = 8.438(8) A, c = 11.239(6) A, beta = 90.994(9) degrees, V = 3685(4) A(3), Z = 4) and (BET-TTF)(2)[Fe(CN)(5)NO].CH(2)Cl(2) (2) (monoclinic space group C2/c with a = 16.237(6) A, b = 18.097(8) A, c = 12.663(7) A, beta = 106.016(9) degrees, V = 3576(3) A(3), Z = 4). In salt 1 the organic BET-TTF molecules are packed …

Bimetallic cyanide-bridged complexes based on the photochromic nitroprusside anion and paramagnetic metal complexes

Abstract Three novel compounds formed by the photochromic nitroprusside anion, [Fe(CN)5NO]2−, and the paramagnetic complexes [Cu(C19H18N6)]2+, [Ni(C6H14N2)2]2+ and [Ni(cyclam)]2+ are reported. The structure of [Cu(C19H18N6)][Fe(CN)5NO] (1) comprises binuclear complexes with a [Fe(CN)5NO]2− anion linked to a [Cu(C19H18N6)]2+ cation. The structure of [Ni(C6H14N2)2][Fe(CN)5NO]·6.5H2O (2) and [Ni(cyclam)][Fe(CN)5NO]·4H2O (3) consists of zigzag chains formed by an alternate array of the paramagnetic cations and [Fe(CN)5NO]2− anions. The three compounds are paramagnets; a fourth compound containing [cis-Ni(en)2]2+ cations and [Fe(CN)5NO]− anions does not show a change in the magnetic properties a…

Unusual packing of ET molecules caused by π–π stacking interactions with TRISPHAT molecules in two [ET][TRISPHAT] salts (ET=bis(ethylenedithio)tetrathiafulvalene, TRISPHAT=(tris(tetrachlorobenzenediolato)phosphate(V)))

Abstract The synthesis, structure and physical properties of two new radical salts formed with the organic donor bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET) and a racemic mixture of the chiral anion (tris(tetrachlorobenzenediolato)phosphate(V)) (TRISPHAT) are reported. The structure of the salts (ET)4[TRISPHAT]4 · 3.5H2O (1) and (ET)(TRISPHAT) · CH2Cl2 · CH3CN (2) has been solved by X-ray single crystal diffraction. Unusual packings of ET molecules are obtained in the two structures. The electrical properties indicate that both compounds are insulators. This is in agreement with the isolation of the ET molecules and their complete ionization. On the other hand, the anisotropy of …

Organized assemblies of magnetic clusters

Abstract In this work we have explored the possibilities to create layered organizations of the Mn 12 single-molecule magnets using the Langmuir–Blodgett technique or attaching these clusters onto a metal surface by preparing self-assembled monolayers (SAMs). In the first part we discuss the use of the Langmuir–Blodgett (LB) technique in order to obtain organized magnetic films formed by monolayers of these clusters. Two strategies have been used with this aim. The first one consists of mixing Mn 12 acetate or benzoate derivatives with an amphiphile, while the second procedure is based on the use of Mn 12 derivatives specifically designed to form LB films. An alternative method is that of p…

Permanent magnetism in apoferritin-encapsulated Pd nanoparticles

Pd nanoparticles have been prepared within the apoferritin cavity. X-Ray powder diffraction, transmission electronic microscopy and magnetization measurements have been used for characterizing the nanoparticles. The nanoparticles exhibit permanent magnetism at room temperature.

Autonomous artificial nanomotor powered by sunlight

Light excitation powers the reversible shuttling movement of the ring component of a rotaxane between two stations located at a 1.3-nm distance on its dumbbell-shaped component. The photoinduced shuttling movement, which occurs in solution, is based on a “four-stroke” synchronized sequence of electronic and nuclear processes. At room temperature the deactivation time of the high-energy charge-transfer state obtained by light excitation is ≈10 μs, and the time period required for the ring-displacement process is on the order of 100 μs. The rotaxane behaves as an autonomous linear motor and operates with a quantum efficiency up to ≈12%. The investigated system is a unique example of an artif…

Structural and magnetic characterization of Pd nanoparticles encapsulated in apoferritin

Pd nanoparticles exhibiting permanent magnetism at room temperature have been prepared within the apoferritin cavity. Pd nanoparticles in air and under an inert atmosphere were synthesized to study the influence of the aerobic and anaerobic conditions in the final magnetic properties. The surface of nanoparticles as well as the type of crystalline phase could determine the magnetic properties. X-ray powder diffraction, including Debye-function analysis, transmission electronic microscopy, and magnetization measurements have been used for characterizing the nanoparticles.

Bimetallic MnIII–FeII hybrid complexes formed by a functionalized MnIII Anderson polyoxometalate coordinated to FeII: observation of a field-induced slow relaxation of magnetization in the MnIII centres and a photoinduced spin-crossover in the FeII centres

The synthesis and crystal structure of an Anderson POM functionalized with two 2,6-di(pyrazol-1-yl)-pyridine (1-bpp) ligands are reported (compound 1). High-frequency electron paramagnetic resonance (HF-EPR) and magnetic measurements show that it presents a significant negative axial zero-field splitting and field-induced slow relaxation of magnetization due to the presence of isolated MnIII anisotropic magnetic ions. Complexation of 1 with FeII gives rise to a 2D cationic network formed by Anderson POMs coordinated to two FeII ions through the two tridentate 1-bpp ligands and to other two FeII ions through two oxo ligands in compound 2, and to an anionic polymeric network formed by Anderso…

Cover Picture: Insertion of a Single-Molecule Magnet inside a Ferromagnetic Lattice Based on a 3D Bimetallic Oxalate Network: Towards Molecular Analogues of Permanent Magnets (Chem. Eur. J. 6/2014)

Spin-crossover compounds based on iron(II) complexes of 2,6-bis(pyrazol-1-yl)pyridine (bpp) functionalized with carboxylic acid and ethyl carboxylic acid

International audience; Four new salts of the iron(II) complex of the 2,6-bis(pyrazol-1-yl)pyridine ligand functionalized with a carboxylic acid group (bppCOOH) of formulas [Fe(bppCOOH)2](BF4)2 (1(BF4)2), [Fe(bppCOOH)2](CF3SO3)2·yMe2CO (1(CF3SO3)2·yMe2CO), [Fe(bppCOOH)2](AsF6)2·yMe2CO (1(AsF6)2·yMe2CO) and [Fe(bppCOOH)2](SbF6)2·yMe2CO (1(SbF6)2·yMe2CO) have been prepared and characterized together with a more complete structural and photomagnetic characterization of the previously reported [Fe(bppCOOH)2](ClO4)2 (1(ClO4)2). Furthermore, the iron(II) complex of the ethyl ester derivative of bppCOOH (bppCOOEt) has been prepared and characterized (compound [Fe(bppCOOEt)2](ClO4)2·yMe2CO, 2(ClO4)…

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

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.

Modeling the magnetic properties and Mössbauer spectra of multifunctional magnetic materials obtained by insertion of a spin-crossover Fe(III) complex into bimetallic oxalate-based ferromagnets.

In this article, we present a theoretical microscopic approach to describe the magnetic and spectroscopic behavior of multifunctional hybrid materials which demonstrate spin crossover and ferromagnetic ordering. The low-spin to high-spin transition is considered as a cooperative phenomenon that is driven by the interaction of the electronic shells of the Fe ions with the full symmetric deformation of the local surrounding that is extended over the crystal lattice via the acoustic phonon field. The proposed model is applied to the analysis of the series [Fe(III)(sal2-trien)] [Mn(II)Cr(III)(ox)3]·solv, in short 1·solv, where solv = CH2Cl2, CH2Br2, and CHBr3.

Hybrid Molecular Materials Based upon Organic π-Electron Donors and Inorganic Metal Complexes. Conducting Salts of Bis(ethylenediseleno)tetrathiafulvalene (BEST) with the Octahedral Anions Hexacyanoferrate(III) and Nitroprusside

Abstract The synthesis, structure and physical characterization of three new radical salts formed by the organic donor bis(ethylenediseleno)tetrathiafulvalene (BEDS-TTF or BEST) and the paramagnetic hexacyanoferrate(III) anion [Fe(CN)6]3− or the photochromic nitroprusside anion [Fe(CN)5NO]2− are reported: (BEST)4[Fe(CN)6] (1), (BEST)3[Fe(CN)6]2·H2O (2) and (BEST)2[Fe(CN)5NO] (3). Salts 1 and 3 show a layered structure with alternating organic (β–type packing) and inorganic slabs. Salt 2 shows an original interpenetrated structure probably due to the unprecedented presence of (BEST)2+ dications. The three salts are semiconductors although salt 1 exhibits a high room temperature conductivity …

Multifunctional magnetic materials obtained by insertion of a spin-crossover Fe(III) complex into bimetallic oxalate-based ferromagnets.

The syntheses, structures and magnetic properties of the compounds of formula [Fe(III)(sal(2)-trien)][Mn(II)Cr(III)(ox)(3)].CH(2)Cl(2) (1; H(2)sal(2)-trien=N,N'-disalicylidenetriethylenetetramine, ox=oxalate), [Fe(III)(sal(2)-trien)][Mn(II)Cr(III)(ox)(3)].CH(3)OH (2), [In(III)(sal(2)-trien)][Mn(II)Cr(III)(ox)(3)].0.25H(2)O.0.25CH(3)OH.0.25CH(3)CN (3), and [In(III)(sal(2)-trien)][Mn(II)Cr(III)(ox)(3)].CH(3)NO(2).0.5H(2)O (4) are reported. The structure of 1 presents a 2D honeycomb anionic layer formed by Mn(II) and Cr(III) ions linked through oxalate ligands and a cationic layer of [Fe(sal(2)-trien)](+) complexes intercalated between the 2D oxalate network. The structures of 2, 3, and 4 pres…

Dual-emitting Langmuir-Blodgett film-based organic light-emitting diodes.

Langmuir-Blodgett (LB) films containing alternating layers of the metallosurfactants bis(4,4'-tridecyl-2,2'-bipyridine)-(4,4'-dicarboxy-2,2'-bipyridine) ruthenium(II)-bis(chloride) (1) and bis[2-(2,4-difluorophenyl)pyridine](4,4'-dinonadecyl-2,2'-bipyridine)iridium(III) chloride (2) have been prepared. Langmuir monolayers at the air-water interface of 1 and 2 with different anions in the subphase have been characterized by pi-A compression isotherms and Brewster angle microscopy (BAM). The transferred LB films have been characterized by IR, UV-vis and emission spectroscopy, and atomic force microscopy (AFM). Electroluminescent devices formed by LB films containing alternating layers of thes…

Spin-crossover iron(ii) complex showing thermal hysteresis around room temperature with symmetry breaking and an unusually high T(LIESST) of 120 K.

We report a Fe(II) complex based on 4′,4′′ carboxylic acid disubstituted dipyrazolylpyridine that shows a spin-crossover close to room temperature associated to a crystallographic phase transition and the LIESST effect with a high T(LIESST) of 120 K.

Magnetic LB films based upon polyoxometalate clusters and single molecule nanomagnets

Abstract By using the adsorption properties of polyoxometalates such as the ferromagnetic cluster [Co 4 (H 2 O) 2 (PW 9 O 34 ] 10− ) along a positively charged monolayer, we have prepared well organized monolayers of the magnetic polyanions. A similar procedure allowed us to obtain Langmuir-Blodgett films (LB films) based on Mn 12 clusters which show a marked hysteresis

Langmuir–Blodgett films based on inorganic molecular complexes with magnetic or optical properties

Langmuir and Langmuir–Blodgett (LB) films of a great variety of molecular metal complexes with interesting magnetic or optical properties have been prepared in the last few years. Some of the results obtained by our group and others are summarized in this article. (i) LB films of polyoxometalates (POM) were first prepared taking advantage of the adsorption properties of these cluster anions along a positively charged monolayer of an organic surfactant spread in water. A correct choice of the POM allowed the preparation of LB films with magnetic, electrochromic, or luminescent properties. Besides this semiamphiphilic method, two new methods to prepare LB films of POMs have been developed by …

Hybrid magnetic materials formed by ferritin intercalated into a layered double hydroxide

A hybrid magnetic material formed by ferritin intercalated into a layered double hydroxide (LDH) of Mg and Al (Mg/Al molar ratio 2) is prepared and characterized through powder X-ray diffraction (XRD), thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR) spectroscopy, electron probe microanalysis (EPMA) and high resolution transmission electron microscopy (HRTEM). One observes an enhancement in the thermal stability of the ferritin molecules when they are inserted in the layered material. Magnetic measurements of the hybrid material exhibit the typical superparamagnetic behaviour of the ferritin molecule. On the other hand, the intercalation of ferritin into the LDH guarante…

Thermal- and photo-induced spin crossover in the 1D coordination polymer [Fe(4-tBupy)3][Au(CN)2]2 (4-tBupy = 4-tert-butylpyridine)

Reaction of the unidentate pyridine ligand containing a bulky t-butyl substituent with Fe2+ and [Au(CN)2]− affords a new type of spin crossover (SCO) coordination polymer in the 1D compound [Fe(4-tBupy)3][Au(CN)2]2⋅0.5H2O (1), which is formed by chains of Fe(II) complexes linked through bridging [Au(CN)2]− with three terminal 4-tBupy and one monodentate [Au(CN)2]− ligands completing the octahedral coordination around Fe(II). Longer reaction times led to the minor products [Fe(4-tBupy)2][Au(CN)2]2 (2), which presents a 2D structure more similar to that found in the other SCO compounds based on [Au(CN)2]−, and the 1D compound [Fe(4-tBupy)2(MeOH)][Au(CN)2]2 (3), in which one of the three termi…

Heteroleptic Iron(II) Spin-Crossover Complexes Based on a 2,6-Bis(pyrazol-1-yl)pyridine-type Ligand Functionalized with a Carboxylic Acid

Two new heteroleptic complexes [Fe- (1bppCOOH)(3bpp-bph)](ClO4)2·solv (1·solv, solv = various solvents; 1bppCOOH = 2,6-bis(1H-pyrazol-1-yl)- isonicotinic acid; 3bpp-bph = 2,6-bis(5-([1,1′-biphenyl]-4- yl)-1H-pyrazol-3-yl)pyridine) and [Fe(1bppCOOH)- (1bppCOOEt)](ClO4)2 ·0.5Me2CO (2·0.5Me2CO, 1bppCOOEt = ethyl 2,6-bis(1H-pyrazol-1-yl)isonicotinate) were designed and prepared. The heteroleptic compound 1· solv was obtained by the combination of stoichiometric amounts of Fe(ClO4)2, 1bppCOOH, and 3bpp-bph, and it was designed to fine-tune the spin crossover (SCO) properties with respect to the previously reported homoleptic compound [Fe(1bppCOOH)2](ClO4)2. Indeed, the introduction of a new subs…

Incorporation of Mn12single molecule magnets into mesoporous silica

The incorporation of four Mn12 derivatives, namely [Mn12O12(O2CR)16(H2O)4] (R = CH3 (1), CH3CH2 (2), C6H5 (3), C6F5 (4)), into the hexagonal channels of the MCM-41 mesoporous silica has been studied. Only the smallest clusters 1 and 2, i.e. those with compatible size with the pores of MCM-41, could enter into the mesoporous silica. Powder X-ray diffraction analysis, HRTEM images and N2 adsorption–desorption isotherm experiments show that the well-ordered hexagonal structure of MCM-41 is preserved and that the Mn12 clusters are inside the pores. The magnetic properties of the MCM-41/2b nanocomposite material obtained in CH2Cl2 indicate that the structure of the cluster is maintained after in…

Toward new organic/inorganic superlattices: Keggin polyoxometalates in Langmuir and Langmuir-Blodgett films

The effect of Keggin heteropolyoxotungstates (XW12O40n- with X = H2, P, Si, B or Co) on Langmuir films has been studied for monolayers of DODA (dimethyldioctadecylammonium) and DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphorylcholine). Marked modifications of the compression isotherms have been observed when the Keggin anions were dissolved in the subphase:  this demonstrates that the polyanions interact with the monolayer. Langmuir−Blodgett (LB) films have been readily obtained from these systems (even with DPPC) for a particular range in polyanion concentration. X-ray diffraction and infrared dichroism experiments have shown a well-defined lamellar structure for these built-up films as well a…

Field-induced slow relaxation of magnetization in a mononuclear Co(II) complex of 2,6-bis(pyrazol-1-yl)pyridine functionalized with a carboxylic acid

Abstract Combining Co(II) with the 2,6-bis-(pyrazol1-yl)pyridine ligand functionalized with a carboxylic acid group (bppCOOH) results in the compound [CoII(bppCOOH)2](ClO4)2·2Me2CO, which shows a field-induced slow relaxation of magnetization as a result of the magnetic anisotropy of the distorted octahedral coordination of high-spin Co(II). Co(II)/Fe(II) solid solutions of bppCOOH have been prepared to study the influence of Co(II) on the spin crossover properties of Fe(II). Magnetic characterization of [Fe0.92Co0.08(bppCOOH)2](ClO4)2 indicates that the Cobalt dopant leads to a reduction of T1/2 and a loss of cooperativity of the spin transition.

Molecular Materials from Polyoxometalates

The present article highlights recent results and provide a perspective of the interest of polyoxometalates as inorganic component of molecular materials with active physical properties. Three different aspects will be presented: i) The interest of the magnetic and mixed valence clusters provided by polyoxometalate chemistry in molecular magnetism; ii) The use of these inorganic anions as magnetic component of crystalline conducting materials based on organic donor molecules; iii) The construction of well-organized films of polyoxometalate monolayers by using the Langmuir-Blodgett technique.

A thermally/chemically robust and easily regenerable anilato-based ultramicroporous 3D MOF for CO 2 uptake and separation

The combination of the properly designed novel organic linker, 3,6-N-ditriazoyil-2,5-dihydroxy-1,4-benzoquinone (trz2An), with CoII ions results in a 3D ultramicroporous MOF with high CO2 uptake capacity and separation efficiency, with particular attention to CO2/N2 and CO2/CH4 gas mixtures. This material consists of 1D chains of octahedrally coordinated CoII ions linked through the anilato ligands in the equatorial positions and to the triazole substituents from two neighbouring chains in the two axial positions. This leads to a 3D microporous structure with voids with an affinity for CO2 molecules and channels that enable the selective entrance of CO2 but not of molecules with larger kine…

Insertion of a [Fe II (pyimH) 3 ] 2+ [pyimH = 2‐(1 H ‐Imidazol‐2‐yl)pyridine] Spin‐Crossover Complex Inside a Ferromagnetic Lattice Based on a Chiral 3D Bimetallic Ox­alate Network

The insertion of the [FeII(pyimH)3]2+ [pyimH = 2-(1H-imidazol-2-yl)pyridine] spin-crossover complex into a ferromagnetic bimetallic oxalate network affords the hybrid compound [FeII(pyimH)3][MnIICrIII(ox)3]2·X (ox = C2O42–). This spin-crossover complex templates the growth of crystals formed by a chiral 3D oxalate network. The magnetic properties of this hybrid magnet show the coexistence of long-range ferromagnetic ordering at 4.5 K and a spin crossover of the intercalated [FeII(pyimH)3]2+ complex above 250 K. The compound presents a light-induced excited spin-state trapping (LIESST) effect below 60 K although with limited photoconversion (less than 8 %).

Langmuir-Blodgett Films of Magnetic Clusters

Abstract The mixed-valence manganese clusters [Mn12O12(carboxylato)16] have been organized in a multilayer architecture. Indeed, well-defined Langmuir-Blodgett (LB) films of the acetate and the benzoate Mn12 clusters can be obtained using behenic acid as organic matrix. Here, we report the magnetic properties of these multilayers, which present a marked hysteresis at 2 K.

A hybrid magnet with coexistence of ferromagnetism and photoinduced Fe(iii) spin-crossover

International audience; The insertion of a [Fe(sal2-trien)]+ complex cation into a 2D oxalate network results in a hybrid magnet with coexistence of magnetic ordering and photoinduced spin-crossover (LIESST effect) in compound [FeIII(sal2-trien)][MnIICrIII(ox)3]*(CH2Cl2) (1). A complete photomagnetic characterization together with a detailed structural analysis of the low-spin (LS) and high-spin (HS) structures of 1 is presented in order to understand such unusual behavior. This very rare and unexpected property in a FeIII spin-crossover complex, has been attributed to the strong distortion exhibited by the metastable HS state. Furthermore, 1 has shown that, in contrast to what has been pre…

Hybrid Molecular Materials Based upon the Photochromic Nitroprusside Complex, [Fe(CN)5NO]2-, and Organic π-Electron Donors. Synthesis, Structure, and Properties of the Radical Salt (TTF)7[Fe(CN)5NO]2 (TTF = Tetrathiafulvalene)

An organic/inorganic hybrid salt is obtained by combination of the photochromic nitroprusside complex with the organic donor TTF. The organic part shows an unprecedented 2D organization formed by an orthogonal arrangement of TTF hexamers and monomers. However, the donor layers are formed by pairs of moderately interacting dimeric (TTF)22+ units surrounded by neutral TTF molecules in such a way that the charge is localized and the compound is a semiconductor. Short contacts between the organic layers and the nitroprusside anions are present that may affect the photophysical properties of the nitroprusside.

Redox and guest tunable spin-crossover properties in a polymeric polyoxometalate

A bifunctionalized polyoxometalate (POM), [V6O19(C16H15N6O)2]2−, which contains a redox active hexavanadate moiety covalently linked to two tridentate 2,6-bis(pyrazol-1-yl)pyridine (1-bpp) ligands, has been prepared and characterized. Reaction of this hybrid molecule with Fe(II) or Zn(II) ions produces crystalline neutral 1D networks of formula Fe[V6O19(C16H15N6O)2]·solv (2) and Zn[V6O19(C16H15N6O)2]·solv (3) (solv = solvent molecules). Magnetic properties of 2 show an abrupt spin-crossover (SCO) with the temperature, which can be induced by light irradiation at 10 K (Light-Induced Excited Spin-State Trapping, LIESST effect). Interestingly, this porous and flexible structure enables reversi…

2D and 3D bimetallic oxalate-based ferromagnets prepared by insertion of different FeIII spin crossover complexes

The syntheses, structures and magnetic properties of the compounds of formula [Fe(III)(5-NO(2)sal(2)-trien)][Mn(II)Cr(III)(ox)(3)]·CH(3)NO(2).0.5H(2)O (1) and [Fe(III)(5-CH(3)Osal(2)-trien)][Mn(II)Cr(III)(ox)(3)] (2) are reported. The structure of 1, that crystallizes in the P2(1) chiral space group, presents a 2D honeycomb anionic layer formed by Mn(II) and Cr(III) ions linked through oxalate ligands and a cationic layer of [Fe(III)(5-NO(2)sal(2)-trien)](+) complexes intercalated between the 2D oxalate network. The structure of 2, that crystallizes in the Pna2(1) acentric space group, presents a 3D achiral anionic network formed by Mn(II) and Cr(III) ions linked through oxalate ligands wit…

Unravelling the spin-state of solvated [Fe(bpp)2]2+ spin-crossover complexes: structure–function relationship

This paper reports firstly the syntheses, crystal structures, and thermal and magnetic properties of spin crossover salts of formulae [Fe(bpp)2]3[Cr(CN)6]2·13H2O (1) and [Fe(bpp)2][N(CN)2]2·H2O (2) (bpp = 2,6-bis(pyrazol-3-yl)pyridine) exhibiting hydrogen-bonded networks of low-spin [Fe(bpp)2]2+ complexes and [Cr(CN)6]3− or [N(CN)2]− anions, with solvent molecules located in the voids. Desolvation of 1 is accompanied by a complete low-spin (LS) to a high-spin (HS) transformation that becomes reversible after rehydration by exposing the sample to the humidity of air. The influence of the lattice water on the magnetic properties of spin-crossover [Fe(bpp)2]X2 complex salts has been documented…

Polyoxometalate Monolayers in Langmuir-Blodgett Films

Langmuir and Langmuir-Blodgett (LB) films of a variety of polyoxometalates of different shapes, sizes, and charges were prepared by taking advantage of the adsorption properties of these polyanions on a positively charged monolayer of an organic surfactant spread on water. Three different aspects were investigated. 1) The electrochemical and electrochromic properties of LB films containing the easily reducible polyoxoanion [P2Mo18O62]6-. Absorbance changes of these LB films deposited onto an ITO substrate have been induced by repeated switching of the applied potential. These changes are due to the formation of the colored reduced forms of the polyanion. Coloration and bleaching of the LB f…

Multifunctionality in hybrid magnetic materials based on bimetallic oxalate complexes.

This tutorial review illustrates the design of multifunctional oxalate-based magnetic materials through the combination of the intrinsic magnetism of the metal–organic framework and the additional properties introduced by several organic/inorganic functional cations.

White Light-Emitting Electrochemical Cells Based on the Langmuir–Blodgett Technique

Light-emitting electrochemical cells (LECs) showing a white emission have been prepared with Langmuir-Blodgett (LB) films of the metallosurfactant bis[2-(2,4-difluorophenyl)pyridine][2-(1-hexadecyl-1H-1,2,3-triazol-4-yl)pyridine]iridium(III) chloride (1), which work with an air-stable Al electrode. They were prepared by depositing a LB film of 1 on top of a layer of poly(N,N'-diphenyl-N,N'-bis(4-hexylphenyl)-[1,1'-biphenyl]-4,4'-diamine (pTPD) spin-coated on indium tin oxide (ITO). The white color of the electroluminescence of the device contrasts with the blue color of the photoluminescence of 1 in solution and within the LB films. Furthermore, the crystal structure of 1 is reported togeth…

The effect of tether groups on the spin states of iron(ii)/bis[2,6-di(pyrazol-1-yl)pyridine] complexes

The synthesis of six 2,6-di(pyrazol-1-yl)pyridine derivatives bearing dithiolane or carboxylic acid tether groups is described: [2,6-di(pyrazol-1-yl)pyrid-4-yl]methyl (R)-lipoate (L1), 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxamido]ethyl (R)-lipoate (L2), 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxy]ethyl (R)-lipoate (L3), N-([2,6-di(pyrazol-1-yl)pyrid-4-ylsulfanyl]-2-aminoethyl (R)-lipoamide (L4), 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxamido]acetic acid (L5) and 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxamido]propionic acid (L6). The iron(ii) perchlorate complexes of all the new ligands exhibit gradual thermal spin-crossover (SCO) in the solid state above room temperature, except L4 who…

Dual-Emissive Photoluminescent Langmuir−Blodgett Films of Decatungstoeuropate and an Amphiphilic Iridium Complex

Langmuir monolayers and Langmuir-Blodgett (LB) films of the decatungstoeuropate [Eu(W(5)O(18))(2)](9-) (EuW(10)) and the amphiphilic Ir complex 1 have been successfully fabricated by using the adsorption properties of the EuW(10) polyanion dissolved in the aqueous subphase onto a positively charged 1 monolayer at the air-water interface. The compression isotherms and Brewster angle microscopy (BAM) of monolayers of 1 on pure water (1 monolayer) and on a subphase containing 10(-6) M EuW(10) and 10(-3) M NaCl (1/EuW(10) monolayer) have been studied. Infrared and UV-vis spectroscopy of the transferred LB films indicate that EuW(10) and 1 molecules are incorporated within these LB films. X-ray …

Magnetic–fluorescent Langmuir–Blodgett films of fluorophore-labeled ferritin nanoparticles

Abstract We have covalently coupled fluorophore 4-(2-hydroxyethoxy)-7-nitro-2,1,3-benzoxadiazole (NBD) to the external ferritin shell through lysine residues. An increase in the luminescence quantum yield of the fluorescent ferritin particles and a blue shift in its emission peak compared to individual fluorophore were observed. The study of the particles by transmission electron microscopy showed that the native iron core ferritin is intact and that no degradation occurs during chemical functionalization of the protein shell. The NBD-labeled ferritin particles are water soluble, which allowed their controlled deposition by the Langmuir–Blodgett (LB) technique. Superparamagnetic and fluores…

Langmuir−Blodgett Films of a Mo-Blue Nanoring [Mo142O429H10(H2O)49(CH3CO2)5(CH3CH2CO2)]30- (Mo142) by the Semiamphiphilic Method

Langmuir monolayers and LB films of the ring-shaped mixed-valence polyoxomolybdate [Mo142O429H10(H2O)49(CH3CO2)5(CH3CH2CO2)]30- (Mo142) dissolved in the aqueous subphase have been successfully fabricated by using the adsorption properties of a DODA monolayer. Infrared and ultraviolet−visible spectroscopy of the LB films indicates that Mo142 and DODA molecules are incorporated within these LB films. X-ray reflectivity experiments indicate that the LB films exhibit a well-defined lamellar structure formed by bilayers of DODA molecules alternating with monolayers of Mo142. Using behenic acid-modified hydrophobic quartz substrate is critical for the formation of the well-defined lamellar struct…

2D and 3D bimetallic oxalate-based ferromagnets prepared by insertion of MnIII-salen type complexes

The syntheses, structures and magnetic properties of the compounds of formulae [Mn((R)-salmen)(CH3OH)(CH3CN)][MnCr(ox)3](CH3OH)0.5(CH3CN)1.25 ((R)-1), [Mn((S)-salmen)(CH3OH)(CH3CN)][MnCr(ox)3](CH3OH)0.5(CH3CN)1.25 ((S)-1), [Mn((R)-salmen)(CH3OH)2][MnCr(ox)3](CH2Cl2)0.375(CH3OH)0.125(H2O)0.375 ((R)-2) and [Mn((S)-salmen)(CH3OH)2][MnCr(ox)3](CH2Cl2)0.375(CH3OH)0.375(H2O)0.125 ((S)-2) (ox = oxalate, salmen2− = N,N′-(1-methylethylene)bis(salicylideneiminate)), [Mn(salpn)(CH3OH)1.5(CH3CN)0.5][MnCr(ox)3](CH3OH)0.82(H2O)0.93 (3) (salpn2− = N,N′-(propane)bis(salicylideneiminate)) and [Mn(saltmen)(CH3OH)(CH3CN)][MnCr(ox)3](CH3OH) (4) (saltmen2− = N,N′-(1,1,2,2-tetramethylethylene)bis(salicylideneimi…

A Comparison of Shuttling Mechanisms in Two Constitutionally Isomeric Bistable Rotaxane-Based Sunlight-Powered Nanomotors

To find out how best to optimize shuttling of the macrocycle in a particular class of photochemically driven molecular abacus, which has the molecular structure of BR-I6+ in its Mark I prototype (Ashton et al., Chem. Eur. J. 2000, 6, 3558), we have synthesized and characterized a Mark II version of this kind of two-station rotaxane comprised of six molecular modules, namely (a) a bisparaphenylene[34]crown-10 electron donor macrocycle M and its dumbbell-shaped component which contains (b) a Ru(ii)-polypyridine photoactive unit P2+ as one of its stoppers, (c) a p-terphenyl-type ring system as a rigid spacer S, (d) 4,4′-bipyridinium (A12+) and (e) 3,3′-dimethyl-4,4′-bipyridinium (A22+) electr…

Magnetic Langmuir-Blodgett films of ferritin with different iron contents.

Magnetic Langmuir-Blodgett films of four ferritin derivatives with different iron contents containing 4220, 3062, 2200, and 1200 iron atoms, respectively, have been prepared by using the adsorption properties of a 6/1 mixed monolayer of methyl stearate (SME) and dioctadecyldimethylammonium bromide (DODA). The molecular organization of the mixed SME/DODA monolayer is strongly affected by the presence of the water-soluble protein in the subphase as shown by pi-A isotherms, BAM images, and imaging ellipsometry at the water-air interface. BAM images reveal the heterogeneity of this mixed monolayer at the air-water interface. We propose that the ferritin is located under the mixed matrix in thos…

Controlling Multivalent Interactions in Triply-Threaded Two-Component Superbundles

We have investigated the (1)H NMR spectra, the absorption spectra, the fluorescence spectra and decays, and the electrochemical properties of i). a tritopic receptor in which three benzo[24]crown-8 macrorings are fused onto a triphenylene core, ii). a trifurcated trication wherein three dibenzylammonium ions are linked 1,3,5 to a central benzenoid core, and iii). their 1:1 adduct which constitutes a triply-threaded, two-component supramolecular bundle. X-Ray crystallography has established the precise geometry of this paucivalent recognition motif in the solid state. In addition to [N(+)-H...O] hydrogen bonding and [C-H...O] interactions between the NH(2) (+) centers on the three dibenzylam…

2D Bimetallic Oxalate‐Based Ferromagnets with Inserted [Fe(4‐Br‐sal 2 ‐trien)] + and [Fe(3‐R‐sal 2 ‐trien)] + (R = Br, Cl and CH 3 O) Fe III Spin‐Crossover Complexes

The syntheses, structures and magnetic properties of the compounds of formula [FeIII(4-Br-sal2-trien)][MnIICrIII(ox)3]0.67Cl0.33·CH3OH_solvate (1), [FeIII(3-Br-sal2-trien)][MnIICrIII(ox)3]·(CH3CN)2 (2), [FeIII(3-Cl-sal2-trien)][MnIICrIII(ox)3]·(CH3OH)2·(CH3CN)2 (3) and [FeIII(3-CH3O-sal2-trien)][MnIICrIII(ox)3]·(CH3OH)·(H2O)1.5·(CH2Cl2)0.5 (4) are reported. The four structures present a 2D honeycomb anionic layer formed by MnII and CrIII ions linked through oxalate ligands and a cationic layer of the FeIII complexes intercalated between the 2D oxalate network. The main differences compared with previous 2D oxalate-based structures are the presence of double layers of cations in compounds 1,…

Insertion of single-ion magnets based on mononuclear Co(II) complexes into ferromagnetic oxalate-based networks

The 1 : 2 and 1 : 1 Co(ii) complexes of the L ligand (L = 6-(3,5-diamino-2,4,6-triazinyl)2,2'-bipyridine) with formulas [CoII(L)2](ClO4)2·0.5MeCN·Et2O (1) and [CoII(L)(CH3CN)2(H2O)](ClO4)2·MeCN (2) have been prepared. The structural and magnetic characterization of the two compounds shows that they contain octahedral high-spin Co(ii) and present a field-induced slow relaxation of the magnetization. 1 has been inserted into a bimetallic oxalate-based network leading to a novel achiral 3D compound of formula [CoII(L)2][MnIICrIII(ox)3]2·(solvate) (3) exhibiting ferromagnetic ordering below 4.6 K. EPR measurements suggest a weak magnetic coupling between the two sublattices.

Synthesis, Structure, and Magnetic Properties of [(S)-[PhCH(CH3)N(CH3)3]][Mn(CH3CN)2/3Cr(ox)3]·(CH3CN)_(solvate), a 2D Chiral Magnet Containing a Quaternary Ammonium Chiral Cation

The synthesis, structure, and magnetic properties of a novel oxalate-based bimetallic magnet obtained by using the chiral (S)-trimethyl-(1-phenyl-ethyl)-ammonium, ((S)-[PhCH(CH3)N(CH3)3](+)), cation as template is reported. This compound can be formulated as [(S)-[PhCH(CH3)N(CH3)3]][Mn(CH3CN)2/3Cr(ox)3] x (CH3CN)_(solvate), and it crystallizes in the chiral trigonal space group P3. It shows a distorted two-dimensional honeycomb structure formed by Mn(II) and Cr(III) ions connected through oxalate anions with [(S)-[PhCH(CH3)N(CH3)3](+) cations and solvent molecules intercalated between the oxalate layers. Two-thirds of the Mn(II) ions of the honeycomb anionic network are heptacoordinated. Th…

ChemInform Abstract: Multifunctionality in Hybrid Magnetic Materials Based on Bimetallic Oxalate Complexes

This tutorial review illustrates the design of multifunctional oxalate-based magnetic materials through the combination of the intrinsic magnetism of the metal–organic framework and the additional properties introduced by several organic/inorganic functional cations.

A family of layered chiral porous magnets exhibiting tunable ordering temperatures.

A simple change of the substituents in the bridging ligand allows tuning of the ordering temperatures, Tc, in the new family of layered chiral magnets A[M(II)M(III)(X2An)3]·G (A = [(H3O)(phz)3](+) (phz = phenazine) or NBu4(+); X2An(2-) = C6O4X2(2-) = 2,5-dihydroxy-1,4-benzoquinone derivative dianion, with M(III) = Cr, Fe; M(II) = Mn, Fe, Co, etc.; X = Cl, Br, I, H; G = water or acetone). Depending on the nature of X, an increase in Tc from ca. 5.5 to 6.3, 8.2, and 11.0 K (for X = Cl, Br, I, and H, respectively) is observed in the MnCr derivative. Furthermore, the presence of the chiral cation [(H3O)(phz)3](+), formed by the association of a hydronium ion with three phenazine molecules, lead…

Apoferritin-encapsulated Ni and Co superparamagnetic nanoparticles

Ni and Co nanoparticles (average diameters 3 and 3.5 nm) have been prepared within the apoferritin cavity. The protein shell prevents bulk aggregation of the metal particles, rendering them water soluble. X-Ray diffraction, transmission electronic microscopy and magnetization measurements have been used for characterizing the nanoparticles. The magnetic study of both nanoparticles confirmed the expected superparamagnetic behavior.

Increasing the Ordering Temperatures in Oxalate-Based 3D Chiral Magnets:  the Series [Ir(ppy)2(bpy)][MIIMIII(ox)3]·0.5H2O (MIIMIII = MnCr, FeCr, CoCr, NiCr, ZnCr, MnFe, FeFe); bpy = 2,2‘-Bipyridine; ppy = 2-Phenylpyridine; ox = Oxalate Dianion)

The synthesis, structure, and physical properties of a novel series of oxalate-based bimetallic magnets obtained by using the Ir(ppy)2(bpy)]+ cation as a template of the bimetallic [MIIMIII(ox)3]- ...

Structural, thermal and photomagnetic properties of spin crossover [Fe(bpp)2]2+ salts bearing [Cr(L)(ox)2]- anions

International audience; This paper is divided into two parts: in the first part, the influence of solvate molecules on the magnetic properties of spin crossover salts of [Fe(bpp)(2)][Cr(L)(ox)(2)]ClO(4) x nS (bpp = 2,6-bis(pyrazol-3yl)pyridine; L = 2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen); ox = oxalate dianion; S = solvent) is analyzed. The second part is devoted to the photomagnetic properties of the previously reported [Fe(bpp)(2)][Cr(L)(ox)(2)](2) family of compounds. The study describes the crystal structure, differential scanning calorimetry (DSC) and magnetic properties of [Fe(bpp)(2)][Cr(bpy)(ox)(2)]ClO(4) x EtOH x 4 H(2)O (1) and [Fe(bpp)(2)][Cr(phen)(ox)(2)]ClO(4) x 1.5 …

Structural, Thermal, and Magnetic Study of Solvation Processes in Spin-Crossover [Fe(bpp)2][Cr(L)(ox)2]2·nH2O Complexes

The influence of lattice water in the magnetic properties of spin-crossover [Fe(bpp)2]X2.nH2O salts [bpp = 2,6-bis(pyrazol-3-yl)pyridine] is well-documented. In most cases, it stabilizes the low-spin state compared to the anhydrous compound. In other cases, it is rather the contrary. Unraveling this mystery implies the study of the microscopic changes that accompany the loss of water. This might be difficult from an experimental point of view. Our strategy is to focus on some salts that undergo a nonreversible dehydration-hydration process without loss of crystallinity. By comparison of the structural and magnetic properties of original and rehydrated samples, several rules concerning the r…

Hexakis-adducts of [60]fullerene as molecular scaffolds of polynuclear spin-crossover molecules

A family of hexakis-substituted [60]fullerene adducts endowed with the well-known tridentate 2,6-bis(pyrazol-1-yl)pyridine (bpp) ligand for spin-crossover (SCO) systems has been designed and synthesized. It has been experimentally and theoretically demonstrated that these molecular scaffolds are able to form polynuclear SCO complexes in solution. UV-vis and fluorescence spectroscopy studies have allowed monitoring of the formation of up to six Fe(ii)–bpp SCO complexes. In addition, DFT calculations have been performed to model the different complexation environments and simulate their electronic properties. The complexes retain SCO properties in the solid state exhibiting both thermal- and …

Mn 12 single-molecule magnets incorporated into mesoporous MCM-41 silica

Abstract The incorporation of four Mn12 derivatives, namely [Mn12O12(O2CR)16(H2O)4] (R=CH3 (1), CH3CH2 (2), C6H5 (3), C6F5 (4)), into the hexagonal channels of the MCM-41 mesoporous silica have been studied. Only the smallest clusters 1 and 2 that are those with compatible size with the pores of MCM-41 could be incorporated into the mesoporous silica. Powder X-ray diffraction (XRD) analysis and N2 adsorption–desorption isotherm experiments show that the well-ordered hexagonal structure of MCM-41 is preserved and that the Mn12 clusters are inside the pores. The magnetic properties of the MCM-41/1 nanocomposite material indicate that the structure of the cluster is maintained after incorporat…

One-dimensional and two-dimensional anilate-based magnets with inserted spin-crossover complexes.

The syntheses, structures, and magnetic properties of a family of bimetallic anilate-based compounds with inserted spin-crossover cationic complexes are reported. The structures of 1-4 present a two-dimensional anionic network formed by Mn(II) and Cr(III) ions linked through anilate ligands with inserted [Fe(III)(sal2-trien)](+) (1), [Fe(III)(4-OH-sal2-trien)](+) (2), [Fe(III)(sal2-epe)](+) (3), or [Fe(III)(5-Cl-sal2-trien)](+) (4) complexes. The structure of 5 is formed by anionic [Mn(II)Cl2Cr(III)(Cl2An)3](3-) chains surrounded by [Fe(II)(tren(imid)3)](2+), Cl(-), and solvent molecules. The magnetic properties indicate that 1-4 undergo a long-range ferrimagnetic ordering at ca. 10 K. On t…

Structural Transformations and Magnetic Effects Induced by Solvent Exchange in the Spin Crossover Complex [Fe(bpp) 2 ][Cr(bpy)(ox) 2 ] 2

Structural, thermal, magnetic and solvent-exchange properties of the spin crossover compound [Fe(bpp)2][Cr(bpy)(ox)2]2 containing paramagnetic anions are given. This complex salt 1 crystallises as a dihydrate with two inequivalent (high-spin and low-spin) FeII sites. The dehydrated compound is a spin-crossover material with T1/2 ↑ = 369 K and T1/2 ↓ = 353 K. Rehydration takes place without loss of crystallinity, yielding a polymorph (2) with 100 % high-spin Fe II sites. The different high-spin fractions in 1 and 2 have been correlated to structural changes in the FeII second coordination sphere. The magnetic response to the presence of different sorbed molecules has also been explored. © Wi…

Influence of Proton Conducting Cations on the Structure and Properties of 2D Anilate-Based Magnets

The syntheses, structures, magnetic, and proton conductivity properties of a family of bimetallic anilate-based compounds with inserted alkylammonium cations are presented. The structures of (Me2NH2)[MnIICrIII(Br2An)3]·2H2O (1), (Et2NH2)[MnIICrIII(Br2An)3] (2), (Et3NH)[MnIICrIII(Cl2An)3] (3), and [(Et)(i-Pr)2NH]-[MnIICrIII(Br2An)3]·(CHCl3)0.5·(H2O) (4) contain a 2D anionic network formed by Mn(II) and Cr(III) ions linked through anilate ligands. In 1, 2, and 3, the hexagonal holes of this network are occupied by Me2NH2+, Et2NH2+, or Et3NH+ cations. Interestingly, the small increase of size of the templating cation in 4 ([(Et)(i-Pr)2NH]+ in the place of Me2NH2+, Et2NH2+ or Et3NH+), gives ris…

Intercalation of decamethylferrocenium cations in bimetallic oxalate-bridged two-dimensional magnets

The structure and magnetic properties of novel hybrid molecule-based magnets formed by combination of two magnetically active sublattices, the bimetallic oxalatobridged honeycomb net [MnIIMIII(ox)3] (MII = Mn, Fe, Co, Cr, Ni, Cu; MIII = Cr, Fe) and the organometallic cation decamethylferrocenium, are reported. Clemente Leon, Miguel, Miguel.Clemente@uv.es ; Coronado Miralles, Eugenio, Eugenio.Coronado@uv.es ; Galan Mascaros, Jose Ramon, Jose.R.Galan@uv.es ; Gomez Garcia, Carlos Jose, Carlos.Gomez@uv.es

Reversible tuning of luminescence and magnetism in a structurally flexible erbium-anilato MOF.

By combining 3,6-N-ditriazolyl-2,5-dihydroxy-1,4-benzoquinone (H2trz2An) with NIR-emitting ErIII ion, two different 3D neutral polymorphic frameworks (1a and 1b), differing for the number of uncoordinated water molecules, formulated as [Er2(trz2An)3(H2O)4]n·xH2O (x = 10, a; x = 7, b), have been obtained. The structure of 1a shows layers with (6,3) topology forming six-membered rings with distorted hexagonal cavities along the bc plane. These 2D layers are interconnected through the N4 atoms of the two pendant arms of the trz2An linkers, leading to a 3D framework, where neighboring layers are eclipsed along the a axis, with hexagonal channels filled with water molecules. In 1b, layers with (…

Photo-induced magnetic bistability in a controlled assembly of anisotropic coordination nanoparticles.

International audience; Anisotropic coordination nanoparticles of the photomagnetic network Cs(I)(2)Cu(II)(7)[Mo(IV)(CN)(8)](4) are obtained through a surfactant-free high-yield synthetic procedure in water. These particles are organised as Langmuir-Blodgett films with a preferential orientation of the nano-objects within the film that exhibit a magnetic bistability below 20 K with a very large coercivity due to an efficient photo-transformation.

Fe(II) spin crossover complexes of a derivative of 2,6-bis(pyrazol-1-yl)pyridine (1-bpp) functionalized with a carboxylic acid in the 3-pyridyl position

Abstract The preparation of a new bis(pyrazol-1-yl)pyridine (1-bpp) derivative functionalized with a carboxylic acid in the 3-pyridyl position, bpp3-COOH ligand is reported together with the structure and spin-crossover (SCO) properties of [FeII(bpp3-COOH)2](ClO4)2·0.5EtOH·0.5H2O (1). Magnetic properties of 1 indicate that LS is favored. Desolvation leads to a gradual and incomplete SCO. Solvated and desolvated compounds show LIESST effect.

Bimetallic Cyanide-Bridged Complexes Based on the Photochromic Nitroprusside Anion and Paramagnetic Metal Complexes. Syntheses, Structures, and Physical Characterization of the Coordination Compounds [Ni(en)2]4[Fe(CN)5NO]2[Fe(CN)6]·5H2O, [Ni(en)2][Fe(CN)5NO]·3H2O, [Mn(3-MeOsalen)(H2O)]2[Fe(CN)5NO], and [Mn(5-Brsalen)]2[Fe(CN)5NO]

The synthesis, crystal structure, and physical characterization of the coordination compounds [Ni(en)2]4[Fe(CN)5NO]2[Fe(CN)6]x5H2O (1), [Ni(en)2][Fe(CN)5NO]x3H2O (2), [Mn(3-MeOsalen)(H2O)]2[Fe(CN)5NO] (3), and [Mn(5-Brsalen)]2[Fe(CN)5NO] (4) are presented. 1 crystallizes in the monoclinic space group P2(1)/n (a = 7.407(4) A, b = 28.963(6) A, c = 14.744(5) A, alpha = 90 degrees, beta = 103.26(4) degrees, gamma = 90 degrees, Z = 2). Its structure consists of branched linear chains formed by cis-[Ni(en)2]2+ cations and ferrocyanide and nitroprusside anions. The presence of two kinds of iron(II) sites has been demonstrated by Mossbauer spectroscopy. 2 crystallizes in the monoclinic space group …

Iron(II) complex of 2-(1H-pyrazol-1-yl)pyridine-4-carboxylic acid (ppCOOH) suitable for surface deposition

The synthesis, structural and magnetic characterization of the tris iron(II) complex of 2-(1H-pyrazol-1-yl)pyridine-4-carboxylic acid (ppCOOH) ligand are reported in [Fe(ppCOOH)3](ClO4)2·0.5H2O·2EtOH. Single crystal structure and magnetic characterization of the bulk compound show that the low-spin state is dominant from 2 to 400 K. ESI-MS and UV–Vis spectroscopy experiments indicate that acetonitrile solutions of this complex are stable with time. ESI-MS confirms the presence of the tris complex in solution. This complex can be deposited onto SiO2 surfaces due to the presence of carboxylic acid groups by immersing the substrates into acetonitrile solutions of the complex. XPS spectra of th…

Graphene related magnetic materials: micromechanical exfoliation of 2D layered magnets based on bimetallic anilate complexes with inserted [FeIII(acac2-trien)]+ and [FeIII(sal2-trien)]+ molecules

The syntheses, structures and magnetic properties of the coordination compounds of formula [FeIII(acac2-trien)][MnIICrIII(Cl2 An)3]·(CH3CN)2 (1), [FeIII(acac2-trien)][MnIICrIII(Br2An)3]·(CH3CN)2 (2) and [GaIII(acac2-trien)][MnIICrIII(Br2An)3]·(CH3CN)2 (3) are reported. They exhibit a 2D anionic network formed by Mn(II) and Cr(III) ions linked through anilate ligands, while the [FeIII(acac2-trien)]+ or [GaIII(acac2-trien)]+ charge-compensating cations are placed inside the hexagonal channels of the 2D network, instead of being inserted in the interlamellar spacing. Thus, these crystals are formed by hybrid layers assembled through van der Waals interactions. The magnetic properties indicate …

Stimuli responsive hybrid magnets : tuning the photoinduced spin-crossover in Fe(III) complexes inserted into layered magnets

The insertion of a [Fe(sal_2 trien)]^+ complex cation into a 2D oxalate network in the presence of different solvents results in a family of hybrid magnets with coexistence of magnetic ordering and photoinduced spin crossover (LIESST effect) in compounds [Fe^{III}(sal_2 trien)][Mn^{II}Cr^{III}(ox)_3]·CHCl_3 (1·CHCl_{3}) [Fe^{III}(sal_{2} trien)][Mn^{II}Cr^{III}(ox)_{3}]·CHBr_{3} (1·CHBr_{3}) and [Fe^{III}(sal_{2} trien)][Mn^{II}Cr^{III}(ox)_{3}]·CH_{2}Br_{2} (1·CH_{2}Br_{2}). The three compounds crystallize in a 2D honeycomb anionic layer formed by Mn^{II} and Cr^{III} ions linked through oxalate ligands and a layer of [Fe(sal_{2} trien)]^{+} complexes and solvent molecules (CHCl_{3} CHBr_{…

Patterning of Magnetic Bimetallic Coordination Nanoparticles of Prussian Blue Derivatives by the Langmuir–Blodgett Technique

We report a novel method to prepare patterns of nanoparticles over large areas of the substrate. This method is based on the adsorption of the negatively charged nanoparticles dispersed in an aqueous subphase onto a monolayer of the phospholipid dipalmitoyl-l-α-phosphatidylcholine (DPPC) at the air-water interface. It has been used to prepare patterns of nanoparticles of Prussian blue analogues (PBA) of different size (K(0.25)Ni[Fe(CN)(6)](0.75) (NiFe), K(0.25)Ni[Cr(CN)(6)](0.75) (NiCr), K(0.25)Ni[Co(CN)(6)](0.75) (NiCo), Cs(0.4)Co[Cr(CN)(6)](0.8) (CsCoCr), and Cs(0.4)Co[Fe(CN)(6)](0.9) (CsCoFe)). The behavior of DPPC monolayer at the air-water interface in the presence of the subphase of P…

Iron(II) Complexes of 2,6-Di[4-(ethylcarboxy)pyrazol-1-yl]pyridine with Reversible Guest-Modulated Spin-Crossover Behavior

Tres solvatomorfos del complejo de hierro(II) de 2,6-di[4-(etilcarboxi)pirazol-1-il]piridina (bpCOOEt2p) de fórmulas [Fe(bpCOOEt2p)2](ClO4)2·1.5MeNO2 (1) , [Fe(bpCOOEt2p)2](ClO4)2·MeNO2 (2) y [Fe(bpCOOEt2p)2](ClO4)2·2MeNO2 (3) han sido preparados y caracterizados. Muestran interesantes propiedades de cruce de espín (SCO) que van desde transiciones de espín térmico parciales a completas y un efecto de captura de estado de espín excitado inducido por la luz (LIESST). En solvatomorph 2, se forma una estructura robusta con canales que permiten la entrada o eliminación de moléculas de solvente por difusión de vapor sin perder la cristalinidad. Por lo tanto, las muestras intercambiadas con disolv…

CCDC 2130642: Experimental Crystal Structure Determination

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CCDC 1491090: Experimental Crystal Structure Determination

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CCDC 2059590: Experimental Crystal Structure Determination

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CCDC 1564530: Experimental Crystal Structure Determination

Related Article: Mario Palacios-Corella, Alejandro Fernández-Espejo, Montse Bazaga-García, Enrique R. Losilla, Aurelio Cabeza, Miguel Clemente-León, Eugenio Coronado|2017|Inorg.Chem.|56|13865|doi:10.1021/acs.inorgchem.7b01965

CCDC 2059587: Experimental Crystal Structure Determination

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CCDC 2059591: Experimental Crystal Structure Determination

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CCDC 2074280: Experimental Crystal Structure Determination

Related Article: Izar Capel Berdiell, Victor García-López, Mark J. Howard, Miguel Clemente-León, Malcolm A. Halcrow|2021|Dalton Trans.|50|7417|doi:10.1039/D1DT01076J

CCDC 1564529: Experimental Crystal Structure Determination

Related Article: Mario Palacios-Corella, Alejandro Fernández-Espejo, Montse Bazaga-García, Enrique R. Losilla, Aurelio Cabeza, Miguel Clemente-León, Eugenio Coronado|2017|Inorg.Chem.|56|13865|doi:10.1021/acs.inorgchem.7b01965

CCDC 953847: Experimental Crystal Structure Determination

Related Article: Matteo Atzori, Samia Benmansour, Guillermo Mínguez Espallargas, Miguel Clemente-León, Alexandre Abhervé, Patricia Gómez-Claramunt, Eugenio Coronado, Flavia Artizzu, Elisa Sessini, Paola Deplano, Angela Serpe, Maria Laura Mercuri, and Carlos J. Gómez García|2013|Inorg.Chem.|52|10031|doi:10.1021/ic4013284

CCDC 2059589: Experimental Crystal Structure Determination

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CCDC 929206: Experimental Crystal Structure Determination

Related Article: Miguel Clemente-León, Eugenio Coronado, Maurici López-Jordà, João C. Waerenborgh, Cédric Desplanches, Hongfeng Wang, Jean-François Létard, Andreas Hauser , and Antoine Tissot|2013|J.Am.Chem.Soc.|135|8655|doi:10.1021/ja402674x

CCDC 929201: Experimental Crystal Structure Determination

Related Article: Miguel Clemente-León, Eugenio Coronado, Maurici López-Jordà, João C. Waerenborgh, Cédric Desplanches, Hongfeng Wang, Jean-François Létard, Andreas Hauser , and Antoine Tissot|2013|J.Am.Chem.Soc.|135|8655|doi:10.1021/ja402674x

CCDC 1917753: Experimental Crystal Structure Determination

Related Article: Víctor García-López, Mario Palacios-Corella, Verónica Gironés-Pérez, Carlos Bartual-Murgui, José Antonio Real, Eric Pellegrin, Javier Herrero-Martín, Guillem Aromí, Miguel Clemente-León, Eugenio Coronado|2019|Inorg.Chem.|58|12199|doi:10.1021/acs.inorgchem.9b01526

CCDC 2074281: Experimental Crystal Structure Determination

Related Article: Izar Capel Berdiell, Victor García-López, Mark J. Howard, Miguel Clemente-León, Malcolm A. Halcrow|2021|Dalton Trans.|50|7417|doi:10.1039/D1DT01076J

CCDC 1828115: Experimental Crystal Structure Determination

Related Article: Víctor García-López, João C. Waerenborgh, Bruno J. C. Vieira, Miguel Clemente-León, Eugenio Coronado|2018|Dalton Trans.|47|9156|doi:10.1039/C8DT01425F

CCDC 1828114: Experimental Crystal Structure Determination

Related Article: Víctor García-López, João C. Waerenborgh, Bruno J. C. Vieira, Miguel Clemente-León, Eugenio Coronado|2018|Dalton Trans.|47|9156|doi:10.1039/C8DT01425F

CCDC 1435556: Experimental Crystal Structure Determination

Related Article: Maria del Carmen Giménez-López, Miguel Clemente-León, Carlos Giménez-Saiz|2018|Dalton Trans.|47|10453|doi:10.1039/C8DT01269E

CCDC 1828117: Experimental Crystal Structure Determination

Related Article: Víctor García-López, João C. Waerenborgh, Bruno J. C. Vieira, Miguel Clemente-León, Eugenio Coronado|2018|Dalton Trans.|47|9156|doi:10.1039/C8DT01425F

CCDC 2130640: Experimental Crystal Structure Determination

Related Article: Noemi Monni, José J. Baldoví, Víctor García-López, Mariangela Oggianu, Enzo Cadoni, Francesco Quochi, Miguel Clemente-León, Maria Laura Mercuri, Eugenio Coronado|2022|Chemical Science|13|7419|doi:10.1039/D2SC00769J

CCDC 1828116: Experimental Crystal Structure Determination

Related Article: Víctor García-López, João C. Waerenborgh, Bruno J. C. Vieira, Miguel Clemente-León, Eugenio Coronado|2018|Dalton Trans.|47|9156|doi:10.1039/C8DT01425F

CCDC 2074282: Experimental Crystal Structure Determination

Related Article: Izar Capel Berdiell, Victor García-López, Mark J. Howard, Miguel Clemente-León, Malcolm A. Halcrow|2021|Dalton Trans.|50|7417|doi:10.1039/D1DT01076J

CCDC 929203: Experimental Crystal Structure Determination

Related Article: Miguel Clemente-León, Eugenio Coronado, Maurici López-Jordà, João C. Waerenborgh, Cédric Desplanches, Hongfeng Wang, Jean-François Létard, Andreas Hauser , and Antoine Tissot|2013|J.Am.Chem.Soc.|135|8655|doi:10.1021/ja402674x

CCDC 1411200: Experimental Crystal Structure Determination

Related Article: Maurici López-Jordà, Mónica Giménez-Marqués, Cédric Desplanches, Guillermo Mínguez Espallargas, Miguel Clemente-León, Eugenio Coronado|2016|Eur.J.Inorg.Chem.||2187|doi:10.1002/ejic.201500790

CCDC 2074283: Experimental Crystal Structure Determination

Related Article: Izar Capel Berdiell, Victor García-López, Mark J. Howard, Miguel Clemente-León, Malcolm A. Halcrow|2021|Dalton Trans.|50|7417|doi:10.1039/D1DT01076J

CCDC 2213981: Experimental Crystal Structure Determination

Related Article: Mario Palacios-Corella, Víctor García-López, Joao Carlos Waerenborgh, Bruno J. C. Vieira, Guillermo Mínguez Espallargas, Miguel Clemente-León, Eugenio Coronado|2023|Chemical Science|14|3048|doi:10.1039/D2SC05800F

CCDC 2130639: Experimental Crystal Structure Determination

Related Article: Noemi Monni, José J. Baldoví, Víctor García-López, Mariangela Oggianu, Enzo Cadoni, Francesco Quochi, Miguel Clemente-León, Maria Laura Mercuri, Eugenio Coronado|2022|Chemical Science|13|7419|doi:10.1039/D2SC00769J

CCDC 973768: Experimental Crystal Structure Determination

Related Article: Alexandre Abhervé, Juan Modesto Clemente-Juan, Miguel Clemente-León, Eugenio Coronado, Jaursup Boonmak, Sujittra Youngme|2014|New J.Chem.|38|2105|doi:10.1039/C3NJ01516E

CCDC 929204: Experimental Crystal Structure Determination

Related Article: Miguel Clemente-León, Eugenio Coronado, Maurici López-Jordà, João C. Waerenborgh, Cédric Desplanches, Hongfeng Wang, Jean-François Létard, Andreas Hauser , and Antoine Tissot|2013|J.Am.Chem.Soc.|135|8655|doi:10.1021/ja402674x

CCDC 2074276: Experimental Crystal Structure Determination

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CCDC 1054373: Experimental Crystal Structure Determination

Related Article: Alexandre Abhervé, Samuel Mañas-Valero, Miguel Clemente-León, Eugenio Coronado|2015|Chemical Science|6|4665|doi:10.1039/C5SC00957J

CCDC 1944601: Experimental Crystal Structure Determination

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CCDC 2074278: Experimental Crystal Structure Determination

Related Article: Izar Capel Berdiell, Victor García-López, Mark J. Howard, Miguel Clemente-León, Malcolm A. Halcrow|2021|Dalton Trans.|50|7417|doi:10.1039/D1DT01076J

CCDC 1054374: Experimental Crystal Structure Determination

Related Article: Alexandre Abhervé, Samuel Mañas-Valero, Miguel Clemente-León, Eugenio Coronado|2015|Chemical Science|6|4665|doi:10.1039/C5SC00957J

CCDC 973767: Experimental Crystal Structure Determination

Related Article: Alexandre Abhervé, Juan Modesto Clemente-Juan, Miguel Clemente-León, Eugenio Coronado, Jaursup Boonmak, Sujittra Youngme|2014|New J.Chem.|38|2105|doi:10.1039/C3NJ01516E

CCDC 1058520: Experimental Crystal Structure Determination

Related Article: Alexandre Abhervé, Mario Palacios-Corella, Juan Modesto Clemente-Juan, Raphael Marx, Petr Neugebauer, Joris van Slageren, Miguel Clemente-León, Eugenio Coronado|2015|J.Mater.Chem.C|3|7936|doi:10.1039/C5TC01089F

CCDC 1917752: Experimental Crystal Structure Determination

Related Article: Víctor García-López, Mario Palacios-Corella, Verónica Gironés-Pérez, Carlos Bartual-Murgui, José Antonio Real, Eric Pellegrin, Javier Herrero-Martín, Guillem Aromí, Miguel Clemente-León, Eugenio Coronado|2019|Inorg.Chem.|58|12199|doi:10.1021/acs.inorgchem.9b01526

CCDC 929205: Experimental Crystal Structure Determination

Related Article: Miguel Clemente-León, Eugenio Coronado, Maurici López-Jordà, João C. Waerenborgh, Cédric Desplanches, Hongfeng Wang, Jean-François Létard, Andreas Hauser , and Antoine Tissot|2013|J.Am.Chem.Soc.|135|8655|doi:10.1021/ja402674x

CCDC 1828113: Experimental Crystal Structure Determination

Related Article: Víctor García-López, João C. Waerenborgh, Bruno J. C. Vieira, Miguel Clemente-León, Eugenio Coronado|2018|Dalton Trans.|47|9156|doi:10.1039/C8DT01425F

CCDC 2130641: Experimental Crystal Structure Determination

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CCDC 1486674: Experimental Crystal Structure Determination

Related Article: Alexandre Abhervé, María José Recio-Carretero, Maurici López-Jordà, Juan Modesto Clemente-Juan, Josep Canet-Ferrer, Andrés Cantarero, Miguel Clemente-León, and Eugenio Coronado|2016|Inorg.Chem.|55|9361|doi:10.1021/acs.inorgchem.6b01508

CCDC 977453: Experimental Crystal Structure Determination

Related Article: Alexandre Abhervé, Miguel Clemente-León, Eugenio Coronado, Carlos J. Gómez-García, Maurici López-Jordà|2014|Dalton Trans.|43|9406|doi:10.1039/C4DT00327F

CCDC 1058519: Experimental Crystal Structure Determination

Related Article: Alexandre Abhervé, Mario Palacios-Corella, Juan Modesto Clemente-Juan, Raphael Marx, Petr Neugebauer, Joris van Slageren, Miguel Clemente-León, Eugenio Coronado|2015|J.Mater.Chem.C|3|7936|doi:10.1039/C5TC01089F

CCDC 2213982: Experimental Crystal Structure Determination

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CCDC 953846: Experimental Crystal Structure Determination

Related Article: Matteo Atzori, Samia Benmansour, Guillermo Mínguez Espallargas, Miguel Clemente-León, Alexandre Abhervé, Patricia Gómez-Claramunt, Eugenio Coronado, Flavia Artizzu, Elisa Sessini, Paola Deplano, Angela Serpe, Maria Laura Mercuri, and Carlos J. Gómez García|2013|Inorg.Chem.|52|10031|doi:10.1021/ic4013284

CCDC 1584808: Experimental Crystal Structure Determination

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CCDC 1491091: Experimental Crystal Structure Determination

Related Article: Mario Palacios-Corella, Alejandro Fernández-Espejo, Montse Bazaga-García, Enrique R. Losilla, Aurelio Cabeza, Miguel Clemente-León, Eugenio Coronado|2017|Inorg.Chem.|56|13865|doi:10.1021/acs.inorgchem.7b01965

CCDC 973770: Experimental Crystal Structure Determination

Related Article: Alexandre Abhervé, Juan Modesto Clemente-Juan, Miguel Clemente-León, Eugenio Coronado, Jaursup Boonmak, Sujittra Youngme|2014|New J.Chem.|38|2105|doi:10.1039/C3NJ01516E

CCDC 2213983: Experimental Crystal Structure Determination

Related Article: Mario Palacios-Corella, Víctor García-López, Joao Carlos Waerenborgh, Bruno J. C. Vieira, Guillermo Mínguez Espallargas, Miguel Clemente-León, Eugenio Coronado|2023|Chemical Science|14|3048|doi:10.1039/D2SC05800F

CCDC 2074277: Experimental Crystal Structure Determination

Related Article: Izar Capel Berdiell, Victor García-López, Mark J. Howard, Miguel Clemente-León, Malcolm A. Halcrow|2021|Dalton Trans.|50|7417|doi:10.1039/D1DT01076J

CCDC 1054372: Experimental Crystal Structure Determination

Related Article: Alexandre Abhervé, Samuel Mañas-Valero, Miguel Clemente-León, Eugenio Coronado|2015|Chemical Science|6|4665|doi:10.1039/C5SC00957J

CCDC 2059588: Experimental Crystal Structure Determination

Related Article: Víctor García-López, Miguel Clemente-León, Eugenio Coronado|2021|J.Appl.Phys.|129|123903|doi:10.1063/5.0046998

CCDC 973771: Experimental Crystal Structure Determination

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CCDC 2074279: Experimental Crystal Structure Determination

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