Interplay between spin crossover and proton migration along short strong hydrogen bonds

The iron(ii) salt [Fe(bpp)2](isonicNO)2·HisonicNO·5H2O (1) (bpp = 2,6-bis(pyrazol-3-yl)pyridine; isonicNO = isonicotinate N-oxide anion) undergoes a partial spin crossover (SCO) with symmetry breaking at T1 = 167 K to a mixed-spin phase (50% high-spin (HS), 50% low-spin (LS)) that is metastable below T2 = 116 K. Annealing the compound at lower temperatures results in a 100% LS phase that differs from the initial HS phase in the formation of a hydrogen bond (HB) between two water molecules (O4W and O5W) of crystallisation. Neutron crystallography experiments have also evidenced a proton displacement inside a short strong hydrogen bond (SSHB) between two isonicNO anions. Both phenomena can al…

Tailoring magnetic properties of electrodeposited thin films of the molecule-based magnet Cr5.5(CN)12 11.5H2O

This paper reports on molecular-based magnetic thin films of Prussian blue analogues (PBA) with high critical temperatures composed of mixed-valence chromium cyanides. The thin films of PBA were synthesized by means of electrodeposition technique. Morphology and magnetic study are presented in a function of electrochemical deposition conditions. We present the electrochemical methods as a promising and effective tool for preparing molecular-based magnetic thin films of Prussian blue analogue.

Exchange coupling in an electrodeposited magnetic bilayer of Prussian blue analogues

Bilayers of Prussian blue analogues (PBA) constituted of hard and soft magnets have been fabricated by means of electrochemical deposition. This method affords a good contact between two PBA thin films of nanometer thickness. Complete characterization of the resulting system has been performed, which has allowed the determination of the preservation of the chemical identity of both materials during the electrodeposition and the establishment of a clear interface between them. The magnetic behavior of the bilayer can be explained in terms of an exchange-spring magnet.

Synthesis of rigid ethynyl-bridged polytopic picolinate ligands for MOF applications

Abstract Segmented homopolytopic ligands that consist of a rigid central arylene platform, ethynylene spacers, and terminal chelating picolinate subunits have been synthesized in good yields in a two-step procedure involving a Sonogashira-type cross coupling reaction between the ester methyl 5-bromopyridine-2-carboxylate and several arylacetylenes, followed by hydrolysis of the resulting methyl picolinates. A similar strategy has been employed for the preparation of heteroditopic ligands containing picolinate and a second non-chelating pyridine or benzoate unit. The compounds are potential candidates for organic linkers in metal–organic frameworks (MOFs).

Spin crossover complexes as building units of hydrogen-bonded nanoporous structures

The paper reports on the synthesis, crystal structure, differential scanning calorimetry (DSC) and magnetic properties of a spin crossover salt of formula [Fe(bpp)2](cis,cis-1,3,5-Hchtc)·5.5 H2O (1) (bpp = 2,6-bis(pyrazol-3yl)pyridine; cis,cis-1,3,5-Hchtc = monoprotonated cyclohexanetricarboxylate dianion). The salt shows a porous structure with water molecules sitting in the channels. The electronic configuration of the Fe2+ ions is high-spin (HS). Desolvation of 1 yields a material exhibiting an abrupt spin crossover with a thermal hysteresis loop located near room temperature (T1/2↑ = 319 K and T1/2↓ = 309 K). Rehydration of this desolvated salt yields an essentially low-spin (LS) materi…

Copper(I) pseudorotaxane monolayers assembled on gold electrodes.

Two new copper (I) pseudorotaxanes bearing a thioctic acid appended unit have been prepared and deposited onto a gold electrode surface, leading to surface-attached electroactive pseudorotaxanes.

Cover Picture: Nanoscale Deposition of Single-Molecule Magnets onto SiO2 Patterns (Adv. Mater. 2/2007)

The cover shows a schematic of scanning probe nanolithography based on the spatial confinement of an oxidation reaction within a water meniscus, and its application for fabricating ordered arrays of cationic Mn12 single-molecule magnets. Romero, Coronado, Garcia, and co-workers report on p. 291 that electrostatic interactions between the molecules and trapped charges within the nanodots drive the positioning of the molecules at the nanoscale.

Polycationic Mn12Single-Molecule Magnets as Electron Reservoirs withS>10 Ground States

Electronic and Magnetic Study of Polycationic Mn-12 Single-Molecule Magnets with a Ground Spin State S=11

International audience; The preparation, magnetic characterization, and X-ray structures of two polycationic Mn-12 single-molecule magnets (Mn12O12(bet)(16)(EtOH)(4)](PF6)(14)center dot 4CH(3)CN center dot H2O (1) and [Mn12O12(bet)(16)(EtOH)(3)(H2O)](PF6)(13)(OH)center dot 6CH(3)CN center dot EtOH center dot H2O (2) (bet = betaine = (CH3)(3)N+-CH2-CO2-) are reported. 1 crystallizes in the centrosymmetric P2/cspace group and presents a (0:2:0:2) arrangement of the EtOH molecules in its structure. 2 crystallizes in the noncentrosymmetric P (4) over bar space group with two distinct Mn-12 polycations, [Mn12O12(bet)(16)(EtOH)(2)(H2O)(2)](14+) (2A) and [Mn12O12(bet)(16)(EtOH)(4)](14+)(2B) per un…

Metal complexes of a picolinate-based nitronyl nitroxide free radical.

A nitronyl nitroxide free radical containing an appended picolinate moiety was synthesized. The resulting tridentate ligand picNN forms neutral mononuclear metal complexes of formula [M(picNN)(2)].3H(2)O (M = Mn, Co, Ni, Zn). These compounds are isostructural and crystallize in the orthorhombic Pnna space group. The metal complexes have a C(2) symmetric structure, with the metal centers lying on the binary axis and surrounded by two equivalent picNN radicals. The magnetic properties of this family of compounds indicate the presence of very strong metal-radical exchange interactions, ranging from J(Ni-rad) = -193 cm(-1) to J(Mn-rad) = -98 cm(-1). Relatively weak (J(rad-rad) = -15 cm(-1)) thr…

Nitroxide Radicals as Templating Agents in the Synthesis of Magnets Based on Three-Dimensional Oxalato-Bridged Heterodimetallic Networks

Ferromagnetism and Chirality in Two-Dimensional Cyanide-Bridged Bimetallic Compounds

The combination of hexacyanoferrate(III) anions, [Fe(CN)(6)](3)(-), with nickel(II) complexes derived from the chiral ligand trans-cyclohexane-1,2-diamine (trans-chxn) affords the enantiopure layered compounds [Ni(trans-(1S,2S)-chxn)(2)](3)[Fe(CN)(6)](2).2H(2)O (1) and [Ni(trans-(1R,2R)-chxn)(2)](3)[Fe(CN)(6)](2).2H(2)O (2). These chiral systems behave as ferromagnets (T(c) = 13.8 K) with a relatively high coercive field (H(c) = 0.17 T) at 2 K. They also exhibit an unusual magnetic behavior at low temperatures that has been attributed to the dynamics of the magnetic domains in the ordered phase.

Synthesis, crystal structures and electronic properties of imidazoline nitroxide radicals bearing active groups in electropolymerisation

Thiophene-, phenylthiophene-, and indole-based nitronyl nitroxide (NN) and imino nitroxide (IN) radicals have been synthesised and their electrochemical and magnetic properties have been studied. Cyclic voltammetry measurements show that NN radicals (1–3) exhibit a one-electron quasi-reversible oxidation process that results in the formation of the corresponding nitrosonium cations. This behaviour pushes the oxidation potential of the other redox-active moiety to very high values. The oxidation of the thiophene subunit occurs at 2.35 V, whereas the oxidation of the phenylthiophene and indole moieties takes place at 1.65 and 1.39 V, respectively. Oxidation of IN radicals (4–5) is irreversibl…

Isolated Mn-12 single-molecule magnets grafted on gold surfaces via electrostatic interactions

Electrostatic interactions drive the adsorption of polycationic single-molecule magnets onto anionic monolayers self-assembled on gold surfaces. Well-isolated magnetic clusters have been deposited and characterized using scanning tunneling microscopy and X-ray photoemission spectroscopy.

Design of chiral magnets: Cyanide-bridged bimetallic assemblies based on cyclohexane-1,2-diamine

Abstract Four magnetic compounds based on chiral ligands trans-(1S,2S)-chxn and trans-(1R,2R)-chxn (chxn: cyclohexane-1,2-diamine), [Ni(trans-(1S,2S)-chxn)2]3[Fe(CN)6]2·2H2O (1), [Ni(trans-(1R,2R)-chxn)2]3[Fe(CN)6]2·2H2O (2), [Cu(trans-(1S,2S)-chxn)2]3[Fe(CN)6]2·4.5H2O (3) and [Cu(trans-(1R,2R)-chxn)2]3[Fe(CN)6]2·4.5H2O (4), are reported. The four compounds are chiral, as confirmed by X-ray analyses and circular dichroism measurements. From the magnetic point of view, 1 and 2 behave as ferromagnets, whereas 3 and 4 show a paramagnetic behavior.

Restricting Magnetic Interaction Pathways in Polyoxometalate Salts of Cationic Nitronyl Nitroxide Free Radicals

Abstract : Salts 1 and 2 that combine the [W 6 O 19 ] 2- Lindqvist anion with the cationic nitronyl nitroxide (NN) free radicals p -MepyNN + and n Bu 3 NCH 2 NN + , respectively, have been synthesized and their structural and magnetic properties have been studied. Keywords: Nitroxide radicals, polyoxometalates, magnetism. Introduction Ferromagnetism based on purely organic materials has raised a lot of interest during the last decade [1]. Most of the studies have been performed with nitronyl nitroxide (NN) radicals due to their persistence, stability and ease of functionalization [2]. Bulk ferromagnetism in these compounds arises from ferromagnetic interactions between open-shell molecules …

Magneto-Optical Properties of Electrodeposited Thin Films of the Molecule-Based Magnet Cr5.5(CN)12·11.5H2O

Prof. E. Coronado , M. Makarewicz , J. P. Prieto-Ruiz , Dr. H. Prima-Garcia , Dr. F. M. Romero Instituto de Ciencia Molecular (ICMol) Universitat de Valencia C/Catedratico Jose Beltran, 2, 46980-Paterna, Spain E-mail: eugenio.coronado@uv.es; helena.prima@uv.es; fmrm@uv.es

One-dimensional organization of free radicals via halogen bonding

Halogen bonds have been applied for the supramolecular organization of organic free radicals in the solid state and their role in the propagation of the magnetic exchange has been studied.

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…

Nanoscale Deposition of Single-Molecule Magnets onto SiO2 Patterns

bet on a silicon oxide template while the rest ofthe macroscopic surface remains free of molecules. Local oxi-dation was used to fabricate silicon oxide nanopatterns, eitherdots or stripes, over a Si (100) surface coated with a SAM.Their width ranged from 30 to 500 nm whereas the lengthcould be modified from a few nanometers up to several mi-crometers. Nanoscale direct assembly arose from a combina-tion of three factors: i) the strength of the attractive electro-static interactions between the molecules and the local oxides;ii) the weak repulsive interaction between the molecules andthe unpatternedsurface; and iii) the size of the nanopattern.Local oxidation nanolithography (LON) allows the…

Stoichiometric Control of the Magnetic Properties in Copper( II ) Cyano‐Bridged Bimetallic Complexes

Control of the Cu2+ ion coordination environment affords a 1D, magnetically diluted compound, [Cu(cis-chxn)2]3[Fe(CN)6]2·7H2O (1) and the 2D ferromagnetic material [Cu(cis-chxn)]3[Fe(CN)6]2·6H2O (2) with a critical temperature, Tc, of 3.5 K. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

A reversible hydrogen‐bond isomerization triggered by an abrupt spin crossover near room temperature.

The spin crossover salt [Fe(bpp) 2 ](isonicNO) 2 ·2.4H 2 O ( 1 ·2.4H 2 O) (bpp = 2,6‐bis(pyrazol‐3‐yl)pyridine; isonicNO = isonicotinate N‐oxide anion) exhibits a very abrupt spin crossover at T 1 /2 = 274.4 K. This triggers a supramolecular linkage (H‐bond) isomerization that responds reversibly towards light irradiation or temperature change. Isotopic effects in the thermomagnetic behaviour reveal the importance of hydrogen bonds in defining the magnetic state. Further, the title compound can be reversibly dehydrated to afford 1 , a material that also exhibits spin crossover coupled to H‐bond isomerization, leading to strong kinetic effects in the thermomagnetic properties.

Hydrogen-bonded networks of [Fe(bpp)2]2+spin crossover complexes and dicarboxylate anions: structural and photomagnetic properties

The paper reports the syntheses, crystal structures, thermal and (photo)magnetic properties of spin crossover salts of formula [Fe(bpp)2](C6H8O4)·4H2O (1·4H2O), [Fe(bpp)2](C8H4O4)·2CH3OH·H2O (2·2MeOH·H2O) and [Fe(bpp)2](C8H4O4)·5H2O (2·5H2O) (bpp = 2,6-bis(pyrazol-3yl)pyridine; C6H8O4 = adipate dianion; C8H4O4 = terephthalate dianion). The salts exhibit an intricate network of hydrogen bonds between low-spin iron(II) complexes and carboxylate dianions, with solvent molecules sitting in the voids. Desolvation is accompanied by a low-spin (LS) to high-spin (HS) transformation in the materials. The dehydrated phase 2 undergoes a two-step transition with a second step showing thermal hysteresis…

Small Gold Nanoparticles Synthesized with Sodium Citrate and Heavy Water: Insights into the Reaction Mechanism

5 páginas, 3 figuras, 1 esquema.

Single-molecule magnetic behavior in a neutral terbium(III) complex of a picolinate-based nitronyl nitroxide free radical

The terdentate anionic picolinate-based nitronyl nitroxide (picNN) free radical forms neutral and robust homoleptic complexes with rare earth-metal ions. The nonacoordinated Tb3+ complex Tb(picNN)3• 6H2O is a single-molecule magnet with an activation energy barrier Δ = 22.8 ± 0.5 K and preexponential factor τ0 = (5.5 ± 1.1) × 10-9 s. It shows magnetic hysteresis below 1 K. © 2011 American Chemical Society.

Multifunctionality in hybrid molecular materials: design of ferromagnetic molecular metals and hybrid magnets

We report on the synthesis and physical properties of novel hybrid organic–inorganic molecular materials combining ferromagnetic bimetallic oxalato-based networks and functional organic molecules as the donor bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) or cationic nitroxide free radicals. # 2002 Elsevier Science B.V. All rights reserved.

Electronic and magnetic properties of Mn 12 molecular magnets on sulfonate and carboxylic acid prefunctionalized gold surfaces

Structural, electronic, and magnetic properties of [Mn 12O 12(bet) 16(EtOH) 4](PF 6) 14·4CH 3CN·H 2O (in short Mn 12bet, bet = betaine = +N(CH 3) 3-CH 2-COO -) single-molecule magnets (SMMs) deposited on previously functionalized gold surfaces have been investigated. Self-assembled monolayers (SAMs) either of sodium mercaptoethanesulfonate (MES) or mercaptopropionic acid (MPA) are used as functionalization to avoid the direct interaction between the Mn 12bet molecules and the Au surface with the aim of preserving the main functional properties of the molecules. Scanning tunneling microscopy (STM) and X-ray photoemission spectroscopy (XPS) analysis show deposited Mn 12bet SMMs well-isolated …

Exploring the binding of Pt drugs to gold nanoparticles for controlled passive release of cisplatin.

Hybrid Magnetic Materials Based on Nitroxide Free Radicals and Extended Oxalato‐Bridged Bimetallic Networks

A series of hybrid organic-inorganic magnets of formula p-rad[MIICr(ox)3] [M = Mn (1), Co (2), Ni (3), Zn (4)] and m-rad[MIICr(ox)3] [M = Mn (5), Co (6)], in which N-methylpyridinium cations bearing a nitronyl nitroxide moiety in positions 3 (m-rad) or 4 (p-rad) of the pyridine ring coexist with the 2D honeycomb-like oxalato-bridged bimetallic lattice, has been prepared and studied by AC and DC magnetic susceptibility measurements and EPR spectroscopy. In general, the physical properties of these magnets are not altered significantly by the insertion of the nitronyl nitroxide radicals although these paramagnetic molecules seem to interact weakly with the inorganic network as demonstrated by…

A Ferroelectric Iron(II) Spin Crossover Material

A dual-function material in which ferroelectricity and spin crossover coexist in the same temperature range has been obtained. Our synthetic strategy allows the construction of acentric crystal structures in a predictable way and is based on the high directionality of hydrogen bonds. The well-known iron(II) spin crossover complex [Fe(bpp)₂]²+ (bpp = 2,6-bis(pyrazol-3-yl)pyridine), a four-fold noncentrosymmetric H-bond donor, was combined with a disymmetric H-bond acceptor such as the isonicotinate (isonic) anion to afford [Fe(bpp)₂](isonic)₂·2H₂O. This low-spin iron(II) compound crystallises in the acentric nonpolar I-4 space group and shows piezoelectricity and SHG properties. Upon dehydra…

Multifunctional molecular materials

Multifuctionality in Molecular Conductors and Magnets

Building multifuntionality in a material is a hot focus of research in contemporary materials science. Molecule-based materials offer unique opportunities in this context since the versatility of molecular chemistry provides the possibility to design materials that combine in the same crystal lattice two or more solid-state properties such as ferromagnetism, conductivity, superconductivity or non-linear optics. This opens new possibilities for potential applications in molecular electronics. A possible approach to reach this goal consists of building up hybrid solids formed by two molecular networks, such as anion/cation salts or host/guest solids, where each network furnishes distinct prop…

Temperature dependence of desolvation effects in hydrogen-bonded spin crossover complexes

The synthesis, crystal structure and (photo)magnetic properties of the anhydrous spin crossover salt of formula [Fe(bpp)2](C6H8O4) (1) (bpp = 2,6-bis(pyrazol-3-yl)pyridine; C6H8O4 = adipate dianion), obtained by desolvation at 400 K of the original tetrahydrate in a single-crystal-to-single-crystal (SC–SC) transformation, are reported. This work offers a comparison between this compound and the previously reported hydrated material ([Fe(bpp)2](C6H8O4)·4H2O, 1·4H2O), highlighting the significance of the thermal conditions used in the dehydration-rehydration processes. In both compounds, a hydrogen-bonded network between iron(II) complexes and adipate anions is observed. The original tetrahyd…

Synthesis, crystal structure and magnetic properties of [Cr2Cu2(bpy)4(ox)5]·2H2O. An oxalato-bridged heterometallic tetramer

A new heterometallic tetramer of formula [Cr2Cu 2(bpy)4(ox)5]·2H2O (1) (bpy=2,2′-bipyridine; ox=oxalate dianion) has been prepared and characterised by single-crystal X-ray diffraction, magnetic susceptibility measurements and ESR spectroscopy. The tetranuclear unit in 1 can be viewed as the combination of two terminal [Cr(bpy)2(ox)]- units with a central oxalato-bridged copper(II) dimer. The chromium ions are in a distorted octahedral environment with metal-ligand distances ranging from 1.944(4) to 2.064(5) A. The copper(II) centres lie in an axially distorted octahedron. The axial positions are occupied by one oxygen atom belonging to the central bridging oxalate anion [O(9)-Cu(1): 2.245(…

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.

Cationic Mn12 Single-Molecule Magnets and Their Polyoxometalate Hybrid Salts

A carboxy-substituted alkylammonium salt, namely, (4-carboxybenzyl)tributylammonium hexafluorophosphate, ZHPF(6), was prepared and used as incoming carboxylate ligand in a ligand-exchange reaction with [Mn(12)O(12)(O(2)CCH(3))(16)(H(2)O)(4)] (1) to afford a new Mn(12) single-molecule magnet (SMM), [Mn(12)O(12)(Z)(16)(H(2)O)(4)][PF(6)](16) (2), bearing 16 cationic units appended in the periphery. This compound behaves as a single-molecule magnet, exhibiting an out-of-phase ac magnetic susceptibility chi' '(M) signal that shows a single maximum in the 3.1-5.4 K temperature range. The frequency dependence of the maximum follows an Arrhenius law, with an effective energy barrier for reorientati…

Layered ferromagnets hosting tetraalkylammonium-substituted nitronyl nitroxide free radicals

This paper describes the structural, magnetic and EPR properties of hybrid organic/inorganic magnets formed by anionic heterometallic oxalato-based layers and cationic nitronyl nitroxide (NN) free radicals of the tetraalkylammonium type. A series of compounds of formula nBu3NCH2NN[MCr(ox)3] (M = Mn (1), Ni (2), Zn (3)) has been prepared and studied by AC and DC magnetic susceptibility measurements and EPR spectroscopy. Magnetic order with critical temperatures ranging from 5 K to 15 K was confirmed. EPR measurements show that the organic spin carriers interact significantly with the inorganic network.

Toward multifunctional single-molecule magnets: characterization of dodecanuclear manganese complexes by electrospray ionization mass spectrometry.

Single-molecule magnets (SMM) based on the dodecanuclear manganese complexes Mn12O12(RCOO)16 can be readily characterized by electrospray ionization mass spectrometry. This facilitates the synthesis of complex multifunctional molecules that have potential use in the organization of SMM into films or surfaces.

Synthesis, crystal structures and magnetic properties of picolinate-bridged copper(II) chains

The paper reports the synthesis, crystal structures, and magnetic properties of two copper(II) coordination polymers, Cu2(L1)4 (1) and Cu3(L2)6 (2), based on rigid ethynylene-bridged ditopic ligands containing one picolinate subunit (L1 = 5-(pyridin-3-ylethynyl)picolinate anion; L2 = 5-((4-(methoxycarbonyl)phenyl)ethynyl)picolinate anion). Both 1 and 2 have a chain structure. In 1, the repeating unit in the chain is a doubly bridged picolinate dicopper(II) complex, whereas 2 is built upon trimeric units where the Cu2+ ions are also connected by double picolinate bridges. Both compounds exhibit antiferromagnetic interactions in the solid state. The magnetic properties of 1 and 2 were analyze…

Magnetic ordering in an (Fe0.2Cr0.8)1.5[Cr(CN)6] Prussian blue analogue studied with synchrotron radiation based spectroscopies

The appearance of magnetic order in the (Fe0.2Cr0.8)1.5[Cr(CN)6]·15H2O Prussian blue analogue at low temperature has been investigated by means of synchrotron radiation-based X-ray absorption spectroscopy and X-ray magnetic circular dichroism. With the help of ligand field multiplet analysis we have been able to identify the oxidation states of the metallic cations present in the sample and their evolution with temperature. Our experiments reveal that the appearance of ferromagnetic order is triggered by the transformation of CrIII cations to CrII high-spin caused by a transfer of electrons from the Fe to the Cr resulting in an increase of the magnetic interactions within the (Cr, Cr) subla…

Gold-nanoparticles ingestion disrupts reproduction and development in the German cockroach.

The present work shows the effects of gold nanoparticles (AuNPs) orally administered on reproduction and development of the insect Blattella germanica. Newly emerged females were provided with food containing AuNPs (87.44μg/g) of a size between 15 and 30nm (mean 21.8nm), and were allowed to mate with males. Food ingestion, mortality, reproductive parameters (time to ootheca formation and eclosion, ootheca viability and fertility) as well as postembryonic developmental parameters of the first ootheca (nymphal survival and life span) were recorded throughout the experiment. Gold from AuNPs was accumulated by adults of B. germanica with a bioaccumulation factor of 0.1. Ingestion of AuNPs did n…

Self-Assembly of a Copper(II)-Based Metallosupramolecular Hexagon

The self-assembly of a 1:1 mixture of copper(II) ions and a rigid heteroditopic ligand L containing phen and terpy binding units gives rise in the solid state to green crystals of a hexanuclear metallamacrocycle 1. X-ray crystallography reveals that 1 consists of molecular hexagons of the grid-type family in which each metal ion is bound to two different ligands through the phen and terpy units, plus a weakly coordinated PF6 (-) anion in a highly distorted octahedral geometry. ES-MS studies of acetonitrile solutions of L and copper(II) in a 1:1 ratio show mixtures of polynuclear complexes in which trinuclear L3Cu3 species are predominant.

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.

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…

Polyoxometalate salts of cationic nitronyl nitroxide free radicals

The cationic nitronyl nitroxide free radical of the N-methylpyridinium type p-MepyNN + has been combined with [Mo 8 0 26 ] 4- and Keggin [SiW 12 0 40 ] 4- polyanions to afford salts ( p-MepyNN) 4 [Mo 8 0 26 ] DMSO (DMSO = dimethylsulfoxide) (1) and (p-MepyNN)4[SiW 12 0 40 ] 6DMF (DMF = dimethylformamide) (2). Herein, their structural and magnetic properties are described.

MOKE magnetometry as a probe of surface magnetic impurities in electropolymerized magnetic thin films of the Prussian blue analogue Fe3[Cr(CN)6]2·15 H2O

A magneto-optical Kerr effect (MOKE) study has been performed on electrodeposited thin films of the Prussian blue analogue Fe3[Cr(CN)6]2·15H2O (1). This study reveals the onset of hysteretic magnetic signals at temperatures above 60 K, in contrast with magnetic susceptibility measurements which indicate a Curie temperature of 23 K for this ferromagnetic film. The origin of this discrepancy is due to the presence of amorphous iron oxide particles that accumulate in the surface of the material. This report illustrates the potential of MOKE magnetometry for the detection of surface chemical impurities that remain elusive using bulk magnetic techniques.

Robust Lanthanoid Picolinate-Based Coordination Polymers for Luminescence and Sensing Applications

Picolinate-based segmented dianionic ligands L12– (5-((4-carboxyphenyl)ethynyl)picolinate) and L22– (5,5′-(ethyne-1,2-diyl)dipicolinate) have been used in the synthesis of the highly robust and luminescent europium(III) coordination polymers [(CH3)2NH2][Eu(H2O)2(L1)2] (1) and [(CH3)2NH2][Eu(L2)2]·H2O·CH3COOH (2). Both 1 and 2 exhibit high selectivity for detection of nitroaromatic compounds since they act as quenchers of the Eu3+ emission. Stern–Volmer plots, using nitrobenzene as a quencher, yielded values of KSV = 150 M–1 and 160 M–1 for 1 and 2, respectively. Luminescence studies in the presence of different metal ions indicate a high selectivity for Fe3+ detection, with KSV values of 47…

Detoxifying antitumoral drugs via nanoconjugation: the case of gold nanoparticles and cisplatin

Nanoparticles (NPs) have emerged as a potential tool to improve cancer treatment. Among the proposed uses in imaging and therapy, their use as a drug delivery scaffold has been extensively highlighted. However, there are still some controversial points which need a deeper understanding before clinical application can occur. Here the use of gold nanoparticles (AuNPs) to detoxify the antitumoral agent cisplatin, linked to a nanoparticle via a pH-sensitive coordination bond for endosomal release, is presented. The NP conjugate design has important effects on pharmacokinetics, conjugate evolution and biodistribution and results in an absence of observed toxicity. Besides, AuNPs present unique o…

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…

A new approach for the synthesis of magnetic materials based on nitroxide free radicals and inorganic coordination polymers

The use of nitronyl nitroxide (NN) radicals as spectators inside extended inorganic magnetic lattices is described. Two possibilities are presently being explored, namely, the design of oxalato-bridged bimetallic networks by using cationic NN radicals of the N-alkylpyridinium type as templating agents, and the design of bimetallic lattices based on hexacyanometalates and nickel(II) diaminocomplexes incorporating anionic NN radicals of the carboxyphenyl type.

Synthesis, structure and magnetic properties of iron (II), cobalt (II) and nickel (II) complexes of 2,6-bis(pyrazol-3-yl)pyridine and paramagnetic counterions

Abstract Iron (II), cobalt (II) and nickel (II) complexes of 2,6-bis(pyrazol-3-yl)pyridine (bpp) with [Cr(C2O4)3]3− have been prepared. They were characterised by single-crystal X-ray diffraction, magnetic susceptibility measurements and thermal gravimetric analyses. All three compounds are isostructural and they are formed by isolated [MII(bpp)2]2+ and [Cr(C2O4)3]3− complexes and free ClO4 −. As expected, only the salt [Fe(bpp)2]2[Cr(C2O4)3]ClO4·5H2O shows a thermal spin transition with transition temperature (T1/2) around 375 K that is correlated to the loss of water molecules.

Pressure-tuning of magnetism and linkage isomerism in iron(II) hexacyanochromate.

A pressure-induced linkage isomerization of the cyanide anion has been observed in single crystals of a chromium(III)-iron(II) Prussian blue analogue of formula K0.4Fe4[Cr(CN)6]2.8 square1.2.16H2O (1). Upon application of pressure in the 0-1200 MPa range, the cyanide ligand rotates and becomes C-bonded to the iron(II) cations, leading to a stabilization of their diamagnetic low-spin states. The result is a decrease of magnetization and magnetic ordering temperatures from TC = 19 K at ambient pressure to 13 K at 1200 MPa. The initial magnetic properties can be restored on pressure release. The reversible movement of cyanide in the solid state can be exploited as a switch of the magnetic inte…

Photoinduced effects on the magnetic properties of the (Fe0.2Cr0.8)1.5[Cr(CN)6] Prussian blue analogue

International audience; One of the most attractive characteristics of some Prussian blue derivatives is the sensitivity of their magnetic properties to the irradiation with light. In this work photoinduced effects in the (Fe0.2Cr0.8)1.5[Cr(CN)6]·15H2O PBA have been studied by means of X-ray-based spectroscopies and magnetometry. It is found that the photosensitivity of this compound is mostly centred on the Fe cations: the exposure to green light induces a transfer of electrons from them to the Cr that provokes a reversal of the previously existing linkage isomerization and increases the elastic strain caused by the misfit of the unit cells of the Fe–NC–Cr and Cr–NC–Cr sublattices. The gree…

Heat-induced charge transfer in cobalt iron cyanide

The heating of Co(2+) ferricyanide above 801C induces an inner charge transfer from Co(2+) towards Fe(III) to form the mixed valence system Co(2+)Co(III) ferri- ferro-cyanide. This charge transfer takes place preserving the material framework and forming a solid solution of the initial and final species. The cell edge of the cubic cell (Fm-3m) of this solid solution follows a regular variation with

Synthesis, Chirality, and Magnetic Properties of Bimetallic Cyanide-Bridged Two-Dimensional Ferromagnets

The assembly of hexacyanoferrate(III) anions and nickel(II) bis-diamino complexes of the chiral ligand trans-cyclohexane-1,2-diamine (trans-chxn) yields cyanide-bridged two-dimensional ferromagnets of the general formula [Ni(trans-chxn)2]3[Fe(CN)6]2‚2H2O. Their crystal structure is built from cyanide-bridged bimetallic planes separated by the bulky chxn ligands, giving rise to a large interlayer distance ( d ) 11.7 A). These materials order ferromagnetically at the Curie temperature TC ) 14 K. AC susceptibility measurements evidence an unusual magnetic behavior below TC, with a marked frequency dependence. A thorough magnetic analysis demonstrates that this complex behavior is due to the pi…

Hexachlororhenate(IV) salts of organic radical cations

Abstract The ionic salts ( p -rad) 2 [ReCl 6 ] ( 1 ) and ( m -rad) 2 [ReCl 6 ] ( 2 ) ( p / m -rad = 2-(4/3- N -methylpyridinium)-4,4,5,5-tetramethyl-4,5-dihydro-1 H -imidazol-1-oxyl-3- N -oxide) have been prepared and their crystal structures determined by single-crystal X-ray diffraction. The nitronyl nitroxide cations in compound 1 show a layered disposition, whereas the [ReCl 6 ] 2− units are placed between these layers. The nitronyl nitroxide cations in compound 2 adopt an hexagonal array but they do not result in layers. Bulk magnetic properties of 1 and 2 have been investigated in the temperature range 2–300 K. Both compounds show weak but significant intermolecular antiferromagnetic …

CCDC 1984964: Experimental Crystal Structure Determination

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CCDC 1577301: Experimental Crystal Structure Determination

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CCDC 1984962: Experimental Crystal Structure Determination

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CCDC 1427507: Experimental Crystal Structure Determination

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CCDC 1491308: Experimental Crystal Structure Determination

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CCDC 1555238: Experimental Crystal Structure Determination

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CCDC 1973926: Experimental Crystal Structure Determination

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CCDC 1973938: Experimental Crystal Structure Determination

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CCDC 1491307: Experimental Crystal Structure Determination

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CCDC 1984958: Experimental Crystal Structure Determination

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CCDC 2013419: Experimental Crystal Structure Determination

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CCDC 1973924: Experimental Crystal Structure Determination

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CCDC 1973940: Experimental Crystal Structure Determination

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CCDC 1984961: Experimental Crystal Structure Determination

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CCDC 1973936: Experimental Crystal Structure Determination

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CCDC 1832988: Experimental Crystal Structure Determination

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CCDC 1577302: Experimental Crystal Structure Determination

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CCDC 1973941: Experimental Crystal Structure Determination

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CCDC 1984957: Experimental Crystal Structure Determination

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CCDC 1507864: Experimental Crystal Structure Determination

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CCDC 1974500: Experimental Crystal Structure Determination

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CCDC 2068875: Experimental Crystal Structure Determination

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CCDC 1491309: Experimental Crystal Structure Determination

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CCDC 1832962: Experimental Crystal Structure Determination

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CCDC 1984960: Experimental Crystal Structure Determination

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CCDC 1973928: Experimental Crystal Structure Determination

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CCDC 1819792: Experimental Crystal Structure Determination

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CCDC 1577300: Experimental Crystal Structure Determination

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CCDC 1984963: Experimental Crystal Structure Determination

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CCDC 1973929: Experimental Crystal Structure Determination

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CCDC 1554603: Experimental Crystal Structure Determination

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CCDC 1427488: Experimental Crystal Structure Determination

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CCDC 1554602: Experimental Crystal Structure Determination

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CCDC 2068840: Experimental Crystal Structure Determination

Related Article: Verónica Jornet-Mollá, Chris Dreessen, Francisco M. Romero|2021|Inorg.Chem.|60|10572|doi:10.1021/acs.inorgchem.1c01229

CCDC 1984959: Experimental Crystal Structure Determination

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CCDC 1873604: Experimental Crystal Structure Determination

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CCDC 1873602: Experimental Crystal Structure Determination

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