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.

Mixed-Valence Molecular Unit for Quantum Cellular Automata: Beyond the Born-Oppenheimer Paradigm through the Symmetry-Assisted Vibronic Approach.

In this article, we focus on the electron-vibrational problem of the tetrameric mixed-valence (MV) complexes proposed for implementation as four-dot molecular quantum cellular automata (mQCA).1 Although the adiabatic approximation explored in ref 2 is an appropriate tool for the qualitative analysis of the basic characteristics of mQCA, like vibronic trapping of the electrons encoding binary information and cell-cell response, it loses its accuracy providing moderate vibronic coupling and fails in the description of the discrete pattern of the vibronic levels. Therefore, a precise solution of the quantum-mechanical vibronic problem is of primary importance for the evaluation of the shapes o…

Heptanuclear hydroxo-bridged copper cluster of the dicubane-like type: structural and magnetic characterisations of [Cu7(OH)6Cl2(pn)6(H2O)2](C(CN)3)4Cl2 (pn = 1,3-diaminopropane)

A new polynuclear copper(II) complex [Cu7(OH)6Cl2- (pn)6(H2O)2](C(CN)3)4Cl2 with hydroxo-bridging ligands has been prepared; the centrosymmetric cluster cation can be described as two Cu4O3Cl distorted cubane units sharing one copper cation. Clemente Juan, Juan Modesto, Juan.M.Clemente@uv.es ; Gomez Garcia, Carlos Jose, Carlos.Gomez@uv.es ; Coronado Miralles, Eugenio, Eugenio.Coronado@uv.es

Single-Component Magnetic Conductors Based on Mo3S7 Trinuclear Clusters with Outer Dithiolate Ligands

A trinuclear cluster complex containing the Mo(3)S(7) central unit coordinated to dithiolate ligands, in particular the organic dmit (1,3-dithia-2-thione-4,5-dithiolate) anion, has been used to prepare a single-component molecular conductor formed by the threefold symmetry magnetic building block Mo(3)S(7)(dmit)(3) (1). The [Mo(3)S(7)(dmit)(3)](2)(-) ([1](2)(-)) diamagnetic anion forms dimers by interaction between the electrophilic cluster axial sulfur atoms and the sulfur atoms of the outer dithiolate ligand. Additional contacts between adjacent dmit ligands result in chain formation. The two-electron oxidation of [1](2)(-) yields to a three-dimensional molecular solid formed by neutral M…

Magnetic Exchange between Orbitally Degenerate Metal Ions: The Problem of Magnetic Anisotropy

Abstract In this paper we show that a strong magnetic anisotropy appears in exchange mixed–valence clusters containing orbitally degenerate metal ions. Combining an effective Hamiltonian approach with the technique of the irreducible tensor operators (ITO) and pseudoangular momentum representation we have solved the problem of magnetic exchange in localized and delocalized (mixed–valence) systems with different overall symmetries ( D 2 h , D 3 h , D 4 h ). The energy pattern as well as the character of the magnetic anisotropy is closely related to the ground term of the ions, electron transfer pathways, and overall symmetry of the system being affected also by the local crystal fields, spin…

Increasing the Nuclearity of Magnetic Polyoxometalates. Syntheses, Structures, and Magnetic Properties of Salts of the Heteropoly Complexes [Ni3(H2O)3(PW10O39)H2O]7-, [Ni4(H2O)2(PW9O34)2]10-, and [Ni9(OH)3(H2O)6(HPO4)2(PW9O34)3]16-

The rational synthesis and the structural and magnetic characterization of three different nickel clusters encapsulated in Keggin trivacant fragments are presented. The three complexes show how it is possible to increase the nuclearity of the clusters (from 3 and 4 to 9) by slightly changing the synthetic conditions. These three anionic clusters crystallize as mixed salts of K+ and Na+. The trimeric complex [Ni3(H2O)3PW10O39H2O]7- (Ni3) crystallizes in the triclinic space group P1 (a = 10.896(6) A, b = 12.869(5) A, c = 20.373(6) A, α = 94.67(6)°, β = 101.12(8)°, γ = 110.72(8)°, Z = 2) and presents a ferromagnetic triangular cluster. The tetranuclear complex [Ni4(H2O)2(PW9O34)2]10- (Ni4) cry…

Can the Double Exchange Cause Antiferromagnetic Spin Alignment?

The effect of the double exchange in a square-planar mixed-valence dn+1&minus

Designing binuclear transition metal complexes: a new example of the versatility of N,N′-bis(2-aminobenzyl)-4,13-diaza-18-crown-6

[Abstract] N,N′-Bis(2-aminobenzyl)-4,13-diaza-18-crown-6 (L) is a versatile receptor able to adapt to the coordinative preferences of different metal cation guests. With first-row transition metal ions, L tends to form binuclear complexes but, depending on the nature of the particular metal ion, the structure of the binuclear complex may be very different. Herein we report a study of the structure and magnetic properties of the corresponding nickel(II) and cobalt(II) complexes. The X-ray crystal structure of the nickel complex (1), with formula [Ni2(L)(CH3CN)4](ClO4)4·CH3CN, shows that this compound presents a symmetric coordination environment with L adopting an anti arrangement. Each Ni(I…

A decacobalt(ii) cluster with triple-sandwich structure obtained by partial reductive hydrolysis of a pentacobalt(ii/iii) Weakley-type polyoxometalate.

Partial reductive hydrolysis of a penta-CoII/III cluster [CoII4(H2O)2(CoIIIW9O34)(PW9O34)]12− (1) leads to the formation of [Co2{Co3(H2O)(Co(OH)2W7O26)(PW9O34)}2]22− (2). This polyoxometalate is made up of two capping [PW9O34]9− units and two bridging [W7O26]10− units that assemble to encapsulate a novel deca-CoII cluster core comprising octahedral and tetrahedral CoII ions.

A unique example of structural and magnetic diversity in four interconvertible copper(II)-azide complexes with the same schiff base ligand: a monomer, a dimer, a chain, and a layer.

Four new Cu(II)-azido complexes of formula [CuL(N(3))] (1), [CuL(N(3))](2) (2), [Cu(7)L(2)(N(3))(12)](n) (3), and [Cu(2)L(dmen)(N(3))(3)](n) (4) (dmen = N,N-dimethylethylenediamine) have been synthesized using the same tridentate Schiff base ligand HL (2-[1-(2-dimethylaminoethylimino)ethyl]phenol, the condensation product of dmen and 2-hydroxyacetophenone). The four compounds have been characterized by X-ray structural analyses and variable-temperature magnetic susceptibility measurements. Complex 1 is mononuclear, whereas 2 is a single mu-1,1 azido-bridged dinuclear compound. The polymeric compound 3 possesses a 2D structure in which the Cu(II) ions are linked by phenoxo oxygen atoms and t…

Parallel implementation of the MAGPACK package for the analysis of high-nuclearity spin clusters

Abstract Molecular clusters are formed by a finite number of exchange-coupled paramagnetic centers and they are model systems between molecules and extended solids. In order to simulate their properties and extrapolate to solids, the size of the systems to be treated should be as large as possible. In this context, the use of efficient parallel codes is essential. We present the parallel programs ParAni and ParIso , for anisotropic and isotropic models, that enable the calculation of large energy matrices in parallel and the subsequent computation of the relevant spectral information. The evaluation of the matrix elements is based on the serial package Magpack that uses the irreducible tens…

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.

MAGPACK1A package to calculate the energy levels, bulk magnetic properties, and inelastic neutron scattering spectra of high nuclearity spin clusters

Anisotropic double exchange in orbitally degenerate mixed valence systems

Abstract The problem of the double exchange is considered for the mixed valence dimers in which one or both transition metal ions possess orbitally degenerate ground states. In the pseudo-angular momentum representation, the general formula is deduced for the matrix elements of double exchange involving the transfer integrals and all spin and orbital quantum numbers. The pairs 3 T 1 t 2 2 – 2 T 2 t 2 1 and 3 T 1 t 2 2 – 4 A 2 t 2 3 are considered in three high-symmetric topologies: edge-shared D2h, corner-shared D4h, and face-shared D3h bioctahedra. The double exchange in orbitally degenerate systems is shown to produce strong magnetic anisotropy of an orbital nature. The character of the a…

Double Exchange in Orbitally Degenerate Mixed Valence Clusters: Magnetic Anisotropy, Vibronic Effects

In this paper we consider the vibronic problem of the double exchange in mixed-valence dimers containing transition metal ions in orbitally degenerate ground states. The vibronic model includes interaction with the breathing local modes (Piepho-Krausz-Schatz-PKS) as well as the modulation of metal-metal distances as suggested by Piepho. The double exchange in orbitally degenerate systems is shown to produce strong magnetic anisotropy of orbital nature. PKS interaction is expected to suppress the magnetic anisotropy of the system, while the intercenter vibrations tend to enhance it. The roles of spin-orbit coupling and temperature are revealed for the systems with different geometries.

Problem of the magnetic anisotropy in orbitally degenerate exchange and mixed-valence clusters

Abstract This contribution summarizes the results obtained in the problem of orbital degeneracy of the metal ions in exchange coupled and mixed-valence (MV) clusters. The theory of the double exchange is generalized and the orbitally degenerate systems are considered. The orbitally dependent double exchange parameter is deduced for the singlet–triplet and triplet–triplet transition metal pairs in three high-symmetric topologies. A new effective Hamiltonian of the magnetic exchange between the ions with unquenched orbital angular momenta is discussed. The technique of the irreducible tensor operators is applied to the problem of the kinetic exchange in these kind of metal clusters. Strong ma…

Synthesis, Crystal Structure and Magneto‐Structural Correlation of an Unusual Thiocyanato‐Bridged Nickel( II ) Compound, [Ni(μ‐NCS)(dpt)(NCS)] 2 [Ni(μ‐NCS)(dpt)(NCS)] 4 [dpt = bis(3‐aminopropyl)amine]

Reaction of Ni(ClO4)2·6H2O with bis(3-aminopropyl)amine (dpt) and ammonium thiocyanate produces the novel thiocyanato-bridged nickel(II) compound [Ni(μ-NCS)(dpt)(NCS)]2[Ni(μ-NCS)(dpt)(NCS)]4, which has been structurally characterised. The structure determination reveals that there are two different molecules in the crystal lattice; one is dinuclear and other is tetranuclear. Low-temperature magnetic measurements show that there are ferro- as well as antiferromagnetic interactions. The ferromagnetic interaction arises from the dinuclear part and the doubly bridged part of the tetranuclear unit; the antiferromagnetic interaction occurs between singly bridged nickel centres in the tetranuclear…

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 …

Jahn-Teller effect in molecular electronics: quantum cellular automata

The article summarizes the main results of application of the theory of the Jahn-Teller (JT) and pseudo JT effects to the description of molecular quantum dot cellular automata (QCA), a new paradigm of quantum computing. The following issues are discussed: 1) QCA as a new paradigm of quantum computing, principles and advantages; 2) molecular implementation of QCA; 3) role of the JT effect in charge trapping, encoding of binary information in the quantum cell and non-linear cell-cell response; 4) spin-switching in molecular QCA based on mixed-valence cell; 5) intervalence optical absorption in tetrameric molecular mixed-valence cell through the symmetry assisted approach to the multimode/mul…

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…

Mixed-valence molecular four-dot unit for quantum cellular automata: Vibronic self-trapping and cell-cell response

Our interest in this article is prompted by the vibronic problem of charge polarized states in the four-dot molecular quantum cellular automata (mQCA), a paradigm for nanoelectronics, in which binary information is encoded in charge configuration of the mQCA cell. Here, we report the evaluation of the electronic levels and adiabatic potentials of mixed-valence (MV) tetra-ruthenium (2Ru(ii) + 2Ru(iii)) derivatives (assembled as two coupled Creutz-Taube complexes) for which molecular implementations of quantum cellular automata (QCA) was proposed. The cell based on this molecule includes two holes shared among four spinless sites and correspondingly we employ the model which takes into accoun…

Single ion magnets based on lanthanoid polyoxomolybdate complexes

Polyoxometalate (POM) chemistry has recently offered excellent examples of single ion magnets (SIMs) and molecular spin qubits. Compared with conventional coordination compounds, POMs provide rigid and highly symmetric coordination sites. However, all POM-based SIMs reported to date exhibit a very limited range of possibilities for chemical processability. We present herein two new families of POM-based SIMs which are soluble in organic solvents: [Ln(β-Mo8O26)2]5− {LnIII = Tb, Dy, Ho, Er, Tm and Yb} and the functionalised POMs [Ln{Mo5O13(OMe)4NNC6H4-p-NO2}2]3− {LnIII = Tb, Dy, Ho, Er, Yb and Nd}. In addition, these two families represent the first SIMs based on polyoxomolybdates. A magneto-…

Electric Field Control of Spin-Dependent Dissipative Electron Transfer Dynamics in Mixed-Valence Molecules

We demonstrate that the borderline class II/III magnetic MV dimers, which can be referred to as single molecule multiferroics, provide a unique possibility to achieve electric field control of the electron transfer (ET) dynamics. As an example, we consider a MV dimer d2-d1 in which an extra electron is delocalized over two spin-cores (s0 = 1/2), and the ET is spin-dependent due to the double exchange mechanism. It is assumed that the “extra” electron is coupled to the only intramolecular vibration, and a weak coupling to the dissipative subsystem (thermal bath) is taken into account. The vibronic energy levels and the wave functions of the isolated dimer (quantum part of the system) are num…

The Use of Polyoxometalates in the Design of Layer‐Like Hybrid Salts Containing Cationic Mn 4 Single‐Molecule Magnets

Herein, we describe the combination of polyoxometalates (POMs) with a polynuclear metallic cluster Mn4 {Mn4 = [Mn4(OAc)2(pdmH)6]2+, (pdmH = deprotonated pyridine-2,6-dimethanol; C7H8NO2)} for the construction of ionic crystals with layered architectures. Choosing a POM with the appropriate charge and size not only allows for the fine tuning of the stacking periodicity, but it also allows modifying the in-plane packing motif and density of the cationic metallic clusters. The isolation of differently layered hybrid crystals with the same Mn4 single-molecule-magnet (SMM) system allowed for the direct comparison of the magnetic properties of such materials. The variation of the slow relaxation …

An updated version of the computational package SIMPRE that uses the standard conventions for Stevens crystal field parameters

The crystal field approach used by SIMPRE is analyzed, verifying the exactness of the results concerning energy levels and magnetic properties calculated by the package. To coincide with the prevailing conventions, we reformulate the presentation of the crystal field parameters, so that the results are now, also from a formal point of view, strictly correct. New calculations are presented to test the influence of neglecting the excited J states, a common but critical approximation employed by SIMPRE. For that, we examine the case of Er(trensal) complex (H3 trensal = 2,2',2″-tris(salicylideneimino)triethylamine) where the influence of this approximation is found to be minimal. A patched vers…

Self-trapping of charge polarized states in four-dot molecular quantum cellular automata: bi-electronic tetrameric mixed-valence species

Abstract Our interest in this article is prompted by the problem of the vibronic self-trapping of charge polarized states in the four-dot molecular quantum cellular automata (mQCA), a paradigm for nanoelectronics, in which binary information is encoded in charge configuration of the mQCA cell. We report the evaluation of the electronic states and the adiabatic potentials of mixed-valence (MV) systems in which two electrons (or holes) are shared among four sites. These systems are exemplified by the two kinds of tetra–ruthenium (2Ru(II)+ 2Ru(III)) clusters (assembled as two coupled Creutz–Taube dimers) for which molecular implementation of mQCA was proposed. The tetra–ruthenium clusters incl…

ChemInform Abstract: Magnetic Exchange Between Metal Ions with Unquenched Orbital Angular Momenta: Basic Concepts and Relevance to Molecular Magnetism

This review article is a first attempt to give a systematic and comprehensive description (in the framework of the unified theoretical approach) of the exchange interactions in polynuclear systems based on orbitally degenerate metal ions in the context of their relevance to the modern molecular magnetism. Interest in these systems is related to the fundamental problems of magnetism and at the same time steered by a number of impressive potential applications of molecular magnets, like high-density memory storage units, nanoscale qubits, spintronics and photoswitchable devices. In the presence of orbital degeneracy, the conventional spin Hamiltonian (Heisenberg–Dirac–van Vleck model) becomes…

MVPACK: a package to calculate energy levels and magnetic properties of high nuclearity mixed valence clusters.

We present a FORTRAN code based on a new powerful and efficient computational approach to solve the double exchange problem for high-nuclearity MV clusters containing arbitrary number of localized spins and itinerant electrons. We also report some examples in order to show the possibilities of the program.

Insight Into The Spin-Vibronic Problem of a Mixed Valence Magnetic Molecular Cell for Quantum Cellular Automata.

The effects of the vibronic coupling in quantum cellular automata (QCA) based on the square planar mixed valence (MV) molecular cells comprising four paramagnetic centers (spin cores) and two excess mobile electrons are analyzed in the important particular case when the Coulomb energy gap between the ground antipodal diagonal-type two-electron configurations and the excited side-type configurations considerably exceeds both the one-electron transfer parameter (strong U-limit) and the vibronic stabilization energy. Under such conditions the developed model involves the second-order double exchange, the Heisenberg-Dirac-Van Vleck (HDVV) exchange and the vibronic coupling of the excess electro…

Soluble Complexes of Cobalt Oxide Fragments Bring the Unique CO2 Photoreduction Activity of a Bulk Material into the Flexible Domain of Molecular Science

The deposition of metal oxides is essential to the fabrication of numerous multicomponent solid-state devices and catalysts. However, the reproducible formation of homogeneous metal oxide films or of nanoparticle dispersions at solid interfaces remains an ongoing challenge. Here we report that molecular hexaniobate cluster anion complexes of structurally and electronically distinct fragments of cubic-spinel and monoclinic Co3O4 can serve as tractable yet well-defined functional analogues of bulk cobalt oxide. Notably, the energies of the highest-occupied and lowest-unoccupied molecular orbitals (HOMO and LUMO) of the molecular complexes, 1, closely match the valence- and conduction-band (VB…

SIMPRE: A software package to calculate crystal field parameters, energy levels, and magnetic properties on mononuclear lanthanoid complexes based on charge distributions

This work presents a fortran77 code based on an effective electrostatic model of point charges around a rare earth ion. The program calculates the full set of crystal field parameters, energy levels spectrum, and wave functions, as well as the magnetic properties such as the magnetization, the temperature dependence of the magnetic susceptibility, and the Schottky contribution to the specific heat. It is designed for real systems that need not bear ideal symmetry and it is able to determine the easy axis of magnetization. Its systematic application to different coordination environments allows magneto-structural studies. The package has already been successfully applied to several mononucle…

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…

Tunable crossover between one- and three-dimensional magnetic dynamics inCoIIsingle-chain magnets organized by halogen bonding

Low-temperature magnetometry, ac susceptibility, and calorimetry have been employed to study Co-based single-chain magnets (SCMs) organized through halogen bonding. Magnetic hysteresis and maxima in the dc and ac susceptibilities, respectively, confirm the SCM behavior of the system. Several characteristic magnetic relaxation regimes are observed at different temperatures, which can be associated with both intra- and interchain exchange interactions. Remarkably, tweaking the rate at which an external magnetic field is swept along the axis of the chains enables a controlled transition between the one- and three-dimensional dynamics. Experiments on an isostructural Co-based SCM system crystal…

Single-crystal EPR spectroscopy of a Co(II) single-chain magnet

Abstract An electron paramagnetic resonance (EPR) study of a single crystal of Co II -based single-chain magnets (SCM) is presented. Discrete resonant absorptions are associated to the presence of magnetic domains within the chains of finite lengths determined by a competition between intra-chain exchange interactions and thermally excited single spin fluctuations. The results are interpreted as a transition from single spin dynamics at high temperature ( T  ∼20 K), associated to the Kramers doublet ground state of the individual Co II ions, to archetypical SCM dynamics at low temperatures, where intra-chain correlations form long magnetic domains, whose average length is imposed by the con…

Deciphering the Role of Dipolar Interactions in Magnetic Layered Double Hydroxides

Layered double hydroxides (LDHs) exhibit unparalleled anion exchange properties and the ability to be exfoliated into 2D nanosheets, which can be used as a building block to fabricate a wide variety of hybrid functional nanostructured materials. Still, if one wants to use LDHs as a magnetic building blocks in the design of complex architectures, the role played by the dipolar magnetic interactions in these layered materials needs to be understood. In this work, we synthesized and characterized a five-membered CoAl-LDH series with basal spacing ranging from 7.5 to 34 Å. A detailed experimental characterization allows us to conclude that the main factor governing the dipolar interactions betw…

Beyond the spin model: exchange coupling in molecular magnets with unquenched orbital angular momenta.

In this critical review we review the problem of exchange interactions in polynuclear metal complexes involving orbitally degenerate metal ions. The key feature of these systems is that, in general, they carry an unquenched orbital angular momentum that manifests itself in all their magnetic properties. Thus, interest in degenerate systems involves fundamental problems related to basic models in magnetism. In particular, the conventional Heisenberg-Dirac-Van Vleck model becomes inapplicable even as an approximation. In the first part we attempt to answer two key questions, namely which theoretical tools are to be used in the case of degeneracy, and how these tools can be employed. We demons…

Spontaneous Magnetization in Heterometallic NiFe-MOF-74 Microporous Magnets by Controlled Iron Doping

We report the direct synthesis of mixed-metal NiFe-MOF-74 solids that display combination of porosity with ferrimagnetic ordering. Compared to the undoped Ni phase, controlled doping with Fe enables to modify intra and interchain magnetic interactions for the onset of spontaneous magnetization at temperatures fixed by the doping level. Synthesis of porous magnets remains somewhat elusive due to the difficulties in isolating foreseeable metal-organic architectures that combine small bridging linkers, for strong magnetic coupling, with polyaromatic connectors responsible for porosity. In turn, we demonstrate that metal doping is better fitted to modify the magnetism of Metal-Organic Framework…

Trans-dicyanobis(acetylacetonato)ruthenate(III) as a precursor to build novel cyanide-bridged RuIII–MII bimetallic compounds [M=Co and Ni]

Abstract The use of the mononuclear complex trans-[Ru(acac)2(CN)2]− as a ligand towards the preformed species [Ni2L(H2O)2Cl2], [Co(dmphen)](NO3)2, [Ni(dmphen)](NO3)2 and [Co(H2O)6](NO3)2 afforded the novel cyanide-bridged bimetallic compounds of formula [{Ru(acac)2(CN)2}{Ni2(L)(H2O)2}]{Ru(acac)2(CN)2}·2H2O (1), [{Ru(acac)2(CN)2}{Co(dmphen)(NO3)}]·H2O (2) and [{Ru(acac)2(CN)2}{Ni(dmphen)(NO3)}]·H2O (3) and [{Ru(acac)2(CN)2}2Co] (4) [Hacac = acetylacetone, dmphen = 2,9-dimethylphenanthroline and H2L = 11,23-dimethyl-3,7,15,19-tetrazatricyclo[19.3.1.19,13]hexacosa-2,7,9,11,13(26),14,19,21(25),22,24-decaene-25,26-diol]. Their syntheses, X-ray crystal structures and magnetic properties are repor…

Large Magnetic Polyoxometalates Containing the Cobalt Cubane ‘[CoIIICo3II(OH)3(H2O)6–m(PW9O34)]3− (m = 3 or 5) as a Subunit

A synthetic procedure is presented to construct new magnetic polyoxometalates (POMs) containing one or two subunits of ‘[CoIIICo3II(OH)3(H2O)6−m(PW9O34)]3−' (m = 3 or 5). The substitution of the water ligands present in these subunits by oxo or hydroxo ligands belonging to other POM fragments, gives rise to four, larger POM anions: [Co7(OH)6(H2O)6(PW9O34)2]9− (2), [Co7(OH)6(H2O)4(PW9O34)2]n9n- (2′), [Co11(OH)5(H2O)5(W6O24)(PW9O34)3]22− (3) and [{Co4(OH)3(H2O)(PW9O34)}2{K⊂(H2W12O41)2}{Co(H2O)4}2]17− (4). The crystal structures, magnetic characterization and stabilities in aqueous solutions of these POM derivatives are also presented.

VIBPACK: A package to treat multidimensional electron-vibrational molecular problems with application to magnetic and optical properties

We present a FORTRAN code based on a new powerful and efficient computational approach to solve multidimensional dynamic Jahn-Teller and pseudo Jahn-Teller problems. This symmetry-assisted approach constituting a theoretical core of the program is based on the full exploration of the point symmetry of the electronic and vibrational states. We also report some selected examples of increasing complexity aimed to display the theoretical background as well as the advantages and capabilities of the program to evaluate of the energy pattern, magnetic and optical properties of large multimode vibronic systems. © 2018 Wiley Periodicals, Inc.

Ab initio calculations of the transfer parameters and coulombic repulsion and estimation of their effects on the electron delocalization and magnetic coupling in mixed-valence Keggin polyoxotungstates

International audience; In this work, we present ab initio calculations on embedded fragments that permit to extract the value of the effective electron transfer integral and coulombic repulsion between W nearest neighbour atoms in a mixed-valence αPW12O40 Keggin polyoxoanion. This allows us to perform a quantitative study of the influence of these two parameters on the magnetic properties of Keggin polyoxoanions reduced by two electrons. We surprisingly find that the electron transfer between edge-sharing and corner-sharing WO6 octahedra have very close values, and show that the punctual charges estimation of coulombic repulsion may not be accurate enough to study the electronic distributi…

Electron Delocalization and Electrostatic Repulsion at the Origin of the Strong Spin Coupling in Mixed-Valence Keggin Polyoxometalates: Ab Initio Calculations of the One- and Two-Electron Processes

International audience; Cet article détaille une procédure générale qui associe l′évaluation de paramètres microscopiques et la prédiction de propriétés macroscopiques. Les principales interactions entre les électrons délocalisés sur des polyoxométalates à valence mixte sont extraites à partir du calcul de la spectroscopie de valence de fragments immergés dans un bain qui reproduit les principaux effets du reste du cristal sur le fragment considéré. Nous avons extrait non seulement la valeur du transfert électronique, du couplage magnétique et du paramètre de "exchange-transfer" entre ions métalliques premiers et seconds voisins, mais encore la valeur de la répulsion électrostatique entre l…

Magnetic Polyoxometalates:  Anisotropic Antiferro- and Ferromagnetic Exchange Interactions in the Pentameric Cobalt(II) Cluster [Co3W(D2O)2(CoW9O34)2]12-. A Magnetic and Inelastic Neutron Scattering Study

The ground-state properties of the pentameric Co(II) cluster [Co(3)W(D(2)O)(2)(CoW(9)O(34))(2)](12-) were investigated by combining magnetic susceptibility and low-temperature magnetization measurements with a detailed inelastic neutron scattering (INS) study on a fully deuterated polycrystalline sample of Na(12)[Co(3)W(D(2)O)(2)(CoW(9)O(34))(2)].46D(2)O. The encapsulated magnetic Co(5) unit consists of three octahedral and two tetrahedral oxo-coordinated Co(II) ions. Thus, two different types of exchange interactions are present within this cluster: a ferromagnetic interaction between the octahedral Co(II) ions and an antiferromagnetic interaction between the octahedral and the tetrahedral…

ChemInform Abstract: Cobalt Clusters with Cubane-Type Topologies Based on Trivacant Polyoxometalate Ligands.

Four novel cobalt-substituted polyoxometalates having cobalt cores exhibiting cubane or dicubane topologies have been synthesized and characterized by IR, elemental analysis, electrochemistry, UV–vis spectroscopy, X-ray single-crystal analysis, and magnetic studies. The tetracobalt(II)-substituted polyoxometalate [Co4(OH)3(H2O)6(PW9O34)]4– (1) consists of a trilacunary [B-α-PW9O34]9– unit which accommodates a cubane-like {CoII4O4} core. In the heptacobalt(II,III)-containing polyoxometalates [Co7(OH)6(H2O)6(PW9O34)2]9– (2), [Co7(OH)6(H2O)4(PW9O34)2]n9n– (3), and [Co7(OH)6(H2O)6(P2W15O56)2]15– (4), dicubane-like {CoII6CoIIIO8} cores are encapsulated between two heptadentate [B-α-PW9O34]9– (in…

Magnetic exchange interaction in a pair of orbitally degenerate ions: Magnetic anisotropy of [Ti2Cl9]−3

The theory of the kinetic exchange in a pair of orbitally degenerate ions developed by the authors [J. Phys. Chem. A 102, 200 (1998)] is applied to the case of face-shared bioctahedral dimer (overall D3h-symmetry). The effective kinetic exchange Hamiltonian is found for a 2T2–2T2 system taking into account all relevant transfer pathways and charge-transfer crystal field states. The influence of different transfer integrals involved in the kinetic exchange on the energy pattern and magnetic properties of the system is examined. The role of other related interactions (trigonal crystal field, spin–orbit coupling) is also discussed in detail. Using the pseudoangular momentum representation and …

ChemInform Abstract: Poly(polyoxotungstate)s with 20 Nickel Centers: From Nanoclusters to One-Dimensional Chains.

Rational Design of Single-Ion Magnets and Spin Qubits Based on Mononuclear Lanthanoid Complexes

Here we develop a general approach to calculating the energy spectrum and the wave functions of the low-lying magnetic levels of a lanthanoid ion submitted to the crystal field created by the surrounding ligands. This model allows us to propose general criteria for the rational design of new mononuclear lanthanoid complexes behaving as single-molecule magnets (SMMs) or acting as robust spin qubits. Three typical environments exhibited by these metal complexes are considered, namely, (a) square antiprism, (b) triangular dodecahedron, and (c) trigonal prism. The developed model is used to explain the properties of some representative examples showing these geometries. Key questions in this ar…

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…

Spin Switching in Molecular Quantum Cellular Automata Based on Mixed-Valence Tetrameric Units

In this article we focus on the study of spin effects in a single square-planar mixed-valence cell comprising two electrons and in coupled molecular cells for quantum cellular automata. Using the vibronic model we demonstrate that the polarizabilities of the cell are different in spin-singlet and spin-triplet states of the electronic pair. Based on this inference the concept of spin switching in molecular quantum cellular automata is proposed, and the conditions under which this effect is feasible are derived. In order to reveal these conditions we have performed a series of quantum-mechanical calculations of the vibronic energy levels of the isolated cell and of the cell subjected to the e…

Exploiting Clock Transitions for the chemical design of resilient molecular spin qubits

Molecular spin qubits are chemical nanoobjects with promising applications that are so far hampered by the rapid loss of quantum information, a process known as decoherence. A strategy to improve this situation involves employing so-called Clock Transitions (CTs), which arise at anticrossings between spin energy levels. At CTs, the spin states are protected from magnetic noise and present an enhanced quantum coherence. Unfortunately, these optimal points are intrinsically hard to control since their transition energy cannot be tuned by an external magnetic field; moreover, their resilience towards geometric distortions has not yet been analyzed. Here we employ a python-based computational t…

High-Nuclearity Magnetic Clusters: Generalized Spin Hamiltonian and Its Use for the Calculation of the Energy Levels, Bulk Magnetic Properties, and Inelastic Neutron Scattering Spectra

A general solution of the exchange problem in the high-nuclearity spin clusters (HNSC) containing arbitrary number of exchange-coupled centers and topology is developed. All constituent magnetic centers are supposed to possess well-isolated orbitally non-degenerate ground states so that the isotropic Heisenberg-Dirac-Van Vleck (HDVV) term is the leading part of the exchange spin Hamiltonian. Along with the HDVV term, we consider higher-order isotropic exchange terms (biquadratic exchange), as well as the anisotropic terms (anisotropic and antisymmetric exchange interactions and local single-ion anisotropies). All these terms are expressed as irreducible tensor operators (ITO). This allows u…

Coherent Spin Dependent Landau-Zener Tunneling in Mixed Valence Dimers

In this contribution we introduce the concept of single molecule ferroelectric based on the vibronic pseudo Jahn-Teller model of mixed valence dimeric clusters belonging to the Robin and Day class II compounds. We elucidate the main factors controlling the nonadiabatic Landau-Zener tunneling between the low lying vibronic levels induced by a pulse of the electric field. The transition probabilities are shown to be dependent on the both time of the pulse and the total spin of the cluster. A possibility to control the spin-dependent Landau-Zener tunneling by applying a static magnetic field is discussed.

Modelling the properties of magnetic clusters with complex structures: how symmetry can help us

The purpose of this article is to answer the question of how symmetry helps us to investigate and understand the properties of nanoscopic magnetic clusters with complex structures. The systems of choice will be the three types of polyoxometalates (POMs): (1) POMs containing localised spins; (2) reduced mixed-valence (MV) POMs; (3) partially delocalised POMs in which localised and delocalised subunits coexist and interact. The theoretical tools based on various kinds of symmetry are the following: (1) irreducible tensor operator (ITO) approach based on the so-called 'spin-symmetry' and MAGPACK program; (2) group-theoretical assignment of the exchange multiplets based on spin- and point symme…

Modelling electric field control of the spin state in the mixed-valence polyoxometalate [GeV14O40]8−

International audience; : The two-electron reduced mixed-valence polyoxometalate [GeV14O40](8-) presents an unusual paramagnetic behaviour as a consequence of the partial trapping of these electrons. The effect of applying an electric field is that of inducing antiferromagnetic coupling between the two delocalized electronic spins.

Magnetic Exchange between Orbitally Degenerate Ions:  A New Development for the Effective Hamiltonian

A new approach to the problem of the kinetic exchange for orbitally degenerate ions is developed. The constituent multielectron metal ions are assumed to be octahedrally coordinated, and strong crystal field scheme is employed, making it possible to take full advantage from the symmetry properties of the fermionic operators and collective electronic states. In the framework of the microscopic approach, the highly anisotropic effective Hamiltonian of the kinetic exchange is constructed in terms of spin operators and standard orbital operators (matrices of the unit cubic irreducible tensors). As distinguished from previous considerations, the effective Hamiltonian is derived for a most genera…

High nuclearity mixed-valence magnetic clusters: theoretical study of the spin coupling in the C602− fulleride ion

Abstract The problem of delocalization of a pair of electrons over the fullerene C 60 is considered, with the aim of elucidating the nature of the ground spin state, as well as the structure of the low-lying energy levels in this mixed-valence molecule C 60 2− . A model that considers the Coulomb interactions between the two extra electrons, as well as the two single-electron transfer processes involved in the electron delocalization, is developed. The influence of these electronic parameters on the spectrum of the low-lying energy levels is discussed. We find that the ground state is always a spin singlet, whatever the relative values of these parameters are.

Purely Spectroscopic Determination of the Spin Hamiltonian Parameters in High-Spin Six-Coordinated Cobalt(II) Complexes with Large Zero-Field Splitting.

Accurate determination of the spin Hamiltonian parameters in transition-metal complexes with large zero-field splitting (ZFS) is an actual challenge in studying magnetic and spectroscopic properties of high-spin transition metal complexes. Recent critical papers have convincingly shown that previous determinations of these parameters, based only on the magnetic data, have low accuracy and reliability. A combination of X-band electron paramagnetic resonance (EPR) spectroscopy and SQUID magnetometry seems to be a more convincing and accurate approach. However, even in this case, the accuracy of the determination of the spin Hamiltonian parameters is strongly limited. In this work, we propose …

Electric Field Control of Spin States in Trigonal Two-Electron Quantum Dot Arrays and Mixed-Valence Molecules: II. Vibronic Problem

In this article, the vibronic model for an electric field switchable mixed-valence trimer containing two delocalized electrons or holes is proposed and examined. The role of the vibronic coupling on the electric field effects is analyzed by means of the semiclassical adiabatic approach and, alternatively, with the aid of the numerical analysis of the Schrodinger equation with due allowance for the kinetic energy of the ions (dynamic problem). The adiabatic potential landscapes have been calculated by taking into account the influence of the electric field. As the adiabatic approximation has a limited frame of validity, the study of the electric field effects has also been performed within m…

Molecular spin qubits based on lanthanide ions encapsulated in cubic polyoxopalladates: design criteria to enhance quantum coherence

The family of cubic polyoxopalladates encapsulating lanthanide ions [LnPd12(AsPh)8O32]5− where Ln = Tb, Dy, Ho, Er and Tm, is magnetically characterised and theoretically described by the Radial Effective Charge (REC) model and a phenomenological crystal-field approach using the full-hamiltonian, in the SIMPRE and CONDON packages respectively. The lack of anisotropy generates an extraordinarily rich energy level structure at low temperatures, which allows us to study how such a structure is affected by lifting the strict cubic symmetry and/or by applying an external magnetic field. In particular, we will explore the possibility of using these cubic Ln complexes as spin-qubits. We will focus…

Light-induced decarboxylation in a photo-responsive iron-containing complex based on polyoxometalate and oxalato ligands.

A new iron-oxalato polyoxometalate exhibits a remarkable photocoloration effect in the solid state based entirely on an intramolecular process.

Molecular anisotropy analysis of single-ion magnets using an effective electrostatic model.

Simple electrostatic models have been shown to successfully rationalize the magnetic properties of mononuclear single molecule magnets based on f-elements and even to predict the direction of the magnetic anisotropy axis in these nanomagnets. In this Article, we go a step forward by showing that these models, conveniently modified to account for the covalency effects, are able to predict not only the easy axis direction but also the three components of the magnetic anisotropy. Thus, by using a lone pair effective charge (LPEC) model we can fully reproduce the angular dependence of the magnetic susceptibility in single crystals of pentamethylcyclopentadienyl-Er-cyclooctatetraene single-ion m…

Localization–Delocalization in Bridged Mixed-Valence Metal Clusters: Vibronic PKS Model Revisited

Here we describe a new vibronic model of mixed valence (MV) dimer inspired by the conventional Piepho, Krausz, and Schatz (PKS) approach. We attempted to partially lift the main restriction of the PKS model dealing with the vibronically independent moieties of a MV molecule. The refined version of the PKS model in which the bridging ligands are included deals with the three main interactions: electron transfer (integral t0) related to the high-symmetric ligand configuration, on-site vibronic coupling (parameter υ) arising from the modulation of the crystal field on the metal sites by the breathing displacements of their nearest ligand surroundings, and intercenter vibronic coupling (paramet…

Origin of the Paramagnetic Properties of the Mixed‐Valence Polyoxometalate [GeV 14 O 40 ] 8– Reduced by Two Electrons: Wave Function Theory and Model Hamiltonian Calculations

The aim of the work is to give an explanation of the magnetic properties of a mixed-valence [GeV14O40]8– polyoxometalate reduced by two electrons, which, in contrast to what happens in other two-electron-reduced polyoxometalates, does not show any magnetic coupling between the two unpaired electrons. For this purpose, a quantitative evaluation of the microscopic electronic parameters (electron transfer, magnetic coupling, magnetic orbital energy, and Coulomb repulsion) of the mixed-valence polyoxometalate cluster is performed. The parameters are extracted from valence-spectroscopy large configuration interaction (CI) calculations on embedded fragments. Then, these parameters are used in an …

Magnetization Relaxation in a Three‐Dimensional Ligated Cobalt Phosphonate Containing Ferrimagnetic Chains

Role of the electron transfer and magnetic exchange interactions in the magnetic properties of mixed-valence polyoxovanadate complexes.

International audience; Modeling the properties of high-nuclearity, high-electron-population, mixed-valence (MV) magnetic systems remains one of the open challenges in molecular magnetism. In this work, we analyze the magnetic properties of a series of polyoxovananadate clusters of formula [V 18O 42] (12-) and [V 18O 42] (4-). The first compound is a fully localized spin cluster that contains 18 unpaired electrons located at the metal sites, while the second one is a MV cluster with 10 unpaired electrons largely delocalized over the 18 metal sites. A theoretical model that takes into account the interplay between electron transfer and magnetic exchange interactions is developed to explain t…

Inside Cover: Poly(polyoxotungstate)s with 20 Nickel Centers: From Nanoclusters to One-Dimensional Chains (Angew. Chem. Int. Ed. 39/2009)

Spin-coupling topology in the copper hexamer compounds A2Cu3O(SO4)3 (A=Na, K)

The compounds ${A}_{2}\mathrm{C}{\mathrm{u}}_{3}\mathrm{O}{(\mathrm{S}{\mathrm{O}}_{4})}_{3}$ $(A=\mathrm{Na},\phantom{\rule{0.16em}{0ex}}\mathrm{K})$ are characterized by copper hexamers that are weakly coupled to realize antiferromagnetic order below ${T}_{N}\ensuremath{\approx}3\phantom{\rule{0.16em}{0ex}}\mathrm{K}$. They constitute quantum spin systems with $S=1$ triplet ground states. We investigated the energy-level splittings of the copper hexamers by inelastic neutron scattering experiments covering the entire range of the magnetic excitation spectra. The observed transitions are governed by very unusual selection rules that we ascribe to the underlying spin-coupling topology. This…

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.

Magnetic Excitations in Polyoxometalate Clusters Observed by Inelastic Neutron Scattering:  Evidence for Ferromagnetic Exchange Interactions and Spin Anisotropy in the Tetrameric Nickel(II) Cluster [Ni4(H2O)2(PW9O34)2]10- and Comparison with the Magnetic Properties

The ground-state properties of the tetranuclear Ni2+ cluster [Ni4(H2O)2(PW9O34)2]10- were investigated by combining magnetic susceptibility and magnetization measurements with a detailed inelastic neutron scattering (INS) study on a fully deuterated sample of K6Na4[Ni4(H2O)2(PW9O34)2]·24H2O. The temperature dependence of the magnetic susceptibility indicates a ferromagnetic coupling of the four constituent Ni2+ ions (s = 1), and a low-temperature magnetization study provides the magnitude of the S = 4 ground-multiplet splitting due to the single-ion anisotropy of the Ni2+ ions. Besides a more direct and precise determination of the anisotropic S = 4 ground-multiplet splitting, INS enabled t…

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…

Influence of Peripheral Substitution on the Magnetic Behavior of Single-Ion Magnets Based on Homo- and Heteroleptic TbIIIBis(phthalocyaninate)

A series of homoleptic ([Tb(III)(Pc)(2) ]) and heteroleptic ([Tb(III)(Pc)(Pc')]) Tb(III) bis(phthalocyaninate) complexes that contain different peripheral substitution patterns (i.e., tert-butyl or tert-butylphenoxy groups) have been synthesized in their neutral radical forms and then reduced into their corresponding anionic forms as stable tetramethylammonium/tetrabutylammonium salts. All of these compounds were spectroscopically characterized and their magnetic susceptibility properties were investigated. As a general trend, the radical forms exhibited larger energy barriers for spin reversal than their corresponding reduced compounds. Remarkably, heteroleptic complexes that contain elect…

Innentitelbild: Poly(polyoxotungstate)s with 20 Nickel Centers: From Nanoclusters to One-Dimensional Chains (Angew. Chem. 39/2009)

Effects of halogen bonding in ferromagnetic chains based on Co(ii) coordination polymers

Two linear cobalt chloride ferromagnetic chains, trans-[CoCl2(3,5-X2py)2] [X = Cl (1), Br (2)], have been prepared and the influence of the halogen bonding on the interchain magnetic interactions has been investigated.

The azido ligand: a useful tool in designing chain compounds exhibiting alternating ferro- and antiferro-magnetic interactions

A one-pot reaction of NiII 1, CoII 2, FeII 3 and MnII 4 with 2,2A-bipyridine (bipy) and azide in water leads to [M(bipy)(N3)2]n chains where the metal ion is alternatively bridged by double end-on (EO) and end-to-end (EE) azido bridges; theoretical analysis of the variable-temperature magnetic susceptibility data of 1 and 4 reveals the occurrence of intrachain alternating ferro- (through EO) and antiferro-magnetic (through EE) interactions. Julve Olcina, Miguel, Miguel.Julve@uv.es ; Lloret Pastor, Francisco, Francisco.Lloret@uv.es ; Clemente Juan, Juan Modesto, Juan.M.Clemente@uv.es

Manipulation of the spin in single molecule magnets via Landau-Zener transitions

We theoretically investigate the effects of a magnetic pulse on a single-molecule magnet (SMM) initially magnetized by a dc field along the easy axis of magnetization. In the Landau\char21{}Zener (LZ) scheme, it is shown that the final spin state is a function of the shape and duration of the pulse, conditioned by the decoherence time of the SMM. In the case of coherent tunneling, the asymmetric pulses are shown to reverse the direction of the magnetization, while the symmetric pulses can only decrease the value of the initial magnetization. It is also demonstrated that the application of an external variable dc field in the hard plane of magnetization provides the possibility to tune the r…

Isolation of Four New CoII/CoIII and NiII Complexes with a Pentadentate Schiff Base Ligand: Syntheses, Structural Descriptions and Magnetic Studies

In this paper we report the temperature and pH dependent syntheses and systematic characterization of four new Co(II)/Co(III) and Ni(II) complexes with a pentadentate Schiff base ligand H(3)L obtained by condensing 1,3,-diaminopropan-2-ol with 2-hydroxyacetophenone in 1:2 molar ratio. The room temperature syntheses involving Co(II) and Ni(II) nitrates and the ligand H(3)L lead to the isolation of the dinuclear species [Co(2)L(2)(H(2)O)] (1), and the mononuclear complex [Ni(LH)] (3), respectively, whereas refluxing at basic pH leads to the tetranuclear complexes, [Co(II)(2)Co(III)(2)L(2)(μ(3)-OMe)(2)(NO(3))(H(2)O)(2)]NO(3)·2(H(2)O) (2), and [Ni(4)L(2)(μ(3)-OMe)(2)(H(2)O)(2)]·2H(2)O (4). 1 is…

Synthesis and Magnetic Properties of a Copper Cube: [Cu 4 (OH) 4 (C 16 H 18 N 2 ) 4 ] 4+ (ClO 4 ) 4 C 3 H 6 O [C 16 H 18 N 2 =( E )‐1,6‐[Di(pyridin‐4‐yl)hex‐3‐ene]

We are grateful to the National Mass Spectrometry Service Center for mass spectra and to the UK National Crystallography Service for data sets. Supplementary Figure S1-S4: IR and UV/Vis spectra of compound 1

Effect of Cyanato, Azido, Carboxylato, and Carbonato Ligands on the Formation of Cobalt(II) Polyoxometalates: Characterization, Magnetic, and Electrochemical Studies of Multinuclear Cobalt Clusters

Five Co(II) silicotungstate complexes are reported. The centrosymmetric heptanuclear compound K(20)[{(B-beta-SiW(9)O(33)(OH))(beta-SiW(8)O(29)(OH)(2))Co(3)(H(2)O)}(2)Co(H(2)O)(2)]47 H(2)O (1) consists of two {(B-beta-SiW(9)O(33)(OH))(beta-SiW(8)O(29)(OH)(2))Co(3)(H(2)O)} units connected by a {CoO(4)(H(2)O)(2)} group. In the chiral species K(7)[Co(1.5)(H(2)O)(7))][(gamma-SiW(10)O(36))(beta-SiW(8)O(30)(OH))Co(4)(OH)(H(2)O)(7)]36 H(2)O (2), a {gamma-SiW(10)O(36)} and a {beta-SiW(8)O(30)(OH)} unit enclose a mononuclear {CoO(4)(H(2)O)(2)} group and a {Co(3)O(7)(OH)(H(2)O)(5)} fragment. The two trinuclear Co(II) clusters present in 1 enclose a mu(4)-O atom, while in 2 a mu(3)-OH bridging group co…

Two pyrazolylborate dysprosium(III) and neodymium(III) single ion magnets modeled by a Radial Effective Charge approach

Abstract A Radial Effective Charge model based on a point charge approach is applied in order to study the magnetic behavior of two lanthanoid single ion magnets coordinated by pyrazole-based ligands that produce a D3h crystal field. We obtain the lowest-lying magnetic levels and the associated wave functions of Dy(H2BPzMe22)3 (1), and the tricapped NdTp3 (2), where H2BPzMe22 = dihydrobis(dimenthylpyrazolyl)borate and Tp = trispyrazolylborate. Results support the observed SMM behavior.

Electric field control of the spin state in mixed-valence magnetic molecules.

Multiferroic molecules for spintronics: In a many-electron mixed-valence dimer with dominant double exchange, as compared with antiferromagnetic superexchange, the electric field is shown to induce a spin crossover from the ferromagnetic spin state to the antiferromagnetic one. This leads to a sharp decrease in the magnetic moment of the molecule and a simultaneous stepwise increase in the electric dipole (see figure).

Mixed-Valence Magnetic Molecular Cell for Quantum Cellular Automata: Prospects of Designing Multifunctional Devices through Exploration of Double Exchange

In this article, we propose to use multielectron square-planar mixed-valence (MV) molecules as molecular cells for quantum cellular automata (QCA) devices. As distinguished from previous proposals ...

Magneto-structural correlations and DFT calculations in two rare tetranuclear copper(II)-clusters with doubly phenoxo and end-on azido bridges: Syntheses, structural variations and EPR studies

International audience; By slightly changing the synthetic conditions, we have prepared two closely related linear tetranuclear CuII complexes with the symmetrical ONNO donor tetradentate Schiff-base ligand [H2L = (OH)C6H4(CH3)Cdouble bond; length as m-dashN(CH2)3Ndouble bond; length as m-dashC(CH3)C6H4(OH)] and with azide ions. These two distinctly coloured crystalline products were characterized by elemental analysis, IR and UV–Vis spectroscopy, CV, EPR spectra and variable temperature magnetic measurements. Single crystal X-ray diffraction studies of the green [Cu4(μ-L)2(μ1,1-N3)2(N3)2] (1) and the red [Cu4(μ-L)2(μ1,1-N3)2(N3)2(H2O)2] (2) crystals show that the coordination environment o…

A New Heptanuclear Cobalt(II) Cluster Encapsulated in a Novel Heteropolyoxometalate Topology:  Synthesis, Structure, and Magnetic Properties of [Co7(H2O)2(OH)2P2W25O94]16-

The synthesis and the structural and magnetic characterization of a novel heptanuclear cobalt cluster encapsulated in a heteropolyoxotungstate is reported. This complex shows how it is possible to control the nuclearity of the Co clusters formed in a tungstate solution by slightly changing the synthetic conditions, and the relevance of pH in this regard. This heptanuclear complex [Co7(H2O)2(OH)2P2W25O94]16- (Co7) crystallizes in the triclinic space group P1 (a = 12.3403(6) A, b = 22.5966(11) A, c = 23.2645(12) A, α = 68.7830(11)°, β = 83.7981(12)°, γ = 78.5423(13)°, V = 5922.4(5) A3, Z = 2) and is formed by six CoO6 octahedra from two Co3 trimers sustained by Keggin trivacant fragments held…

Magnetism in Polyoxometalates: Anisotropic Exchange Interactions in the Co Moiety of [Co3W(D2O)2(ZnW9O34)2]12−—A Magnetic and Inelastic Neutron Scattering Study

The ground-state properties of a Co moiety encapsulated in a polyoxometalate anion were investigated by combining measurements of specific heat, magnetic susceptibility, and low-temperature magnetization with a detailed inelastic neutron scattering (INS) study on a fully deuterated polycrystalline sample of Na12[Co3W(D2O)2(ZnW9O34)2]⋅40 D2O (Co3). The ferromagnetic Co3O14 cluster core consists of three octahedrally oxo-coordinated CoII ions. According to the single-ion anisotropy and spin–orbit coupling of the octahedral CoII ions, the appropriate exchange Hamiltonian to describe the ground-state properties of the Co3 spin cluster is anisotropic and is expressed as ℋ=−2Σ(JŜ1αŜ2α+JŜ2αŜ3α), w…

Magnetic clusters from polyoxometalate complexes

Abstract The present article highlights the increasing interest of polyoxometalates in molecular magnetism, providing at the same time a perspective of the state-of-the-art in this area. The main focus is the polyoxotungstates. The first aspect we discuss is that of the coordination chemistry of these metal–oxide ligands. We show that this chemistry leads to remarkable examples of well-insulated magnetic clusters of controlled nuclearity and topology. In these clusters detailed information on the nature of the magnetic exchange interactions can be extracted by using, in addition to the classical magnetic techniques (magnetic susceptibility, magnetization and EPR spectroscopy), other physica…

Mononuclear Lanthanide Complexes: Use of the Crystal Field Theory to Design Single-Ion Magnets and Spin Qubits

Supramolecular 2D/3D isomerism in a compound containing heterometallic Cu(II)2Co(II) nodes and dicyanamide bridges.

Three new heterometallic copper(II)-cobalt(II) complexes [(CuL(2))2Co{dca}2]·H2O(1), [(CuL(1))2Co{dca}2]n (2a), and [(CuL(1))2Co{dca}2]n (2b) [dca(-) = dicyanamide = N(CN)2(-)] have been synthesized by reacting the "metallo-ligand" [CuL(1)] or [CuL(2)] with cobalt(II) perchlorate and sodium dicyanamide in methanol-water medium (where H2L(1) = N,N'-bis(salicylidene)-1,3-propanediamine and H2L(2) = N,N'-bis(α-methylsalicylidene)-1,3-propanediamine). The three complexes have been structurally and magnetically characterized. Complex 1 is a discrete trinuclear species in which two metallo-ligands coordinate to a cobalt(II) ion through the phenoxido oxygen atoms along with two terminally coordina…

Synthesis, crystal structure and magnetic properties of a new cyanide-bridged iron(III)–nickel(II) ferromagnetic chain

Abstract The reaction of the iron(III) unit fac-[Fe{HB(pz)3}(CN)3]− [ HB ( pz ) 3 - = hydrotris ( 1 - pyrazolyl ) borate ] as the lithium salt (1) with the nickel(II) complex mer-[Ni(dpt)(H2O)3](ClO4)2 [dpt = dipropylenetriamine] in water affords the heterometallic compound of formula {[FeIII{HB(pz)3}(CN)3]2[NiII(dpt)]}n · 3nH2O (2). The structure of 2 has been determined by X-ray diffraction on single crystals and their magnetic properties have been investigated in the temperature range 1.9–300 K. Compound 2 is a zigzag chain compound with regular alternating bis-monodentate [Fe(1){HB(pz)3}(CN)3]− units and [Ni(dpt)]2+ cations, the six coordination around the nickel atom being achieved by …

Electrically switchable magnetic exchange in the vibronic model of linear mixed valence triferrocenium complex

In this article, we report our development of a vibronic model for the electric-field control of antiferromagnetic superexchange in the mixed-valence (MV) triferrocenium complex FeIII-FeII-FeIII proposed as a possible candidate for the molecular implementation of a quantum logic gate. Along with the electronic interactions, such as electron transfer between the iron ions in different oxidation degrees and Coulomb repulsion of the extra holes, the proposed model of the triferrocenium complex also takes into account the vibronic coupling as an inherent ingredient of the problem of mixed valency. The latter is described by the conventional Piepho-Krauzs-Shatz (PKS) model adapted to the linear …

Electric field controllable magnetic coupling of localized spins mediated by itinerant electrons: a toy model

In this paper, we propose a toy model to describe the magnetic coupling between the localized spins mediated by the itinerant electron in partially delocalized mixed-valence (MV) systems. This minimal model takes into account the key interactions that are common for all such systems, namely, electron transfer in the valence-delocalized moiety and magnetic exchange between the localized spins and the delocalized electrons. The proposed descriptive model is exactly solvable which allows us to qualitatively and quantitatively discuss the main features of the whole class of partially delocalized MV systems. In the case of relatively strong exchange coupling, the combined action of these two int…

A Diferrous Single‐Molecule Magnet

The diferrous complex [Fe2(acpypentO)(NCO)3] (1),(acpypentO– = the anion of 1,5-bis[2-pyridyl(1-ethylimino)]pentane-3-ol) was studied by spectroscopic (dual-mode X-band EPR and 57Fe-Mossbauer) and magnetic (AC magnetic susceptibility) techniques. Complex 1 (A. K. Boudalis et al., Inorg. Chem.2004, 43, 1574) was previously shown to exhibit an intramolecular ferromagnetic coupling with important single-ion anisotropies with marked differences in the single-ion electronic parameters of the two iron sites. In this contribution, additional studies are carried out to probe its dynamic magnetic properties. Mossbauer spectra recorded at liquid helium temperatures indicate slow paramagnetic relaxati…

Hexanuclear iron(III) salicylaldoximato complexes presenting the [Fe6(mu3-O)2(mu2-OR)2]12+ core: syntheses, crystal structures, and spectroscopic and magnetic characterization.

The use of salicylaldehyde oxime (H2salox) in iron(III) carboxylate chemistry has yielded two new hexanuclear compounds [Fe6(mu3-O)2(O2CPh)10(salox)2(L)2].xMeCN.yH2O [L = MeCONH2, x = 6, y = 0 (1); L = H2O, x = 2, y = 3 (2)]. Compound 1 crystallizes in the triclinic space group P with (at 25 degrees C) a = 13.210(8) A, b = 13.87(1) A, c = 17.04(1) A, alpha = 105.79(2) degrees , beta = 96.72(2) degrees , gamma = 116.69(2) degrees , V = 2578.17(2) A(3), and Z = 1. Compound 2 crystallizes in the monoclinic space group C2/c with (at 25 degrees C) a = 21.81(1) A, b = 17.93(1) A, c = 27.72(1) A, beta = 111.70(2) degrees , V = 10070(10) A(3), and Z = 4. Complexes 1 and 2 contain the [Fe6(mu3-O)2(m…

Construction of a General Library for the Rational Design of Nanomagnets and Spin Qubits Based on Mononuclear f-Block Complexes. The Polyoxometalate Case

This paper belongs to a series of contributions aiming at establishing a general library that helps in the description of the crystal field (CF) effect of any ligand on the splitting of the J ground states of mononuclear f-element complexes. Here, the effective parameters associated with the oxo ligands (effective charges and metal-ligand distances) are extracted from the study of the magnetic properties of the first two families of single-ion magnets based on lanthanoid polyoxometalates (POMs), formulated as [Ln(W5O18)2](9-) and [Ln(β2-SiW11O39)2](13-) (Ln = Tb, Dy, Ho, Er, Tm, Yb). This effective CF approach provides a good description of the lowest-lying magnetic levels and the associate…

Electron delocalization in mixed-valence Keggin polyoxometalates. Ab initio calculation of the local effective transfer integrals and its consequences on the spin coupling.

We present a quantitative evaluation of the influence of the electron transfer on the magnetic properties of mixed-valence polyoxometalates reduced by two electrons. For that purpose, we extract from valence-spectroscopy ab initio calculations on embedded fragments the value of the transfer integrals between W nearest-neighbor atoms in a mixed-valence alphaPW(12)O(40) polyoxowolframate Keggin anion. In contradiction with what is usually assumed, we show that the electron transfer between edge-sharing and corner-sharing WO(6) octahedra have very close values. Considering fragments of various ranges, we analyze the accuracy of calculations on fragments based on only two WO(5) pyramids which s…

Vibronic Model for Intercommunication of Localized Spins via Itinerant Electron

In this article, we propose a vibronic pseudo Jahn–Teller model for partially delocalized mixed-valence molecules aimed to describe the magnetic coupling between the localized spins mediated by the delocalized electron. The simplest partially delocalized system that retains the main studied features is assumed to consist of a one-electron mixed-valence dimer, which is connected to the two terminal magnetic ions. The model involves the following key interactions: electron transfer in the spin-delocalized subsystem of a mixed-valence molecule, which is mimicked by a dimeric unit, coupling of the itinerant electrons with the molecular vibrations, and isotropic magnetic exchange between the loc…

Modeling the properties of uranium-based single ion magnets

We analyze the magnetic behavior of the five uranium-based SIMs reported in the literature. By combining a corrected crystal field model with the magnetic experimental data, we obtain the lowest-lying magnetic levels and the associated wave functions of the nanomagnets, which are found to be compatible with the observed SMM behavior. Additionally, this approach has allowed us to propose some geometrical considerations and practical advice for experimentalists aiming for the rational design of SIMs and spin qubits based on uranium.

Synthese, Struktur und magnetische Eigenschaften eines achtkernigen Nickel(II)-Komplexes mit einer zentralenhexahedro-Ni8-Einheit

Magnetic Properties of Mixed-Valence Clusters: Theoretical Approaches and Applications

Magnetic Excitations in Polyoxometalate Clusters Observed by Inelastic Neutron Scattering:  Evidence for Anisotropic Ferromagnetic Exchange Interactions in the Tetrameric Cobalt(II) Cluster [Co4(H2O)2(PW9O34)2]10-. Comparison with the Magnetic and Specific Heat Properties

The ground-state properties of the tetranuclear Co2+ cluster [Co4(H2O)2(PW9O34)2]10- were investigated by combining specific heat, magnetic susceptibility, and magnetization measurements with a detailed inelastic neutron scattering (INS) study on a fully deuterated sample of K10[Co4(H2O)2(PW9O34)2]·22H2O. As a result of the single ion anisotropy of the octahedral Co2+, the appropriate exchange Hamiltonian of the Co4 spin cluster is anisotropic. INS turns out to be essential for the determination of energy splittings in the ground state resulting from the coupling. Besides the energy pattern, INS provides information about the wave functions of the split ground-state components of the spin c…

Electric field control of the optical properties in magnetic mixed-valence molecules

We propose the use of an electric field stimulus to strongly affect the optical properties of ferromagnetic mixed-valence (MV) dimers. This proposal is based on the prediction of an anomalous Stark effect in the intervalence absorption bands of these multi-electron MV systems. As distinguished from the conventional Stark effect observed in one-electron dimers, a strong change of the intervalence bands accompanies the crossing of the different spin levels caused by the application of an electric field. This new effect can be referred to as giant spin-dependent Stark effect. In spintronics this opens up the possibility for optical detection of the spin state in these magnetic molecules.

Magnetic exchange interaction in clusters of orbitally degenerate ions. II. Application of the irreducible tensor operator technique

Abstract The irreducible tensor operator technique in R3 group is applied to the problem of kinetic exchange between transition metal ions possessing orbitally degenerate ground states in the local octahedral surrounding. Along with the effective exchange Hamiltonian, the related interactions (low-symmetry crystal field terms, Coulomb interaction between unfilled electronic shells, spin–orbit coupling and Zeeman interaction) are also taken into account within a unified computational scheme. Extension of this approach to high-nuclearity systems consisting of transition metal ions in the orbital triplet ground states is also demonstrated. As illustrative examples, the corner-shared D4h dimers…

Mononuclear lanthanide single molecule magnets based on the polyoxometalates [Ln(W5O18)2]9- and [Ln(beta2-SiW11O39)2]13- (Ln(III) = Tb, Dy, Ho, Er, Tm, and Yb).

The first two families of polyoxometalate-based single-molecule magnets (SMMs) are reported here. Compounds of the general formula [Ln(W(5)O(18))(2)](9-) (Ln(III) = Tb, Dy, Ho, and Er) and [Ln(SiW(11)O(39))(2)](13-) (Ln(III) = Tb, Dy, Ho, Er, Tm, and Yb) have been magnetically characterized with static and dynamic measurements. Slow relaxation of the magnetization, typically associated with SMM-like behavior, was observed for [Ln(W(5)O(18))(2)](9-) (Ln(III) = Ho and Er) and [Ln(SiW(11)O(39))(2)](13-) (Ln(III) = Dy, Ho, Er, and Yb). Among them, only the [Er(W(5)O(18))(2)](9-) derivative exhibited such a behavior above 2 K with an energy barrier for the reversal of the magnetization of 55 K. …

SIMPRE1.2: Considering the hyperfine and quadrupolar couplings and the nuclear spin bath decoherence

SIMPRE is a fortran77code which uses an effective electrostatic model of point charges to predict the magnetic behavior of rare-earth-based mononuclear complexes. In this manuscript, we present SIMPRE1.2, which now takes into account two further phenomena.Firstly, SIMPRE now considers the hyperfine and quadrupolar interactions within the rare-earth ion, resulting in a more complete and realistic set of energy levels and wave functions. Secondly,and in order to widen SIMPRE’s predictive capabilities regarding potential molecular spin qubits, it now includes a routine that calculates an upper-bound estimate of the decoherence time considering only the dipolar coupling between the electron spi…

Gd-based single-ion magnets with tunable magnetic anisotropy: Molecular design of spin qubits

et al.

Supramolecular diversity and magnetic properties of novel heterometallic Cu(II)/Cr(III) complexes prepared from copper powder, Reineckes salt and ethylenediamine

Abstract Three novel heterometallic complexes [Cu(en) 2 Cr(NCS) 4 (NH 3 ) 2 ][Cr(NCS) 4 (NH 3 ) 2 ] · 6dmf ( 1 ), [Cu(en) 2 Cr(NCS) 4 (NH 3 ) 2 ](OAc) ( 2 ) and [{Cu(en) 2 } 3 {Cr(NCS) 4 (NH 3 ) 2 } 2 (NCS) 2 ](NCS) 2 ( 3 ) have been synthesized in a one-pot reaction from copper powder, Reineckes salt, NH 4 X [X −  = OAc − ( 2 ), NCS − ( 3 )] in a dmf ( 1 ) or CH 3 CN ( 2 , 3 ) solution of ethylenediamine (en). X-ray studies showed that 1 and 2 consist of cationic polymeric chains, formed by Cu ( en ) 2 2 + and Cr ( NCS ) 4 ( NH 3 ) 2 - building blocks that bridged through thiocyanate anions. In both complexes, distinct hydrogen bonds are present and serve to increase the dimensionality of …

Metal Phosphonates Based on {[(Benzimidazol‐2‐ylmethyl)imino]bis(methylene)}bis(phosphonic Acid): Syntheses, Structures and Magnetic Properties of the Chain Compounds [M{(C 7 H 5 N 2 )CH 2 N(CH 2 PO 3 H) 2 }](M = Mn, Fe, Co, Cu, Cd)

Five compounds based on {[(benzimidazol-2-ylmethyl)imino]bis(methylene)}bis(phosphonic acid) [(C7H5N2)CH2N(CH2PO3H2)2], namely [M{(C7H5N2)CH2N(CH2PO3H)2}] [M = Mn (1), Fe (2), Co (3), Cu (4), Cd (5)] have been synthesized under hydrothermal conditions. These compounds are isostructural, crystallizing in the orthorhombic space group Pbca, with a = 15.331(2), b = 10.7150(16), and c = 16.715(2) A for 1; a = 15.320(3), b = 10.477(2), and c = 16.764(3) A for 2; a = 15.207(2), b = 10.4626(16), and c = 16.794(3) A for 3; a = 15.101(3), b = 10.3517(17), and c = 16.997(3) A for 4; and a = 15.4679(19), b = 10.8923(13), and c = 16.6175(19) for 5. Each compound shows a one-dimensional chain structure w…

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.

Electronic and vibronic problems of nanosized mixed valence clusters: Advances and challenges

Here we discuss the electronic and vibronic problems of mixed valency (MV) in molecular clusters which are of current interest in areas as diverse as solid-state chemistry, biochemistry, and molecular magnetism. Modern research in these areas is focused on the nanosized clusters at the border between classical and quantum scales and for this reason they are particularly difficult to study. First, we describe a general approach to the evaluation of the energy pattern of MV systems containing arbitrary number of localized spins and itinerant electrons with due account for the double exchange and other relevant interactions, like interelectronic Coulomb repulsion in instantly localized configu…

Toward multifunctional molecular cells for quantum cellular automata: exploitation of interconnected charge and spin degrees of freedom

We discuss the possibility of using mixed-valence (MV) dimers comprising paramagnetic metal ions as molecular cells for quantum cellular automata (QCA). Thus, we propose to combine the underlying idea behind the functionality of QCA of using the charge distributions to encode binary information with the additional functional options provided by the spin degrees of freedom. The multifunctional ('smart') cell is supposed to consist of multielectron MV d(n)-d(n+1)-type (1 ≤ n ≤ 8) dimers of transition metal ions as building blocks for composing bi-dimeric square planar cells for QCA. The theoretical model of such a cell involves the double exchange (DE), Heisenberg-Dirac-Van Vleck (HDVV) excha…

Structural and magnetic studies of tetranuclear heterometallic M/Cr (M = Co, Mn) complexes self-assembled from zerovalent cobalt or manganese, Reineckes salt and diethanolamine

Abstract Four novel heterometallic complexes [Co2Cr2(NCS)4(HDea)2(Dea)2]·4dmf (1), [Co2Cr2(NCS)4(HDea)2(Dea)2]·4dmso (2), [Mn2Cr2(NCS)4(HDea)2(Dea)2(dmf)2]·2dmf (3) and [Mn2Cr2(NCS)4(HDea)2(Dea)2(dmso)2]·4dmso (4) have been prepared using zerovalent cobalt (1, 2) or manganese (3, 4), Reineckes salt, ammonium thiocyanate and a non-aqueous solution of diethanolamine (H2Dea) in air. The single X-ray analysis reveals that all compounds have similar centrosymmetric crystal structures based on a tetranuclear {M2Cr2(μ3-O)2(μ-O)4} (M = Co, Mn) core. Variable-temperature magnetic susceptibility measurements of 1, 2 and 4 show antiferromagnetic coupling between the magnetic centers, while 3 exhibits …

A symmetry adapted approach to the dynamic Jahn-Teller problem: Application to mixed-valence polyoxometalate clusters with keggin structure

In this article, we present a symmetry-adapted approach aimed to the accurate solution of the dynamic vibronic problem in large scale Jahn-Teller (JT) systems. The algorithm for the solution of the eigen-problem takes full advantage of the point symmetry arguments. The system under consideration is supposed to consist of a set of electronic levels mixed by the active JT and pseudo JT vibrational modes. Applying the successive coupling of the bosonic creation operators, we introduce the irreducible tensors that are called multivibronic operators. Action of the irreducible multivibronic operators on the vacuum state creates the vibrational symmetry adapted basis that is subjected to the Gram-…

Magnetic exchange between metal ions with unquenched orbital angular momenta: basic concepts and relevance to molecular magnetism

This review article is a first attempt to give a systematic and comprehensive description (in the framework of the unified theoretical approach) of the exchange interactions in polynuclear systems based on orbitally degenerate metal ions in the context of their relevance to the modern molecular magnetism. Interest in these systems is related to the fundamental problems of magnetism and at the same time steered by a number of impressive potential applications of molecular magnets, like high-density memory storage units, nanoscale qubits, spintronics and photoswitchable devices. In the presence of orbital degeneracy, the conventional spin Hamiltonian (Heisenberg–Dirac–van Vleck model) becomes…

Quantum Cellular Automata: a Short Overview of Molecular Problem

International audience

Breathing effect in a cobalt phosphonate upon dehydration/rehydration: a single-crystal-to-single-crystal study.

Two cobalt phosphonates, [Co2(2,2′-bpy)2(H2O)(pbtcH)] (1) and [Co2(H2O)(pbtcH)(phen)2] (2; pbtcH5=5-phosphonatophenyl-1,2,4-tricarboxylic acid, 2,2′-bpy=2,2′-bipyridine, phen=1,10-phenanthroline), with layer structures are reported. Compound 1 contains O-C-O and O-P-O bridged tetramers of Co4, which are further connected by pbtcH(4-) units to form a layer. In compound 2, the cobalt tetramers made up of water-bridged Co2 dimers and O-P-O linkages are connected into a layer by pbtcH(4-) units. Upon dehydration, compounds 1 and 2 experience single-crystal-to-single-crystal (SC-SC) structural transformations to form [Co2(2,2′-bpy)2(pbtcH)] (1 a) and [Co2(pbtcH)(phen)2] (2 a), respectively. The …

Magnetic polyoxometalates: from molecular magnetism to molecular spintronics and quantum computing.

In this review we discuss the relevance of polyoxometalate (POM) chemistry to provide model objects in molecular magnetism. We present several potential applications in nanomagnetism, in particular, in molecular spintronics and quantum computing.

Coherent Manipulation of Polarization in Mixed-Valence Compounds by Electric Pulse via Landau–Zener Transitions

In this contribution, we predict and theoretically investigate the effects of the electric field pulse in mixed valence (MV) dimers. These systems exhibit bistability with a large internal dipole moment mediated by the itinerant electron trapped by the vibronic coupling. In this sense, they are similar to single molecular magnets (SMMs) that are bistable systems possessing large long-living magnetization and exhibiting Landau−Zener (LZ) transitions. We propose a scheme for a controllable LZ tunnelling in MV systems that provides also a possibility to control the dipole moment of a dimeric MV unit. It is supposed that the static electric field initially polarizes the system, and then the uni…

A rare polymeric azido-bridged copper(II) chain with a pentameric repeating unit: Synthesis, structure and magnetic properties

International audience; The novel polymeric chain copper(II) complex [Cu4(μ-Mesalpn)2(μ1,1,1-N3)2(μ1,1-N3)2Cu]n (1) was prepared by the reaction of Cu(NO3)2·3H2O with Mesalpn in the presence of an excess of NaN3. A single-crystal X-ray diffraction study showed an unusual 1D polymeric chain based on pentanuclear Cu5 units with both μ1,1,1-N3 and μ1,1-N3 bridges, and with three independent Cu(II) ions presenting three different coordination numbers (4, 5 and 6). The magnetic susceptibility data show the presence of dominant anti-ferromagnetic interactions.

Modeling the properties of lanthanoid single-ion magnets using an effective point-charge approach

Herein, we present two geometrical models based on an effective point-charge approach to provide a full description of the lowest sublevels in lanthanoid single ion magnets (SIMs). The first one, named as the Radial Effective Charge (REC) model, evaluates the crystal field effect of spherical ligands, e.g. F(-), Cl(-) or Br(-), by placing the effective charge along the Ln-ligand axes. In this case the REC parameters are obtained fitting high-resolution spectroscopic data for lanthanoid halides. The second model, named as the Lone Pair Effective Charge (LPEC) model, has been developed in order to provide a realistic description of systems in which the lone pairs are not pointing directly tow…

Alternating antiferromagnetic and ferromagnetic exchange interactions in the S = 1 Heisenberg chain. Theory and magnetic properties

Abstract We focus on the magnetic properties of the S = 1 Heisenberg chain with alternating antiferromagnetic and ferromagnetic exchange interactions J 1 and J 2 . The magnetic behavior of this system is calculated as a function of the alternation parameter α = J 2 /| J 1 |, from a general numerical procedure based on closed spin chains of increasing length. These theoretical results are fitted to rational unified expressions, which are subsequently used to describe the magnetic behavior of a nickel (II) complex, [Ni(bipy)(N 3 ) 2 ] n , exhibiting an alternating chain structure with a dominant ferromagnetic exchange.

Synthesis, Crystal Structure, Thermal Analysis and Magnetic Behavior of a Novel One‐Dimensional Polymeric Pyridinium Chlorocuprate( II ): (Hpy) 2 [Cu 3 Cl 8 (H 2 O) 2 ]

A one-dimensional polymeric pyridinium chlorocuprate (HPy)2[Cu3Cl8(H2O)2], an intermediate between (HPy)CuCl3 and CuCl2·2H2O, has been synthesized and characterized by X-ray analysis [monoclinic, P21/c, a = 7.8950(10), b = 14.144(2), c = 9.921(10) A, β = 99.20(2)°]. The structure contains [Cu3Cl8(H2O)2]n2n− chains in which both square-pyramidal and octahedral CuII exist. The chains are composed of linked [Cu2Cl6]2− dimers and CuCl2(H2O)2 monomeric units. On being heated in the solid state the compound undergoes dehydration followed by dehydrohalogenation to produce a pyridine complex of CuII: [Cu3Py2Cl6]. Other compounds, (HPy)2[CuCl4], CuPyCl2 and CuPy2Cl2, also produce [Cu3Py2Cl6] as an i…

Electrically switchable magnetic molecules: inducing a magnetic coupling by means of an external electric field in a mixed-valence polyoxovanadate cluster.

International audience; Herein we evaluate the influence of an electric field on the coupling of two delocalized electrons in the mixed-valence polyoxometalate (POM) [GeV14 O40 ](8-) (in short V14 ) by using both a t-J model Hamiltonian and DFT calculations. In absence of an electric field the compound is paramagnetic, because the two electrons are localized on different parts of the POM. When an electric field is applied, an abrupt change of the magnetic coupling between the two delocalized electrons can be induced. Indeed, the field forces the two electrons to localize on nearest-neighbors metal centers, leading to a very strong antiferromagnetic coupling. Both theoretical approaches have…

Exploration of the double exchange in quantum cellular automata: proposal for a new class of cells

In this communication we propose to considerably extend the class of systems suitable as cells for quantum cellular automata by including magnetic quantum dots and molecular mixed valence dimers exhibiting double exchange. As distinguished from the previous works we propose to use not only charges as the information carriers but also spin degrees of freedom. In this context we focus on the two key points: (1) properties of the magnetic cell as reservoir for charges carrying binary information, and (2) identification of conditions under which spin degrees of freedom can be employed.

Spin-lattice relaxation via quantum tunneling in anEr3+-polyoxometalate molecular magnet

We investigate the mechanism of spin-lattice relaxation of Er ions encapsulated in polyoxometalate clusters, which below 4 K can only reverse its spin via quantum tunneling processes. The temperature-independent rate −1 is, at zero field, ten orders of magnitude larger than the rates predicted for direct phonon-induced processes. In addition, we observe that −1 is suppressed by external magnetic bias and hyperfine interactions but enhanced by increasing the concentration of Er ions. The observed relaxation agrees with predictions for pure quantum tunneling, showing that this phenomenon drives the thermalization of electronic spins. A possible link between these two phenomena is discussed, i…

Cobalt Clusters with Cubane-Type Topologies Based on Trivacant Polyoxometalate Ligands.

Four novel cobalt-substituted polyoxometalates having cobalt cores exhibiting cubane or dicubane topologies have been synthesized and characterized by IR, elemental analysis, electrochemistry, UV-vis spectroscopy, X-ray single-crystal analysis, and magnetic studies. The tetracobalt(II)-substituted polyoxometalate [Co4(OH)3(H2O)6(PW9O34)](4-) (1) consists of a trilacunary [B-α-PW9O34](9-) unit which accommodates a cubane-like {Co(II)4O4} core. In the heptacobalt(II,III)-containing polyoxometalates [Co7(OH)6(H2O)6(PW9O34)2](9-) (2), [Co7(OH)6(H2O)4(PW9O34)2]n(9n-) (3), and [Co7(OH)6(H2O)6(P2W15O56)2](15-) (4), dicubane-like {Co(II)6Co(III)O8} cores are encapsulated between two heptadentate [B…

Kinetic exchange Hamiltonian for orbitally degenerate ions

Abstract A new approach to the problem of the kinetic exchange for orbitally degenerate ions is developed. The highly anisotropic effective Hamiltonian is expressed in terms of unit irreducible tensor operators and spin operators. All parameters of the exchange Hamiltonian are expressed through relevant transfer integrals, crystal field and Racah parameters for the metal ions. As an example the edge-shared ( D 2 h ) bioctahedral cluster is discussed and some comments on the considerations of Anderson, Goodenough and Kanamori and McConnell are given.

A Symmetry Adapted Approach to the Dynamic Jahn-Teller Problem

In this article we present a symmetry-adapted approach aimed to the accurate solution of the dynamic Jahn-Teller (JT) problem. The algorithm for the solution of the eigen-problem takes full advantage of the point symmetry arguments. The system under consideration is supposed to consist of a set of electronic levels \({\Gamma }_{1},{\Gamma }_{2}\ldots {\Gamma }_{n}\) labeled by the irreducible representations (irreps) of the actual point group, mixed by the active JT and pseudo JT vibrational modes \({\Gamma }_{1},{\Gamma }_{2}\ldots {\Gamma }_{f}\) (vibrational irreps). The bosonic creation operators b +(Γγ) are transformed as components γ of the vibrational irrep Γ. The first excited vibra…

Antisymmetric exchange in triangular tricopper(II) complexes: correlation among structural, magnetic, and electron paramagnetic resonance parameters.

Two new trinuclear copper(II) complexes, [Cu(3)(μ(3)-OH)(daat)(Hdat)(2)(ClO(4))(2)(H(2)O)(3)](ClO(4))(2)·2H(2)O (1) and [Cu(3)(μ(3)-OH)(aaat)(3)(H(2)O)(3)](ClO(4))(2)·3H(2)O (2) (daat = 3,5-diacetylamino-1,2,4-triazolate, Hdat = 3,5-diamino-1,2,4-triazole, and aaat = 3-acetylamino-5-amino-1,2,4-triazolate), have been prepared from 1,2,4-triazole derivatives and structurally characterized by X-ray crystallography. The structures of 1 and 2 consist of cationic trinuclear copper(II) complexes with a Cu(3)OH core held by three N,N-triazole bridges between each pair of copper(II) atoms. The copper atoms are five-coordinate with distorted square-pyramidal geometries. The magnetic properties of 1 …

Synthesis, Structure, Spectroscopic Studies and Magnetic Properties of the Tetrakis(5,7‐dichloro‐8‐quinolinolato)gadolinium(III) Complex

The synthesis and structural characterization of the neutral gadolinium tetrakis-type complex with 5,7-dichloro-8-quinolinolato (H5,7ClQ) ligands, [Gd(5,7ClQ)2(H5,7ClQ)2Cl], is reported. The GdIII ion is epta coordinated to one chloride ion and to four ligands: two N,O-chelated monoanions and two as zwitterionic (+NH and O–) monodentate oxygen donors. Electronic and vibrational spectra provide suitable markers to distinguish the presence of deprotonated and protonated ligands. The magnetic behaviour of this compound was investigated and explained by taking into account that π–π stacking interactions between the (H5,7ClQ) ligands give rise to a ferromagnetic interaction between the gadoliniu…

Poly(polyoxotungstate)s with 20 Nickel Centers: From Nanoclusters to One-Dimensional Chains

A Nonanuclear Iron(II) Single-Molecule Magnet

Copper-, cobalt-, and manganese-containing 17-tungsto-2-germanates.

The sandwich-type tungstogermanates [Cu(3)(H(2)O)(B-beta-GeW(9)O(33)(OH))(B-beta-GeW(8)O(30)(OH))](12-) (1), [Co(H(2)O)(2){Co(3)(B-beta-GeW(9)O(33)(OH))(B-beta-GeW(8)O(30)(OH))}(2)](22-) (2), and [Mn(H(2)O)(2){Mn(3)(H(2)O)(B-beta-GeW(9)O(33)(OH))(B-beta-GeW(8)O(30)(OH))}(2)](22-) (3) were synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, thermogravimetric analysis, and infrared spectroscopy. Polyanion 1 is composed of two nonequivalent Keggin units, (B-beta-GeW(8)O(31)) and (B-beta-GeW(9)O(34)), linked to each other via three copper(II) ions in such a way that there is a plane of symmetry passing through both Ge atoms and the unique Cu atom, resulting in…

Synthesis, Crystal Structure, and Magnetic Properties of an Octanuclear Nickel(II) Complex with ahexahedro-Ni8 Core

A ferromagnetic tetranuclear nickel(II) Schiff-base complex with an asymmetric Ni4O4 cubane core

Abstract The ferromagnetic tetranuclear nickel(II) complex [Ni4(L)4(CH3OH)2]·2MeOH·8H2O (1) has been synthesized by reacting nickel nitrate hexahydrate with the Schiff base ligand H2L (H2L = N-(2-hydroxyphenyl)-3-methoxy-salicylideneamine). Complex 1 was characterized by analytical, thermogravimetric, optical and magnetic techniques. The solid state structure of 1 was established by single crystal X-ray diffraction analysis. Crystal structure determination shows the formation of a distorted Ni4O4 cubane moiety encapsulated by four Schiff base ligands. Compound 1 crystallizes in the triclinic space group P 1 ¯ with a = 12.7624(9) A, b = 15.0477(9) A, c = 16.8589(10) A, α = 94.732(2)°, β = 94…

A Comparative Structural and Magnetic Study of Three Compounds Based on the Cluster Unit M4Cl8(THF)6 (M=Mn, Fe, Co)

Treatment of anhydrous M Cl 2 phases with THF under refluxing conditions leads to excision of the clusters M 4 Cl 8 (THF) 6 ( M =Fe (1), Co (3)) and dimensional reduction to the chain of clusters, {Mn 4 Cl 8 (THF) 6 (Mn(THF) 2 Cl 2 } ∞ , (2). All three compounds were isolated in high yields as crystalline materials and subjected to comprehensive magnetic studies. X-ray structures of the three compounds were performed to verify the nature of the compounds, but only the Mn derivative is discussed in detail due to the fact that the structures of the Fe and Co clusters were reported earlier. The molecular structures of M 4 Cl 8 (THF) 6 ( M =Fe, Co) consist of a rhombic arrrangement of metal ion…

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 …

Role of Orbital Degeneracy in the Single Molecule Magnet Behavior of a Mononuclear High-Spin Fe(II) Complex

To explain the single-molecule magnet behavior of the mononuclear complex [(tpaMes)Fe](-) we have developed a model that takes into account the trigonal ligand field splitting of the atomic (5)D term of the Fe(II) ion, and the spin-orbital splitting and mixing of the ligand field terms. The ground ligand field term is shown to be the orbital doublet (5)E possessing an unquenched orbital angular momentum. We demonstrate that the splitting of this term cannot be described by the conventional zero-field splitting Hamiltonian proving thus the irrelevance of the spin-Hamiltonian formalism in the present case. The first-order orbital angular momentum is shown to lead to the strong magnetic anisot…

Cobalt-Containing Silicotungstate Sandwich Dimer [{Co3(B-β-SiW9O33(OH))(B-β-SiW8O29(OH)2)}2]22-

The 6-cobalt-substituted [{Co3(B-beta-SiW9O33(OH))(B-beta-SiW8O29(OH)2)}2]22- has been characterized by IR and UV-vis spectroscopy, elemental analysis, magnetic studies, electrochemistry, and gel filtration chromatography. A single-crystal X-ray analysis was carried out on K10Na12[{Co3(B-beta-SiW9O33(OH))(B-beta-SiW8O29(OH)2)}2].49H2O (KNa-1), which crystallizes in the monoclinic system, space group P2(1)/n, with a=19.9466(8) A, b=24.6607(10) A, c=34.0978(13) A, beta=102.175(1) degrees, and Z=2. Polyanion 1 represents a novel class of asymmetric sandwich-type polyanions. It contains three cobalt ions, which are encapsulated between an unprecedented (B-beta-SiW9O34) fragment and a (B-beta-Si…

Magnetic polyoxometalates: anisotropic exchange interactions in the moiety of [(NaOH2)Co3(H2O)(P2W15O56)2]17-.

The magnetic exchange interactions in a C0(3)(11) moiety encapsulated in Na(17) [(NaOH(2))Co(3)(H(2)O)(P(2)W(15)O(56))(2)] (NaCo(3)) were studied by a combination of magnetic measurements (magnetic susceptibility and low-temperature magnetization), with a detailed Inelastic Neutron Scattering (INS) investigation. The novel structure of the salt was determined by X-ray crystallography. The ferromagnetic Co(3)O(14) triangular cluster core consists of three octahedrally oxo-coordinated Co(II) ions sharing edges. According to the single-ion anisotropy and spin-orbit coupling usually assumed for octahedral Co(II) ions, the appropiate exchange Hamiltonian to describe the ground-state properties o…

High-nuclearity Ni-substituted polyoxometalates: a series of poly(polyoxotungstate)s containing 20–22 nickel centers.

Three high-nuclearity Ni-substituted polyoxotungstates (POTs)--[Ni(enMe)2(H2O)2]2[Ni(H2O)6]2[Ni(enMe)2][Ni(H2O)2]1.5[HNi20X4W34(OH)4O136(H2O)6(enMe)8]·11 H2O (3), [Ni(en)2(H2O)]2[H8Ni21X4W34(OH)4O136(en)10(H2O)5]·22 H2O (4), and [Ni(enMe)2]2[H6Ni22X4W34(OH)4O136(H2O)6(enMe)10]·18 H2O (5), in which en = ethylenediamine, enMe = 1,2-diaminopropane, X = 0.5 P+0.5 Ge--were made under hydrothermal conditions and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. The structures of 3–5 can be viewed as novel derivatives of [H6Ni20P4W34(OH)4O136(enMe)8(H2O)6]·12 H 2O (1) and [Ni(en)2(H2O)]2[H8Ni20P4W34(OH)…

Molecular analog of multiferroics: Electric and magnetic field effects in many-electron mixed-valence dimers

We show here that mixed-valence (MV) magnetic molecules with a significant electron delocalization are extremely sensitive to an external electric field. In particular, we focus on the symmetric many-electron MV binuclear complexes that are on the borderline between Robin and Day classes II and III. In these molecules, the double-exchange, which has been shown to lead to the ferromagnetic ground spin state, competes with the electric field, which tends to localize the spin, thus creating an electric dipole and stabilizing the spin states with lower multiplicities. This provides an efficient and easy way to control the ground spin state of the molecule through the double-exchange mechanism. …

Magnetic exchange interaction in clusters of orbitally degenerate ions. I. Effective Hamiltonian

Abstract A new effective Hamiltonian is reported for the kinetic exchange between two arbitrary terms 2S A +1 Λ A and 2S B +1 Λ B that can be ground or excited in octahedrally coordinated transition metal ions. This Hamiltonian is applicable to both homo- and heterometallic clusters. For the homonuclear cluster the resonance part of the effective Hamiltonian is also presented for the case when one of the ions is excited. The operator part of the exchange Hamiltonian contains symmetry adapted products of the cubic irreducible tensors acting in orbital spaces ΛA and ΛB and scalar product of site spin operators. The parameters of the Hamiltonian are defined by the relevant intercenter transfer…

Quantum Error Correction with magnetic molecules

Quantum algorithms often assume independent spin qubits to produce trivial $|\uparrow\rangle=|0\rangle$, $|\downarrow\rangle=|1\rangle$ mappings. This can be unrealistic in many solid-state implementations with sizeable magnetic interactions. Here we show that the lower part of the spectrum of a molecule containing three exchange-coupled metal ions with $S=1/2$ and $I=1/2$ is equivalent to nine electron-nuclear qubits. We derive the relation between spin states and qubit states in reasonable parameter ranges for the rare earth $^{159}$Tb$^{3+}$ and for the transition metal Cu$^{2+}$, and study the possibility to implement Shor's Quantum Error Correction code on such a molecule. We also disc…

Electric Field Generation and Control of Bipartite Quantum Entanglement between Electronic Spins in Mixed Valence Polyoxovanadate [GeV14O40]8–

As part of the search for systems in which control of quantum entanglement can be achieved, here we consider the paramagnetic mixed valence polyoxometalate K2Na6[GeV14O40]·10H2O in which two electrons are delocalized over the 14 vanadium ions. Applying a homogeneous electric field can induce an antiferromagnetic coupling between the two delocalized electronic spins that behave independently in the absence of the field. On the basis of the proposed theoretical model, we show that the external field can be used to generate controllable quantum entanglement between the two electronic spins traveling over a vanadium network of mixed valence polyoxoanion [GeV14O40]8–. Within a simplified two-lev…

Orbitally dependent kinetic exchange in cobalt(II) pairs: origin of the magnetic anisotropy

Abstract A comprehensive theoretical study of the magnetic exchange between Co 2+ ions is reported. Using the microscopic background we deduce the general Hamiltonian for a corner-shared bioctahedral system involving kinetic exchange, spin–orbit coupling and low-symmetry local crystal field. This Hamiltonian acting within orbitally degenerate ground manifold 4 ( T 1g ) A ⊗ 4 ( T 1g ) B of the cobalt pair is expressed in terms of orbital and spin operators. We elucidate the major electronic factors controlling the exchange anisotropy in the Co(II) pairs. The degree of the magnetic anisotropy is shown to depend on the strength of the cubic crystal field and on the relative efficiency of two k…

Lanthanoid single-ion magnets based on polyoxometalates with a 5-fold symmetry: The series [LnP5W30O110]12– (Ln3+ = Tb, Dy, Ho, Er, Tm, and Yb)

A robust, stable and processable family of mononuclear lanthanoid complexes based on polyoxometalates (POMs) that exhibit single-molecule magnetic behavior is described here. Preyssler polyanions of general formula [LnP 5W 30O 110] 12- (Ln 3+ = Tb, Dy, Ho, Er, Tm, and Yb) have been characterized with static and dynamic magnetic measurements and heat capacity experiments. For the Dy and Ho derivatives, slow relaxation of the magnetization has been found. A simple interpretation of these properties is achieved by using crystal field theory. © 2012 American Chemical Society.

A family of enneanuclear iron(II) single-molecule magnets.

Complexes [Fe 9 (X) 2 -(02CMe)8{(2-py) 2 CO 2 } 4 ] (X - = OH (1), N 3 - (2), and NCO- (3)) have been prepared by a route previously employed for the synthesis of analogous Co 9 and Ni 9 complexes, involving hydroxide substitution by pseudohalides (N 3 - , NCO-). As indicated by DC magnetic susceptibility measurements, this substitution induced higher ferromagnetic couplings in complexes 2 and 3, leading to higher ground spin states compared to that of 1. Variable-field experiments have shown that the ground state is not well isolated from excited states, as a result of which it cannot be unambiguously determined. AC susceptometry has revealed out-of-phase signals, which suggests that these…

ChemInform Abstract: Lanthanoid Single-Ion Magnets Based on Polyoxometalates with a 5-Fold Symmetry: The Series [LnP5W30O110]12-(Ln3+: Tb, Dy, Ho, Er, Tm, and Yb).

The compounds K12LnP5W30O110 ·nH2O (Ln3+: Tb, Dy, Ho, Er, Tm, and Yb) are prepared from aqueous solutions of K12.5Na1.5 [NaP5W30O110] and LnCl3 (autoclave, 160 °C, 24 h) and characterized by static and dynamic magnetic measurements.

CCDC 1446096: Experimental Crystal Structure Determination

Related Article: José J. Baldoví, Yan Duan, Carlos Bustos, Salvador Cardona-Serra, Pierre Gouzerh, Richard Villanneau, Geoffrey Gontard, Juan M. Clemente-Juan, Alejandro Gaita-Ariño, Carlos Giménez-Saiz, Anna Proust, Eugenio Coronado|2016|Dalton Trans.|45|16653|doi:10.1039/C6DT02258H

CSD 1790045: Experimental Crystal Structure Determination

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CCDC 990028: Experimental Crystal Structure Determination

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CCDC 1538254: Experimental Crystal Structure Determination

Related Article: Yan Duan, Juan M. Clemente-Juan, Carlos Giménez-Saiz, Eugenio Coronado|2018|Frontiers in Chemistry|6|231|doi:10.3389/fchem.2018.00231

CCDC 1482838: Experimental Crystal Structure Determination

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CCDC 1446095: Experimental Crystal Structure Determination

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CCDC 1482841: Experimental Crystal Structure Determination

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CCDC 990027: Experimental Crystal Structure Determination

Related Article: Saptarshi Biswas, Carlos J. Gómez-García, Juan M. Clemente-Juan, Samia Benmansour, Ashutosh Ghosh|2014|Inorg.Chem.|53|2441|doi:10.1021/ic4023536

CCDC 912971: Experimental Crystal Structure Determination

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CCDC 1482842: Experimental Crystal Structure Determination

Related Article: José J. Baldoví, Yan Duan, Carlos Bustos, Salvador Cardona-Serra, Pierre Gouzerh, Richard Villanneau, Geoffrey Gontard, Juan M. Clemente-Juan, Alejandro Gaita-Ariño, Carlos Giménez-Saiz, Anna Proust, Eugenio Coronado|2016|Dalton Trans.|45|16653|doi:10.1039/C6DT02258H

CCDC 990029: Experimental Crystal Structure Determination

Related Article: Saptarshi Biswas, Carlos J. Gómez-García, Juan M. Clemente-Juan, Samia Benmansour, Ashutosh Ghosh|2014|Inorg.Chem.|53|2441|doi:10.1021/ic4023536

CCDC 1538255: Experimental Crystal Structure Determination

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CCDC 1446094: Experimental Crystal Structure Determination

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CCDC 1446097: Experimental Crystal Structure Determination

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CCDC 912969: Experimental Crystal Structure Determination

Related Article: Tao Zheng, Juan M. Clemente-Juan, Jing Ma, Lin Dong, Song-Song Bao, Jian Huang, Eugenio Coronado, Li-Min Zheng|2013|Chem.-Eur.J.|19|16394|doi:10.1002/chem.201302514

CCDC 1482839: Experimental Crystal Structure Determination

Related Article: José J. Baldoví, Yan Duan, Carlos Bustos, Salvador Cardona-Serra, Pierre Gouzerh, Richard Villanneau, Geoffrey Gontard, Juan M. Clemente-Juan, Alejandro Gaita-Ariño, Carlos Giménez-Saiz, Anna Proust, Eugenio Coronado|2016|Dalton Trans.|45|16653|doi:10.1039/C6DT02258H

CCDC 912972: Experimental Crystal Structure Determination

Related Article: Tao Zheng, Juan M. Clemente-Juan, Jing Ma, Lin Dong, Song-Song Bao, Jian Huang, Eugenio Coronado, Li-Min Zheng|2013|Chem.-Eur.J.|19|16394|doi:10.1002/chem.201302514

CCDC 1482840: Experimental Crystal Structure Determination

Related Article: José J. Baldoví, Yan Duan, Carlos Bustos, Salvador Cardona-Serra, Pierre Gouzerh, Richard Villanneau, Geoffrey Gontard, Juan M. Clemente-Juan, Alejandro Gaita-Ariño, Carlos Giménez-Saiz, Anna Proust, Eugenio Coronado|2016|Dalton Trans.|45|16653|doi:10.1039/C6DT02258H

CCDC 1446093: Experimental Crystal Structure Determination

Related Article: José J. Baldoví, Yan Duan, Carlos Bustos, Salvador Cardona-Serra, Pierre Gouzerh, Richard Villanneau, Geoffrey Gontard, Juan M. Clemente-Juan, Alejandro Gaita-Ariño, Carlos Giménez-Saiz, Anna Proust, Eugenio Coronado|2016|Dalton Trans.|45|16653|doi:10.1039/C6DT02258H

CSD 2075252: Experimental Crystal Structure Determination

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CCDC 1446092: Experimental Crystal Structure Determination

Related Article: José J. Baldoví, Yan Duan, Carlos Bustos, Salvador Cardona-Serra, Pierre Gouzerh, Richard Villanneau, Geoffrey Gontard, Juan M. Clemente-Juan, Alejandro Gaita-Ariño, Carlos Giménez-Saiz, Anna Proust, Eugenio Coronado|2016|Dalton Trans.|45|16653|doi:10.1039/C6DT02258H

CCDC 912970: Experimental Crystal Structure Determination

Related Article: Tao Zheng, Juan M. Clemente-Juan, Jing Ma, Lin Dong, Song-Song Bao, Jian Huang, Eugenio Coronado, Li-Min Zheng|2013|Chem.-Eur.J.|19|16394|doi:10.1002/chem.201302514

CSD 1790044: Experimental Crystal Structure Determination

Related Article: Yan Duan, João C. Waerenborgh, Juan M. Clemente-Juan, Carlos Giménez-Saiz, Eugenio Coronado|2017|Chemical Science|8|305|doi:10.1039/C6SC01919F

CCDC 1538253: Experimental Crystal Structure Determination

Related Article: Yan Duan, Juan M. Clemente-Juan, Carlos Giménez-Saiz, Eugenio Coronado|2018|Frontiers in Chemistry|6|231|doi:10.3389/fchem.2018.00231

CCDC 1538256: Experimental Crystal Structure Determination

Related Article: Yan Duan, Juan M. Clemente-Juan, Carlos Giménez-Saiz, Eugenio Coronado|2018|Frontiers in Chemistry|6|231|doi:10.3389/fchem.2018.00231

CCDC 912973: Experimental Crystal Structure Determination

Related Article: Tao Zheng, Juan M. Clemente-Juan, Jing Ma, Lin Dong, Song-Song Bao, Jian Huang, Eugenio Coronado, Li-Min Zheng|2013|Chem.-Eur.J.|19|16394|doi:10.1002/chem.201302514