Tetranuclear {CoII2CoIII2}, Octanuclear {CoII4CoIII4}, and Hexanuclear {CoIII3DyIII3} Pivalate Clusters: Synthesis, Magnetic Characterization, and Theoretical Modeling.

New tetranuclear and octanuclear mixed-valent cobalt(II/III) pivalate clusters, namely, [NaCo4(O2CCMe3)6(HO2CCMe3)2(teaH)2(N3)]·2H2O (in two polymorphic modifications, 1 and 1a) and [Co8(O2CCMe3)10(teaH)4(N3)](Me3CCO2)·MeCN·H2O (2) have been synthesized by ultrasonic treatment of a dinuclear cobalt(II) pivalate precursor with sodium azide and triethanolamine (teaH3) ligand in acetonitrile. The use of Dy(NO3)3·6H2O in a similar reaction led to the precipitation of a tetranuclear [NaCo4(O2CCMe3)4(teaH)2(N3)(NO3)2(H2O)2]·H2O (3) cluster and a heterometallic hexanuclear [Co3Dy3(OH)4(O2CCMe3)6(teaH)3(H2O)3](NO3)2·H2O (4) cluster. Single-crystal X-ray analysis showed that 1 (1a) and 3 consist of a tetranuclear pivalate/teaH3 mixed-ligand cluster [CoII2CoIII2(O2CCMe3)4(teaH)2(N3)]+ decorated with sodium pivalates [Na(O2CCMe3)2(HO2CCMe3)2]- (1 or 1a) or sodium nitrates [Na(NO3)2]- (3) to form a square-pyramidal assembly. In 2, the cationic [Co8(O2CCMe3)10(teaH)4(N3)]+ cluster comprises a mixed-valent {CoII4CoIII4} core encapsulated by an azide, 4 teaH2- alcoholamine ligands, and 10 bridging pivalates. Remarkably, in this core, the µ4-N3- ligand joins all four CoII atoms. The heterometallic hexanuclear compound 4 consists of a cationic [CoIII3DyIII3(OH)4(O2CCMe3)6(teaH)3(H2O)3]2+ cluster, two NO3- anions, and a crystallization water molecule. The arrangement of metal atoms in 4 can be approximated as the assembly of a smaller equilateral triangle defined by three Dy sites with a Dy···Dy distance of 3.9 Å and a larger triangle formed by Co sites [Co···Co, 6.1-6.2 Å]. The interpretation of the magnetic properties of clusters 2-4 was performed in the framework of theoretical models, taking into account the structural peculiarities of clusters and their energy spectra. The behavior of clusters 2 and 3 containing CoII ions with orbitally nondegenerate ground states is determined by the zero-field splitting of these states and Heisenberg exchange interaction between the ions. To get a good understanding of the observed magnetic behavior of cluster 4, we take into consideration the crystal fields acting on the DyIII ions, the ferromagnetic coupling of neighboring DyIII ions, and the intercluster antiferromagnetic exchange. For all examined clusters, the developed models describe well the observed temperature dependence of the magnetic susceptibility and the field dependence of magnetization. The computational results apparently show that in cluster 4 two DyIII ions with similar nearest surroundings demonstrate single-molecule-magnet (SMM) behavior, while the strong rhombicity of the ligand surrounding hinders the SMM behavior of the third DyIII ion.

Strong Direct Magnetic Coupling in a Dinuclear Co(II) Tetrazine Radical Single-Molecule Magnet.

The ligand-centered radical complex [(CoTPMA)2 -µ-bmtz(.-) ](O3 SCF3 )3 ⋅CH3 CN (bmtz=3,6-bis(2'-pyrimidyl)-1,2,4,5-tetrazine, TPMA=tris-(2-pyridylmethyl)amine) has been synthesized from the neutral bmtz precursor. Single-crystal X-ray diffraction studies have confirmed the presence of the ligand-centered radical. The Co(II) complex exhibits slow paramagnetic relaxation in an applied DC field with a barrier to spin reversal of 39 K. This behavior is a result of strong antiferromagnetic metal-radical coupling combined with positive axial and strong rhombic anisotropic contributions from the Co(II) ions.

Charge-transfer-induced spin transitions in crystals containing cyanide-bridged Co-Fe clusters: role of intra- and intercluster interactions.

A theoretical model has been developed to explain at the electronic level the charge-transfer-induced spin transition (CTIST) in crystals based on cyano-bridged binuclear Fe-Co clusters. The CTIST is considered as a cooperative phenomenon (phase transformation) driven by the long-range electron-deformational interaction via the acoustic phonons field that is taken into account within the mean field approach. The model for CTIST includes also the metal-metal electron transfer and intracluster magnetic exchange. The conditions that favor the CTIST are discussed. The qualitative explanation of the experimental data is given.

A model of spin crossover in manganese(III) compounds: effects of intra- and intercenter interactions.

A microscopic approach to the problem of cooperative spin crossover in the [MnL2]NO3 crystal, which contains Mn(III) ions as structural units, is elaborated on, and the main mechanisms governing this effect are revealed. The proposed model also takes into account the splitting of the low-spin 3T1 (t(2)(4)) and high-spin 5E (t(2)(3)e) terms by the low-symmetry crystal field. The low-spin → high-spin transition has been considered as a cooperative phenomenon driven by interaction of the electronic shells of the Mn(III) ions with the all-around full-symmetric deformation that is extended over the crystal lattice via the acoustic phonon field. The model well explains the observed thermal dependencies of the magnetic susceptibility and the effective magnetic moment.

Redox properties of manganese-containing zirconia solid solution catalysts analyzed by in situ UV-vis spectroscopy and crystal field theory.

The optical absorption spectra of manganese-promoted sulfated zirconia, a highly active alkane isomerization catalyst, were found to be characterized by oxygen-to-manganese charge-transfer transitions at 300-320 nm and d-d transitions of manganese ions at 580 and 680 nm. The latter were attributed to Mn(4+) and Mn(3+) ions, which are known to be incorporated in the zirconia lattice. The oxygen surroundings of these ions were modeled assuming a substitutional solid solution. The crystal field splittings, vibronic coupling constants, and oscillator strengths of the manganese ions were calculated on the basis of a cluster model that considers the manganese center as a complex with the adjacent ions of the lattice as ligands. The ratio of Mn(3+) to Mn(4+) ions was determined using the spectra and the model, and the relative concentrations of Mn(2+), Mn(3+), and Mn(4+) ions were determined with the help of the average valence known from X-ray absorption data in the literature. The redox behavior of manganese-promoted sulfated zirconia in oxidizing and inert atmosphere was elucidated at temperatures ranging from 323 to 773 K.

Enhancing the blocking temperature in single-molecule magnets by incorporating 3d-5d exchange interactions.

We report the first single-molecule magnet (SMM) to incorporate the [Os(CN)(6)](3-) moiety. The compound (1) has a trimeric, cyanide-bridged Mn(III)-Os(III)-Mn(III) skeleton in which Mn(III) designates a [Mn(5-Brsalen)(MeOH)](+) unit (5-Brsalen=N,N'-ethylenebis(5-bromosalicylideneiminato)). X-ray crystallographic experiments reveal that 1 is isostructural with the Mn(III)-Fe(III)-Mn(III) analogue (2). Both compounds exhibit a frequency-dependent out-of-phase χ''(T) alternating current (ac) susceptibility signal that is suggestive of SMM behaviour. From the Arrhenius expression, the effective barrier for 1 is found to be Δ(eff)/k(B)=19 K (τ(0)=5.0×10(-7) s; k(B)=Boltzmann constant), whereas only the onset (1.5 kHz, 1.8 K) of χ''(T) is observed for 2, thus indicating a higher blocking temperature for 1. The strong spin-orbit coupling present in Os(III) isolates the E'(1g(1/2))(O(h)*) Kramers doublet that exhibits orbital contributions to the single-ion anisotropy. Magnetic susceptibility and inelastic neutron-scattering measurements reveal that substitution of [Fe(CN)(6)](3-) by the [Os(CN)(6)](3-) anion results in larger ferromagnetic, anisotropic exchange interactions going from quasi-Ising exchange interactions in 2 to pure Ising exchange for 1 with J(parallel)(MnOs)=-30.6 cm(-1). The combination of diffuse magnetic orbitals and the Ising-type exchange interaction effectively contributes to a higher blocking temperature. This result is in accordance with theoretical predictions and paves the way for the design of a new generation of SMMs with enhanced SMM properties.

Single-ion anisotropy and exchange interactions in the cyano-bridged trimers MnIII2MIII(CN)6 (MIII = Co, Cr, Fe) species incorporating [Mn(5-Brsalen)]+ units: an inelastic neutron scattering and magnetic susceptibility study.

The electronic structures of the compounds K[(5-Brsalen)(2)(H(2)O)(2)-Mn(2)M(III)(CN)(6)].2H(2)O (M(III) = Co(III), Cr(III), Fe(III)) have been determined by inelastic neutron scattering (INS) and magnetic susceptibility studies, revealing the manganese(III) single-ion anisotropy and exchange interactions that define the low-lying states of the Mn-M(III)-Mn trimeric units. Despite the presence of an antiferromagnetic intertrimer interaction, the experimental evidence supports the classification of both the Cr(III) and Fe(III) compounds as single-molecule magnets. The value of 17(2) cm(-1) established from AC susceptibility measurements for a spin-reversal barrier of K[(5-Brsalen)(2)(H(2)O)(2)-Mn(2)Cr(CN)(6)].2H(2)O may be readily rationalized in terms of the energy level diagram determined directly by INS. AC susceptibility measurements on samples of K[(5-Brsalen)(2)(H(2)O)(2)-Mn(2)Fe(CN)(6)].2H(2)O are contrary to those previously reported, exhibiting but the onset of peaks below temperatures of 1.8 K at oscillating frequencies in the range of 100-800 Hz. INS measurements reveal an anisotropic ferromagnetic manganese(III)-iron(III) exchange interaction, in accordance with theoretical expectations based on the unquenched orbital angular momentum of the [Fe(CN)(6)](3-) anion, giving rise to an M(s) approximately +/-9/2 ground state, isolated by approximately 11.5 cm(-1) from the higher-lying levels. The reported INS and magnetic data should now serve as a benchmark against which theoretical models that aim to inter-relate the electronic and molecular structure of molecular magnets should be tested.

Highly anisotropic exchange interactions in a trigonal bipyramidal cyanide-bridged Ni(II)3Os(III)2 cluster.

This article is a part of our efforts to control the magnetic anisotropy in cyanide-based exchange-coupled systems with the eventual goal to obtain single-molecule magnets with higher blocking temperatures. We give the theoretical interpretation of the magnetic properties of the new pentanuclear complex {[Ni(II)(tmphen)(2)](3)[Os(III)(CN)(6)](2)} x 6 CH(3)CN (Ni(II)(3)Os(III)(2) cluster). Because the system contains the heavy Os(III) ions, spin-orbit coupling considerably exceeds the contributions from the low-symmetry crystal field and exchange coupling. The magnetic properties of the Ni(II)(3)Os(III)(2) cluster are described in the framework of a highly anisotropic pseudo-spin Hamiltonian that corresponds to the limit of strong spin-orbital coupling and takes into account the complex molecular structure. The model provides a good fit to the experimental data and allows the conclusion that the trigonal axis of the bipyramidal Ni(II)(3)Os(III)(2) cluster is a hard axis of magnetization. This explains the fact that in contrast with the isostructural trigonal bipyramidal Mn(III)(2)Mn(II)(3) cluster, the Ni(II)(3)Os(III)(2) system does not exhibit the single-molecule magnetic behavior.

A highly anisotropic cobalt(II)-based single-chain magnet: exploration of spin canting in an antiferromagnetic array.

In this article we report for the first time experimental details concerning the synthesis and full characterization (including the single-crystal X-ray structure) of the spin-canted zigzag-chain compound [Co(H2L)(H2O)]infinity [L = 4-Me-C6H4-CH2N(CPO3H2)2], which contains antiferromagnetically coupled, highly magnetically anisotropic Co(II) ions with unquenched orbital angular momenta, and we also propose a new model to explain the single-chain magnet behavior of this compound. The model takes into account (1) the tetragonal crystal field and the spin-orbit interaction acting on each Co(II) ion, (2) the antiferromagnetic Heisenberg exchange between neighboring Co(II) ions, and (3) the tilting of the tetragonal axes of the neighboring Co units in the zigzag structure. We show that the tilting of the anisotropy axes gives rise to spin canting and consequently to a nonvanishing magnetization for the compound. In the case of a strong tetragonal field that stabilizes the orbital doublet of Co(II), the effective pseudo-spin-1/2 Hamiltonian describing the interaction between the Co ions in their ground Kramers doublet states is shown to be of the Ising type. An analytical expression for the static magnetic susceptibility of the infinite spin-canted chain is obtained. The model provides an excellent fit to the experimental data on both the static and dynamic magnetic properties of the chain.

Iridates from the molecular side.

New exotic phenomena have recently been discovered in oxides of paramagnetic Ir(4+) ions, widely known as 'iridates'. Their remarkable properties originate from concerted effects of the crystal field, magnetic interactions and strong spin-orbit coupling, characteristic of 5d metal ions. Despite numerous experimental reports, the electronic structure of these materials is still challenging to elucidate, and not attainable in the isolated, but chemically inaccessible, [IrO6](8-) species (the simplest molecular analogue of the elementary {IrO6}(8-) fragment present in all iridates). Here, we introduce an alternative approach to circumvent this problem by substituting the oxide ions in [IrO6](8-) by isoelectronic fluorides to form the fluorido-iridate: [IrF6](2-). This molecular species has the same electronic ground state as the {IrO6}(8-) fragment, and thus emerges as an ideal model for iridates. These results may open perspectives for using fluorido-iridates as building-blocks for electronic and magnetic quantum materials synthesized by soft chemistry routes.

Highly anisotropic orbitally dependent superexchange in cyano-bridged clusters containing Mn(III) and Mn(II) ions.

We study the orbitally dependent magnetic exchange in cyanide-based clusters as a source of the barrier for reversal magnetization. We consider the Mn(III)-CN-Mn(II) dimer and linear Mn(II)-NC-Mn(III)-CN-Mn(II) trimer containing octahedrally coordinated Mn(III) and Mn(II) ions with special emphasis on the magnetic manifestations of the orbital degeneracy of the Mn(III) ion. The kinetic exchange mechanism involves the electron transfer from the single occupied t(2) orbitals of the Mn(II) ion [6A1(t2(3)e2) ground state] to the singly occupied t(2) orbitals of the Mn(III) ion [3T1(t2(4)) ground state] resulting in the charge-transfer 5T2(t2(2)e2)Mn(III) - 2T2(t2(5))Mn(II) state of the pair. The deduced effective exchange Hamiltonian that takes into account orbital degeneracy leads to an essentially non-Heisenberg energy pattern. The energy levels are shown to be dependent on both spin and orbital quantum numbers, thus providing direct information about the magnetic anisotropy of the system. Along with the magnetic exchange, the model includes an axial component of the crystal field and spin-orbit coupling operating within the ground 3T1(t2(4)) cubic term of the Mn(III) ion. We have shown that under certain conditions both named interactions lead to the occurrence of the barrier for the reversal of magnetization, which significantly increases when passing from the dimer to the trimer. This provides a possible way for raising the magnetic barrier in the family of cyano-bridged manganese clusters.

Origin of the single chain magnet behavior of the Co(H2L)(H2O) compound with a 1D structure.

The paper is aimed at the elucidation of the main factors responsible for the single-chain magnet behavior of the cobalt(II) disphosphonate compound Co(H2L)(H2O) with a 1D structure. The model takes into account the spin-orbit interaction, the axial component of the octahedral crystal field acting on the ground-state cubic 4T1 terms of the Co(II) ions, the antiferromagnetic exchange interaction between Co(II) ions as well as the difference in the crystallographic positions of these ions. The conditions that favor the single-chain magnet behavior based on spin canting in a 1D chain containing inequivalent Co(II) centers are discussed. The peculiarities of this behavior in chains containing orbitally degenerate ions are revealed. The qualitative explanation of the experimental data is given.

Control of the Barrier in Cyanide Based Single Molecule Magnets Mn(III)2Mn(II)3: Theoretical Analysis.

The aim of this communication is to probe the possibility of increasing the barrier for reversal of magnetization in the family of new cyano-bridged pentanuclear Mn(III)2Mn(II)3 clusters in which single molecule magnet behavior has been recently discovered. In this context, we analyze the global magnetic anisotropy arising from the unquenched orbital angular momenta of ground terms (3)T1(t2(4)) of the two apical Mn(III) ions. The model takes into account the trigonal component of the crystal field, spin-orbit interaction in (3)T1(t2(4)), and an isotropic exchange interaction between Mn(III) and Mn(II) ions. The height of the barrier is shown to be sensitive to the change of the trigonal field stabilizing orbital doublet (3)E, which carries the first-order orbital magnetic contribution and enhances with an increase of the trigonal field. This result is expected to be useful for the more rational design of new cyano-bridged SMMs with high blocking temperatures.

Role of the orbitally degenerate Mn(III) ions in the single-molecule magnet behavior of the cyanide cluster ([MnII(tmphen)2]3[Mn(III)(CN)6]2) (tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline).

We report a new theoretical model that accounts for the unusual magnetic properties of the cyanide cluster ([MnII(tmphen)2]3[MnIII(CN)6]2) (tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline). The model takes into account (1) the spin-orbit interaction, (2) the trigonal component of the crystal field acting on the ground-state cubic (3)T(1) terms of the apical Mn(III) ions, and (3) the isotropic contribution to the exchange interaction between Mn(III) and Mn(II) ions. The ground state of the cluster was shown to be the state with the total angular momentum projection |M(J)| = 15/2; the energies of the low-lying levels obtained from this treatment increase with decreasing |M(J)| values, a situation that leads to a barrier for the reversal of magnetization (U(eff) approximately 30 cm(-1)). The new model explains the recently discovered single-molecule magnet behavior of the ([MnII(tmphen)2]3[MnIII(CN)6]2)in contrast to the traditional approach that takes into account only the ground-state spin (S) and a negative zero-field splitting parameter (D(S) < 0).