Spin-frustrated trinuclear Cu(II) clusters with mixing of 2(S = 1/2) and S = 3/2 states by antisymmetric exchange. 2. Orbital origin of in-plane Dzialoshinsky-Moriya exchange parameters

The microscopic origin of the in-plane (Gx, Gy) and out-of-plane (Gz) Dzialoshinsky-Moriya (DM) exchange parameters is considered for the Cu3(II) clusters. For the systems with the d(x2-y2) ground state of the Cu ions, only Z components of the pair DM exchange parameters are active (Gz not equal to 0, G(x,y) = 0) in the cases of the orientations of the local anisotropy axes zi| (zi||Z) and perpendicular (zi perpendicular Z, xi||(- Z)) to the molecular trigonal Z axis. The dependences of the Gx, Gy, and Gz DM exchange parameters on the tilt of the local magnetic orbitals were obtained for the antiferromagnetic (AFM) clusters with the d(x2-y2) and d(z2) ground state of the Cu ions. The tilt of the local d(x2-y2) orbitals results in the change of the Gz parameter and appearance of the in-plane DM exchange interactions (Gx or/and Gy parameters). The dependence of the Gz and Gx,Gy DM exchange parameters on the tilt angle is essentially different. The in-plane DM exchange coupling (Gx,Gy parameters) can significantly exceed the out-of-plane DM coupling (Gz parameter). The nonzero Gz and Gx,Gy parameters can be positive or negative. For the {Cu3} nanomagnet with the d(x2-y2) ground state and relatively strong DM coupling, the model explains the three DM exchange parameters of the same value (|Gz| = |Gx| = |Gy|) by the small tilt of the local anisotropy axes zi of the CuO4 local groups of the trimer from the positions zi perpendicular Z. The dependence of the DM exchange parameters (Gz, Gx, Gy) on the tilt for the AFM Cu3 clusters with the d(z2) ground states of the Cu ions differs significantly from that for the AFM systems with the ground state d(x2-y2) of the individual ions. Large in-plane DM exchange parameters Gx or/and Gy result in the mixing of the 2(S = 1/2) and S = 3/2 states and zero-field splitting (ZFS) 2D(DM) of the excited S = 3/2 state. The DM exchange contribution 2D(DM) to ZFS of the excited S = 3/2 state possesses the significant dependence on the tilt of the local magnetic orbitals.     

Spectroscopic demonstration of a large antisymmetric exchange contribution to the spin-frustrated ground state of a D3 symmetric hydroxy-bridged trinuclear Cu(II) complex: ground-to-excited state superexchange pathways

The magnetic and electronic properties of a spin-frustrated ground state of an antiferromagnetically coupled 3-fold symmetric trinuclear copper complex (TrisOH) is investigated using a combination of variable-temperature variable-field magnetic circular dichroism (VTVH MCD) and powder/single-crystal EPR. Direct evidence for a low-lying excited S = (1)/(2) state from the zero-field split ground (2)E state is provided by the nonlinear dependence of the MCD intensity on 1/T and the nesting of the VTVH MCD isotherms. A consistent zero-field splitting (Delta) value of approximately 65 cm(-1) is obtained from both approaches. In addition, the strong angular dependence of the single-crystal EPR spectrum, with effective g-values from 2.32 down to an unprecedented 1.2, requires in-state spin-orbit coupling of the (2)E state via antisymmetric exchange. The observable EPR intensities also require lowering of the symmetry of the trimer structure, likely reflecting a magnetic Jahn-Teller effect. Thus, the Delta of the ground (2)E state is shown to be governed by the competing effects of antisymmetric exchange (G = 36.0 +/- 0.8 cm(-1)) and symmetry lowering (delta = 17.5 +/- 5.0 cm(-1)). G and delta have opposite effects on the spin distribution over the three metal sites where the former tends to delocalize and the latter tends to localize the spin of the S(tot) = (1)/(2) ground state on one metal center. The combined effects lead to partial delocalization, reflected by the observed EPR parallel hyperfine splitting of 74 x 10(-4) cm(-1). The origin of the large G value derives from the efficient superexchange pathway available between the ground d(x2-y2) and excited d(xy) orbitals of adjacent Cu sites, via strong sigma-type bonds with the in-plane p-orbitals of the bridging hydroxy ligands. This study provides significant insight into the orbital origin of the spin Hamiltonian parameters of a spin-frustrated ground state of a trigonal copper cluster.     

Isotropic and antisymmetric double-exchange, zero-field, Zeeman, and hyperfine splittings in trinuclear valence-delocalized [Cu3(7+)] clusters

Valence delocalization in the [Cu3(7+)] trimer is considered in the model of the double-exchange coupling, in which full delocalization corresponds to the migration of the single d(x2-y2) hole and relatively strong isotropic double-exchange coupling. Strong double exchange results in the pairing of the individual spins in the delocalized trimer even at room temperature. The model explains the delocalized singlet 1A1 ground state in the planar Cu3(mu3-O) core by strong double exchange with positive double-exchange parameter t(0), whereas the delocalized triplet ground state of the [Cu3(7+)] trimer, which was observed in the Cu3(mu3-S)2 cluster, may be explained by the double exchange with relatively weak positive t(0): 0 < t(0) < 2J (degenerate 3E ground state) or negative t(0) (triplet 3A2 ground state). An analysis of the splitting of the delocalized degenerate 3E term requires inclusion of the antisymmetric double-exchange interaction, which takes into account the spin-orbit coupling in the double-exchange model. The cluster parameter KZ of the antisymmetric double-exchange coupling is proportional to t(0) and anisotropy of the g factor Deltag(parallel)[Cu(II)], KZ < t(0). Antisymmetric double exchange is relatively large in the [Cu3(7+)] cluster with the d(x2-y2) magnetic orbitals lying in the Cu3 plane [Cu3(mu3-O) core], whereas for the d(x2-y2) magnetic orbitals lying in the plane perpendicular to Cu3, antisymmetric double-exchange coupling is weak [Cu3(mu3-S)2 cluster]. The antisymmetric double-exchange coupling results in the linear zero-field splitting DeltaK = 2[equation: see text]KZ (approximately t(0)) of the delocalized degenerate 3E term that leads to strong anisotropy of the Zeeman splittings in the external magnetic field and a complex electron paramagnetic resonance (EPR) spectrum. The delocalized model of hyperfine interaction explains the hyperfine structure [10 hyperfine lines with the relative intensities 1:3:6:10:12:12:10:6:3:1 and the interval a/3] of the EPR transitions in the triplet states that was observed in the EPR spectra of the Cu3(mu3-S)2 cluster.     

New Ni(II)Cu(II)Ni(II) trinuclear complexes with an 5=3/2 high-spin ground

Four new heterotrinuclear complexes have been synthesized and characterized, namely {[Ni(L)₂]₂[Cu(opba)]}(ClO₄)₂, where opba denotes o-phenylenebis(oxamato) and L stands for 1,10-phenanthroline(phen) (1), 5-nitro-l,10-phenanthroline(NO₂-phen) (2), 2,2′-bipyridyl(bpy) (S) and 4,4′-dimethyl-2,2′-bipyridyl(Me₂bpy) (4). The temperature dependence of the magnetic susceptibility of {[Ni(phen)₂]₂[Cu(opba)]}(ClO₄)₂3H₂O has been studied in the 4–300 K range, giving the exchange integral J—109 cm^?1. The HMT vs. T plot exhibits a minimum at about 100 K, characteristic of this kind of coupled polymetallic complex with an irregular spin-state structure.     

Antisymmetric exchange in the trinuclear clusters of copper (II)

The magnetic susceptibility of Cu₃(C₆H₅N₂O)₃(OH)SO₄ · 10.5 H₂O crystals was measured in the temperature interval 4.2–11 K and magnetic field range 0–50 kOe. The theoretical analysis of the effects of antisymmetric exchange was performed. An adequate interpretation of the experimental results may be done in terms of an antisymmetric exchange which is about 12 cm^?1 in the crystals discussed. The rhombic distortions of the trigonal cluster were shown to reduce the antisymmetric exchange.     

Structural and magnetic properties of Mn(III) and Cu(II) tetranuclear azido polyoxometalate complexes: multifrequency high-field EPR spectroscopy of Cu4 clusters with S = 1 and S = 2 ground states

Two new azido-bridged polyoxometalate compounds were synthesized in acetonitrile/methanol media and their molecular structures have been determined by X-ray crystallography. The [[(gamma-SiW10O36)Mn2(OH)2(N3)(0.5)(H2O)(0.5)]2(mu-1,3-N3)](10-) (1 a) tetranuclear Mn(III) complex, in which an end-to-end N3- ligand acts as a linker between two [(gamma-SiW10O36)Mn2(OH)2]4- units, represents the first manganese-azido polyoxometalate. The magnetic properties have been studied considering the spin Hamiltonian H = -J1(S1S2+S1*S2*)-J2(S1S1*), showing that antiferromagnetic interactions between the paramagnetic centers (g = 1.98) occur both through the di-(mu-OH) bridge (J1 = -25.5 cm(-1)) and the mu-1,3-azido bridge (J2 = -19.6 cm(-1)). The [(gamma-SiW10O36)2Cu4(mu-1,1,1-N3)2(mu-1,1-N3)2]12- (2 a) tetranuclear Cu(II) complex consists of two [gamma-SiW10O36Cu2(N3)2]6- subunits connected through the two mu-1,1,1-azido ligands, the four paramagnetic centers forming a lozenge. The magnetic susceptibility data have been fitted. This reveals ferromagnetic interactions between the four Cu(II) centers, leading to an S=2 ground state (H = -J1(S1S2+S1*S2*)-J2(S2S2*), J1 = +294.5 cm(-1), J2 = +1.6 cm(-1), g = 2.085). The ferromagnetic coupling between the Cu(II) centers in each subunit is the strongest ever observed either in a polyoxometalate compound or in a diazido-bridged Cu(II) complex. Considering complex 2 a and the previously reported basal-basal di-(mu-1,1-N3)-bridged Cu(II) complexes in which the metallic centers are not connected by other magnetically coupling ligands, the linear correlation J1 = 2639.5-24.95*theta(av) between the theta(av) bridging angle and the J1 coupling parameter has been proposed. The electronic structure of complex 2 a has also been investigated by using multifrequency high-field electron paramagnetic resonance (HF-EPR) spectroscopy between 95 and 285 GHz. The spin Hamiltonian parameters of the S = 2 ground state (D = -0.135(2) cm(-1), E = -0.003(2) cm(-1), g(x) = 2.290(5), g(y) = 2.135(10), g(z) = 2.158(5)) as well as of the first excited spin state S = 1 (D = -0.960(4) cm(-1), E = -0.080(5) cm(-1), g(x) = 2.042(5), g(y) = 2.335(5), g(z) = 2.095(5)) have been determined, since the energy gap between these two spin states is very small (1.6 cm(-1)).     

An S = 2 cyanide-bridged trinuclear Fe(III)2Ni(II) single-molecule magnet

Treatment of [NEt4][(pzTp)Fe(III)(CN)3] (1) with Ni(II)(OTf)2 (OTf = trifluoromethanesulfonate) and 1,5,8,12-tetraazadodecane (L) affords {[(pzTp)Fe(III)(CN)3]2[Ni(II)L]} x 1/2MeOH (2), while 2,2'-bipyridine (bipy) affords {[(pzTp)Fe(III)(CN)3]2[Ni(II)(bipy)2]} x 2 H2O (3). Magnetic measurements indicate that 2 and 3 have S = 2 ground states and that 3 exhibits slow relaxation of the magnetization above 2 K.     

Electronic properties and 1/3 magnetization plateau of the S=1/2 magnetism Cu3(P2O6OH)2

First, the geometrical structure, energy band structure, density of states, and overlap population of the copper hydroxydiphosphate ( ) are investigated systematically using the first‐principles density functional method. The generalized gradient approximations (GGA)+U method is adopted to consider the on‐site coulomb repulsion on Cu 3d orbits. The theoretical structural results obtained by the geometry optimization agree well with the experimental data. Energy band structures show that the belongs to a semiconductor. It is found that the on‐site Coulomb repulsion plays a key role in the opening of the energy gap. The uppest valence band is found to be mainly contributed from O 2p and Cu 3d states, but the lowest conduction band is characterized by Cu 3d state. Furthermore, a strong hybridization between O‐2p and Cu‐3d orbits is observed. Then, the magnetization, bipartite entanglement, and the nearest‐neighbor correlations in such a cuprate are calculated by the infinite time‐evolving block decimation algorithm. Distinctive magnetization plateaus accompanied with some interesting bipartite entanglement and correlation plateaus are observed at T=0 k in the thermodynamic limit. © 2014 Wiley Periodicals, Inc.     

Stabilization of 3:1 site-differentiated cubane-type clusters in the [Fe(4)S(4)](1+) core oxidation state by tertiary phosphine ligation: synthesis, core structural diversity, and S = 1/2 ground states

An extensive series of 3:1 site-differentiated cubane-type clusters [Fe(4)S(4)(PPr(i)(3))(3)L] (L = Cl(-), Br(-), I(-), RO(-), RS(-), RSe(-)) has been prepared in 40-80% yield by two methods: ligand substitution of [Fe(4)S(4)(PPr(i)(3))(4)](1+) in tetrahydrofuran (THF)/acetonitrile by reaction with monoanions, and reductive cleavage of ligand substrates (RSSR, RSeSeR, I(2)) by the all-ferrous clusters [Fe(8)S(8)(PPr(i)(3))(6)]/[Fe(16)S(16)(PPr(i)(3))(8)] in THF. These neutral clusters are stable and do not undergo ligand redistribution reactions involving charged species in benzene and THF solutions. X-ray structural studies confirm the cubane stereochemistry but with substantial and variable distortions of the [Fe(4)S(4)](1+) core from idealized cubic core geometry. Based on Fe-S bond lengths, seven clusters were found to have compressed tetragonal distortions (4 short and 8 long bonds), and the remaining seven display other types of distortions with different combinations of long, short, and intermediate bond lengths. These results further emphasize the facile deformabililty of this core oxidation state previously observed in [Fe(4)S(4)(SR)(4)](3-) clusters. The Fe(2.25+) mean oxidation state was demonstrated from (57)Fe isomer shifts, and the appearance of two quadrupole doublets arises from the spin-coupled |9/2,4,1/2> state. The S = 1/2 ground state was further supported by electron paramagnetic resonance spectra and magnetic susceptibility data.     

EPR of Cu(II)-doped seven-coordinate inclusion compounds, M(stpy)3(NO3)2 x 1/2stpy (M = Cd(II) and Zn(II), stpy = trans-4-styrylpyridine): low symmetry effects in admixture of ground states

Single crystal EPR of Cu(II)-doped low symmetry pentagonal bipyramidal Werner-type clathrate inclusion complexes of Cd(stpy)3(NO3)2 x 1/2stpy(1) and Zn(stpy)3(NO3)2 x 1/2stpy(2) (stpy = trans-4-styrylpyridine) is reported. The spin Hamiltonian parameters are found to be orthorhombic with g33 = 2.298, g22 = 2.108, g11 = 2.066, A33 = 107.3, A22 = 54.4 and A11 = 23.1 x 10(-4) cm(-1) for 1 and g33 = 2.292, g22 = 2.111, g11 = 2.067, A33 = 107.5, A22 = 54.7 and A11 = 22.9 x 10(-4) cm(-1) for 2. Angular variation studies for both 1 and 2 suggest that the Cu(II) ions are substitutionally incorporated in the host lattices. The magnitude of Cu(II) hyperfine coupling constant (A33) in both 1 and 2 are found to be low, in comparison to those of the pure Cu(II) complex, indicative of low symmetry for the substitutional sites in accordance with the crystal data. Such large reductions in Cu(II) hyperfine coupling are explicable in terms of a mixed d(x2 - y2)/dz2 ground state and delocalization of unpaired spin density onto the ligands.     

NMR paramagnetic relaxation due to the S=5/2 complex, Fe(III)-(tetra-p-sulfonatophenyl)porphyrin: central role of the tetragonal fourth-order zero-field splitting interaction

The metalloporphyrins, Me-TSPP [Me=Cr(III), Mn(III), Mn(II), Fe(III), and TSPP=meso-(tetra-p-sulfonatophenyl)porphyrin], which possess electron spins S=3/2, 2, 5/2, and 5/2, respectively, comprise an important series of model systems for mechanistic studies of NMR paramagnetic relaxation enhancement (NMR-PRE). For these S>1/2 spin systems, the NMR-PRE depends critically on the detailed form of the zero-field splitting (zfs) tensor. We report the results of experimental and theoretical studies of the NMR relaxation mechanism associated with Fe(III)-TSPP, a spin 5/2 complex for which the overall zfs is relatively large (D approximately = 10 cm(-1)). A comparison of experimental data with spin dynamics simulations shows that the primary determinant of the shape of the magnetic relaxation dispersion profile of the water proton R1 is the tetragonal fourth-order component of the zfs tensor. The relaxation mechanism, which has not previously been described, is a consequence of zfs-induced mixing of the spin eigenfunctions of adjacent Kramers doublets. We have also investigated the magnetic-field dependence of electron-spin relaxation for S=5/2 in the presence of a large zfs, such as occurs in Fe(III)-TSPP. Calculations show that field dependence of this kind is suppressed in the vicinity of the zfs limit, in agreement with observation.     

An integrated approach to the mid-spin state (S = 3/2) in six-coordinate iron(III) chiroporphyrins

An intermediate-spin state very close to the mid-spin state (S = 3/2) can be stabilized in a ferric porphyrin by an integrated approach which combines the favorable effects of a weak axial field strength and of a small macrocycle hole. Axial ligand exchange by reaction of chloroiron(III)tetramethylchiroporphyrin [(TMCP)FeCl] with silver perchlorate in ethanol-chloroform leads to ethanol-ligated ferric chiroporphyrins. Two distinct crystalline products containing a bisethanol complex [[(TMCP)FeIII(EtOH)2]ClO4] and three variants of a mixed ethanol-water complex [[(TMCP)FeIII(EtOH)(H2O)]ClO4] have been structurally characterized in the solid state. The small hole of the ruffled chiroporphyrin and the weak axial oxygen ligation result in strongly tetragonally distorted complexes. The six-coordinate species exhibit long axial Fe-O bond distances (2.173(5)-2.272(4) A) and the shortest equatorial Fe-N(av) distances (1.950(5)-1.978(7) A) found as yet in a ferric porphyrin, reflecting a singly occupied dz2 orbital and a largely depopulated dx2-y2 orbital. An intriguing case of bond-stretch isomerism is seen for the axial Fe-O bonds in two crystallographically independent mixed ethanol-water species, and it is accounted for by their distinct intra- and intermolecular hydrogen-bond arrays. The M?ssbauer spectrum (delta = 0.35(1) mm s-1 and delta EQ = 3.79(1) mm s-1 at 77 K) indicates a strong tetragonal distortion around the ferric ion, in agreement with the structural data. The value of the magnetic moment (mu eff = 3.8 mu B in the range 50-300 K) strongly supports a mid-spin state (S = 3/2). The EPR spectrum at 80 K (g perpendicular approximately 4.0, g parallel approximately 2.00) is consistent with a nearly pure mid-spin state (4A2) with little rhombic distortion. The 1H NMR spectra in CDCl3-EtOH exhibit upfield-shifted resonances for the pyrrole protons (delta approximately -30 ppm) which are consistent with the depopulated iron dx2-y2 orbital. Solution equilibria with water and various alcohols, and the spin state of the corresponding species, are discussed on the basis of the NMR data. The bisethanol and ethanol-water species are potential models of unknown hemoprotein ligation states such as Tyr(OH)/Tyr(OH) or Tyr(OH)/H2O that could be obtained by site-directed mutagenesis.     

Magnetic anisotropy of two trinuclear and tetranuclear Cr(III)Ni(II) cyanide-bridged complexes with spin ground states S = 4 and 5

The trinuclear and the tetranuclear complexes [[iPrtacnCr(CN)3]2[Ni(cyclam)]](NO3)2.5H2O 1 (cyclam = 1,4,8,11-tetraazacyclotetradecane, iPrtacn = 1,4,7-tris-isopropyl-1,4,7-triazacyclononane) and [[iPrtacnCr(CN)3Ni(Me2bpy)2]2](ClO4)4.2CH3CN 2 (Me2bpy = 4,4-dimethyl-2,2-bipyridine) were synthesized by reacting (iPrtacn)Cr(CN)3 with [Ni(cyclam)](NO3)2 and [Ni(Me2bpy)2(H2O)2](ClO4)2, respectively. The crystallographic structure of the two compounds was solved. The molecular structure of complex 1 consists of a linear Cr-Ni-Cr arrangement with a central Ni(cyclam) unit surrounded by two Cr(iPrtacn)(CN)3 molecules through bridging cyanides. Each peripheral chromium complex has two pending CN ligands. Complex 2 has a square planar arrangement with the metal ions occupying the vertices of the square. Each Cr(iPrtacn)(CN)3 molecule has two bridging and one non-bridging cyanide ligands. The magnetic properties of the two complexes were investigated by susceptibility vs. temperature and magnetization vs. field studies. As expected from the orthogonality of the magnetic orbitals between Cr(III) (t2g3) and Ni(II) (e(g)2) metal ions, a ferromagnetic exchange interaction occurs leading to a spin ground states S = 4 and 5 for 1 and 2, respectively. The magnetization vs. field studies at T = 2, 3 and 4 K showed the presence of a magnetic anisotropy within the ground spin states leading to zero-field splitting parameters obtained by fitting the data D4 = 0.36 cm(-1) and D5 = 0.19 cm(-1) (the indices 4 and 5 refer to the ground states of complexes 1 and 2, respectively). In order to quantify precisely the magnitude of the axial (D) and the rhombic (E) anisotropy parameters, High-field high frequency electron paramagnetic resonance (HF-HFEPR) experiments were carried out. The best simulation of the experimental spectra (at 190 and 285 GHz) gave the following parameters for 1: D4 = 0.312 cm(-1), E4/D4 = 0.01, g4x = 2.003, g4y = 2.017 and g4z = 2.015. For complex 2 two sets of parameters could be extracted from the EPR spectra because a doubling of the resonances were observed and assigned to the presence of complexes with slightly different structures at low temperature: D5 = 0.154 (0.13) cm(-1), E5/D5 = 0.31 (0.31) cm(-1), g4x = 2.04 (2.05), g4y = 2.05 (2.05) and g4z = 2.03 (2.02). The knowledge of the magnetic anisotropy parameters of the mononuclear Cr(iPrtacn)(CN)3, Ni(cyclam)(NCS)2 and Ni(bpy)2(NCS)2 complexes by combining HF-HFEPR studies and calculation using a software based on the angular overlap model (AOM) allowed to determine the orientation of the local D tensors of the metal ions forming the polynuclear complexes. We, subsequently, show that the anisotropy parameters of the polynuclear complexes computed from the projection of the local tensors are in excellent agreement with the experimental ones extracted from the EPR experiments.     

Investigations of zero-field splitting (ZFS) and local distortion parameters of ZnAl2S4:Mn2+ by theoretical analysis

Fourth-order perturbation formula on the basis of the dominant spin-orbit coupling mechanism is employed to investigate the local environment around Mn2+ centers in ZnAl2S4 single crystals. The zero-field splitting (ZFS) parameter D is calculated for the Mn2+ ions at the Al3+ site with local symmetry D3d using the different orbital reduction factors. Both the contributions of the lattice distortions to the crystal-field (CF) parameters and the D are examined by means of different cases. The comparison between the calculated results in this study and the previous experimental and theoretical values reveals a good agreement and reasonable distortion parameters for Mn2+ ions at Al3+ sites.     

钼(钨)/铜/硫三核簇合物[A]2[MS4(CuCN)2] (M=Mo,W;A=Et4N,PPh4)的合成及晶体结构

合成了四个三核簇合物[A]2[MS4(CuCN)2](1A＝Et4N,M＝Mo;2A＝PPh4,M＝W;3A＝Et4N,M＝W;4A＝PPh4,M＝Mo),测定了[Et4N]2[MoS4(CuCN)2]*H2O(1*H2O)和[PPh4]2[WS4(CuCN)2]*0.5DMF*H2O(2*0.5DMF*H2O)的晶体结构.1和2的簇阴离子[MS4(CuCN)2]2-(M＝Mo,W)均具有一个双齿配体MS42-和两个CuCN形成的近似D2d对称性结构.     

Tin-capped trinuclear nickel clusters: redox isomerism between micro(3)-stannyl and micro(3)-stannylene clusters of the class [Ni(3)(dppm)(3)(micro3-I)(micro3-SnCl(x)](n+) (x = 2, n = 1; x = 3, n = 0)

The reaction of Ni(3)(dppm)(3)(micro(3)-I)(2)) with sodium trichlorostannate affords the first tin-capped nickel cluster Ni(3)(dppm)(3)(micro(3)-I)(micro(3)-SnCl(3) (1). A site of coordinative unsaturation at tin can be introduced by the reaction of 1 with Tl[PF(6)] yielding the stannylene-capped cluster [Ni(3)(dppm)(3)(micro(3)-I)(micro(3)-SnCl(2)](+) (2). Clusters 1 and 2 were characterized by 31P NMR, X-ray diffraction, and cyclic voltammetry (CV). Clusters 1 and 2 exhibit single electron redox chemistries, [Ni(3)(dppm)(3)(micro(3)-I)(micro(3)-SnCl3](0/*-), [Ni(3)(dppm)(3)(micro(3)-I)(micro(3)-SnCl(2)](+/0), that together comprise a redox equilibrium. Thus, electrochemical reduction of 1 produces first the 49e- cluster radical anion [Ni(3)(dppm)(3)(micro(3)-I)(micro(3)-SnCl(3)](*-) which then yields the reduced form of 2, [Ni(3)(dppm)(3)(micro(3)-I)(micro(3)-SnCl(2)], upon chloride dissociation.     

Effects of 3d-4f magnetic exchange interactions on the dynamics of the magnetization of Dy(III)-M(II)-Dy(III) trinuclear clusters

[{Dy(hfac)(3)}(2){Fe(bpca)(2)}] x CHCl(3) ([Dy(2)Fe]) and [{Dy(hfac)(3)}(2){Ni(bpca)(2)}]CHCl(3) ([Dy(2)Ni]) (in which hfac(-)=1,1,1,5,5,5-hexafluoroacetylacetonate and bpca(-)=bis(2-pyridylcarbonyl)amine anion) were synthesized and characterized. Single-crystal X-ray diffraction shows that [Dy(2)Fe] and [Dy(2)Ni] are linear trinuclear complexes. Static magnetic susceptibility measurements reveal a weak ferromagnetic exchange interaction between Ni(II) and Dy(III) ions in [Dy(2)Ni], whereas the use of the diamagnetic Fe(II) ion leads to the absence of magnetic exchange interaction in [Dy(2)Fe]. Dynamic susceptibility measurements show a thermally activated behavior with the energy barrier of 9.7 and 4.9 K for the [Dy(2)Fe] and [Dy(2)Ni] complexes, respectively. A surprising negative effect of the ferromagnetic exchange interaction has been found and has been attributed to the structural conformation of these trinuclear complexes.     

New Binuclear Copper Complexes [(9S3)Cu(CN)Cu(9S3)]Xn (X=BF4, n=1; X=TCNQ,n=2) (9S3=1, 4, 7‐trithiacyclononane): Syntheses,Crystal Structures and Magnetic Properties

The binuclear Cu complex salts of 1, 4, 7‐trithiacyclononane (9S3) with an inorganic anion (BF₄)^‐ and with an organic radical anion TCNQ^‐ (7, 7′, 8, 8′‐tetracyanoquinodimethanide) were synthesized and their molecular and crystal structures were examined in connection with the magnetic properties. The new complex cation [Cu(9S3)CN(9S3)Cu]⁺ varies its charges and magnetic properties depending on the counter anions; [Cu(9S3)CN(9S3)Cu](BF₄) ( 1 ) was obtained as diamagnetic colorless crystals, while [Cu(9S3)CN(9S3)Cu](TCNQ)₂ ( 2 ) was obtained as dark blue crystals with antiferromagnetic properties. Complex 1 crystallized in the monoclinic space group C2/c with a = 26.863(2), b = 7.0878(5), c = 13.4864(8) Å, β = 116.318(2)°. Complex 2 crystallized in the triclinic space group P1¯ with a = 12.521(1), b = 20.2698(8), c = 8.0205(4) Å, α = 100.688(4), β = 93.846(5), γ = 94.953(4)°. Both complexes are comprised of cyano‐bridged two Cu(9S3) ions with tetrahedral coordination. The X‐ray structural study revealed that 1 has two crystallographically equivalent copper(I) atoms, while 2 has two crystallographically independent Cu^I/II sites. The two Cu^I/II sites could not be distinguished from the X‐ray structural study. For 2 the IR spectra show that both crystallographically independent TCNQ species were monoanions and are strongly dimerized due to π‐stacking, which well explains their diamagnetic contribution to the magnetic susceptibility and the highly insulating property of this salt. The temperature‐dependent magnetic susceptibility of 2 showed a deviation from the Curie‐Weiss behaviour around 60 K, which indicates a strong antiferromagnetic intermolecular interaction between the copper complexes and that such intermolecular interaction should partly occur via the TCNQ radical anion dimer.