Tuning the magnetic properties of Li(x)CrTi0.25Se2 (0.03 < or = x < or = 0.7) by directed deintercalation of lithium

X-ray diffraction (XRD), in situ energy-dispersive X-ray diffraction (EDXRD), X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and magnetic measurements were applied to investigate the effects of lithium deintercalation on pseudolayered Li(0.70)CrTi(0.25)Se(2). A detailed picture of structural changes during the deintercalation process was obtained by combining the results of EDXRD and EXAFS. Removal of Li from the host-guest complex leads to anisotropic contraction of the unit cell with stronger impact on the c axis, which is the stacking axis of the layers. The EDXRD experiments evidence that the shrinkage of the lattice parameters with decreasing x(Li) in Li(x)CrTi(0.25)Se(2) is nonlinear in the beginning and then becomes linear. Analysis of the EXAFS spectra clearly shows that the Cr/Ti-Se distances are affected in a different manner by Li removal. The Cr-Se bond lengths decrease, whereas the Ti-Se bonds lengthen when the Li content is reduced, which is consistent with XRD data. Magnetic measurements reveal a change from predominantly antiferromagnetic exchange (theta(p) = -300 K) interactions for the pristine material to ferromagnetic exchange interactions (theta = 25 K) for the fully intercalated material. Thus, the magnetic properties can be altered under ambient conditions by directed adjustment of the dominant magnetic exchange. The unusual magnetic behavior can be explained on the basis of the variation of the metal-metal distances and the Cr-Se-Cr angles with x, which were determined by Rietveld refinements. Owing to competing ferromagnetic and antiferromagnetic exchange interactions and disorder, the magnetic ground state of the intercalated materials is characterized by spin-glass or spin-glass-like behavior.     

Photoluminescence of Cd1-xMnxS (x < or = 0.3) nanowires

Cd1-xMnxS (x = 0.1-0.3) nanowires were synthesized by using the chemical vapor deposition method. They all consist of a single-crystalline wurtzite CdS structure with a [010] or [011] growth direction. The X-ray diffraction pattern reveals the contraction of the lattice constants due to the incorporation of Mn. The Mn2+ emission at approximately 2.15 eV, originating from the d-d (4T1 --> 6A1) transition, appears below 50-80 K. Its decay time is in the range of 0.55-1 ms, showing a decrease with increasing Mn content. The Mn doping reduces significantly the decay time of band-edge emission from 590 ps to 20-30 ps. Upon applying magnetic field (up to 7 T), the Mn2+ emission is suppressed and donor-acceptor pair emission becomes dominant, suggesting the energy transfer from the band electrons to the Mn2+ ions.     

Ca(2+)/vacancies and O2-/F- ordering in new oxyfluoride pyrochlores Li(2x)Ca1.5-x square 0.5-xM2O6F (M = Nb,Ta) for 0 < or = x < or = 0.5

New oxyfluorides Li(2x)Ca(1.5-x) square (0.5-x)M2O6F (M = Nb, Ta), belonging to the cubic pyrochlore structural type (Z = 8, a approximately 10.5 angstroms), were synthesized by solid state reaction for 0 < or = x < or = 0.5. XRD data allowed us to determine their structures from single crystals for the two alpha and beta-Ca(1.5) square (0.5)Nb2O6F forms and from powder samples for the others. This characterisation was completed by TEM and solid state 19F NMR experiments. For the Ca(1.5) square (0.5)M2O6F (x = 0) pyrochlore phases, the presence of a double ordering phenomenon is demonstrated, involving on one hand the Ca(2+) ions and the vacancies and on the other hand the oxide and the fluoride anions which are strictly located in the 8b sites of the Fd3m aristotype space group. The Ca(2+) ions/vacancies ordering leads to a reversible phase transition, a (P4(3)32) <--> beta (Fd3m). The 19F NMR study strongly suggests that, in the beta-phases, the fluoride ions are only on average at the centre of the Ca3 square tetrahedron. It shows that slightly different Ca-F distances occuring in alpha-Ca(1.5) square (0.5)Nb2O6F may be related to a more difficult thermal ionic and vacancies diffusion process than in the tantalate compound. This may explain the hysteresis phenomenon presented by the phase transition. A solid solution Li(2x)Ca(1.5-x) square (0.5-x) Ta2O6F (0 < or = x < or = 0.5) was prepared and the order-disorder phase transition observed for Ca(1.5) square (0.5)M2MO6F compounds disappears for all the other compositions where less or no more vacancies exist in the 16d sites. In the LiCaM2O6F compounds, the 19F NMR study allows us to determine the Ca(2+) and Li+ ions distributions around the fluoride ions and shows that the [FLi2Ca2] environment is clearly favoured.     

Structural study of the T#2-LixCoO2 (0.52 < x < or = 0.72) phase

The metastable O2-LiCoO(2) phase undergoes several reversible phase transitions upon lithium deintercalation. The first transition leads to an unusual oxygen stacking in such layered compounds. This stacking is found to be stable for 0.52 < x < or = 0.72 in Li(x)()CoO(2) and is called T(#)2. We studied this phase from a structural viewpoint using X-ray and neutron diffraction (ab initio method). The new stacking derives from the O2 one by gliding every second CoO(2) slab by (1/3, 1/6, 0). The lithium ions are found to occupy very distorted tetrahedral sites in this structure. We also discuss the possibility of this T(#)2 phase to exhibit stacking faults, whose amount depends on the method used to prepare this deintercalated phase.     

Chemical size effect on the magnetic and electrical properties in the (Tb(1-)(x)Eu(x))MnO(3) (0 < or = x < or = 1.0) system

The effect of isovalent chemical substitution of Eu3+ into the Tb3+ sites on the magnetic and electrical properties of (Tb1-xEux)MnO3 (0 相似文献   

Relationship between the electrochemical behavior and Li arrangement in Li(x)M(y)Mn(2-y)O4 (M = Co, Cr) with spinel structure

The relationship between the electrochemical behavior and the arrangement of lithium/vacancies has been investigated with electrochemical Li removal in Li(x)M(y)Mn(2-y)O4 (x < or = 1.0, 0.0 < or = y < or = 0.3, M = Co, Cr). It was shown that the electrochemical removal proceeds via two voltage regions: (1) approximately 3.9 V at x > or = approximately 0.5 and (2) approximately 4.2 V at x < or = approximately 0.5. To understand the stepwise behavior, entropy measurement of reaction, DeltaS(obs), was performed by using the electrochemical methods. The changes of the sign in deltaS(obs) from negative to positive at the composition x approximately 0.50 in Li(x)M(y)Mn(2-y)O4 indicated that the ordered arrangement of Li/vacancies was formed with electrochemical Li removal. Moreover, such an ordering was suppressed by the substitution of Co3+ and Cr3+ for Mn3+. To clarify the nature and origin of Li/vacancy ordering, the Monte Carlo simulation was performed in view of Coulombic interaction. The simulation reproduced the formation of a new phase arising from Li/vacancy ordering at x = 0.50 in Li(x)Mn2O4. In addition, the ordered arrangement of Li/vacancy at x = 0.5 was perturbed by the trivalent M3+ replacement in spinel structure due to the local clustering of Li+ around M3+. Consequently, the electrochemical behavior in spinel LiMn2O4 was deeply related to the Coulombic interactions, proved by the fact that experimentally observed changes in entropy agreed well with Monte Carlo simulation based on the Coulombic interaction.     

DFT study of unligated and ligated manganese(II) porphyrins and phthalocyanines

A theoretical study of the electronic structure, bonding, and properties of unligated and ligated manganese(II) porphyrins and phthalocyanines has been carried out "in detail" using a density functional theory (DFT) method. While manganese tetraphenylporphine (MnTPP) in the crystal is high spin (S = 5/2) with the Mn(II) atom out of the porphyrin plane, the present calculations find that the free manganese porphine (MnP) molecule has no obvious tendency to distort from planarity even in the high-spin state. The ground state of the planar structure is found to be intermediate spin (S = 3/2). Manganese phthalocyanine (MnPc) is calculated to have a 4E(g) ground state, in agreement with the more recent magnetic circular dichroism (MCD) and UV-vis measurements of the molecule in an argon matrix but different from the early magnetic measurements of solid MnPc. The effect of the crystal structure on the electronic state of MnPc is examined by the calculations of a model system. For the six-coordinate adducts with two pyridine (py) ligands, the strong-field axial ligands raise the energy of the Mn d(z2)-orbital, thereby making the Mn(II) ion low spin (S = 1/2). The recent assignment of MnPc(py)2 as an intermediate-spin state proves to be incorrect. Some issues involved in the reduced products have also been clarified. Five-coordinate MnP(py) and MnPc(py) complexes are high spin and intermediate spin, respectively.     

Lithium dimer formation in the Li-conducting garnets Li(5+x)Ba(x)La(3-x)Ta2O12 (0 < x < or =1.6)

The garnet system Li(5+x)Ba(x)La(3-x)Ta2O12 shows an unprecedented Li+ content (x < or = 1.6) and short Li-Li distances of ca 2.44 A between majority occupied sites suggesting that the high Li+ mobility requires a complex cooperative mechanism.     

Influence of oxygen defects on the crystal structure and magnetic properties of the (Tb1-xNax)MnO3-y (0<or=x<or=0.3) system

The crystallographic and magnetic behaviors of (Tb1-xNax)MnO3-y (0相似文献   

Electronically driven structural distortions in lithium intercalates of the n = 2 Ruddlesden-Popper-type host Y2Ti2O5S2: synthesis, structure, and properties of LixY2Ti2O5S2 (0 < x < 2)

Lithium intercalation into the oxide slabs of the cation-deficient n = 2 Ruddlesden-Popper oxysulfide Y(2)Ti(2)O(5)S(2) to produce Li(x)Y(2)Ti(2)O(5)S(2) (0 < x < 2) is described. Neutron powder diffraction measurements reveal that at low levels of lithium intercalation into Y(2)Ti(2)O(5)S(2), the tetragonal symmetry of the host is retained: Li(0.30(5))Y(2)Ti(2)O(5)S(2), I4/mmm, a = 3.80002(2) A, c = 22.6396(2) A, Z = 2. The lithium ion occupies a site coordinated by four oxide ions in an approximately square planar geometry in the perovskite-like oxide slabs of the structure. At higher levels of lithium intercalation, the symmetry of the cell is lowered to orthorhombic: Li(0.99(5))Y(2)Ti(2)O(5)S(2), Immm, a = 3.82697(3) A, b = 3.91378(3) A, c = 22.2718(2) A, Z = 2, with ordering of Li(+) ions over two inequivalent sites. At still higher levels of lithium intercalation, tetragonal symmetry is regained: Li(1.52(5))Y(2)Ti(2)O(5)S(2), I4/mmm, a = 3.91443(4) A, c = 22.0669(3) A, Z = 2. A phase gap exists close to the transition from the tetragonal to orthorhombic structures (0.6 < x < 0.8). The changes in symmetry of the system with electron count may be considered analogous to a cooperative electronically driven Jahn-Teller type distortion. Magnetic susceptibility and resistivity measurements are consistent with metallic properties for x > 1, and the two-phase region is identified as coincident with an insulator to metal transition.     

Lithium exchange processes in the conduction network of the Nasicon LiTi2-xZrx(PO4)3 Series (0 < or = x < or = 2)

Structural sites occupied by lithium in the rhombohedral LiTi2-xZrx(PO4)3 series (0 < or = x < or = 2) have been investigated by 7Li NMR spectroscopy. At room temperature, the XRD patterns of the end-members of the series display rhombohedral R3c symmetry in LiTi2(PO4)3 and triclinic C in LiZr2(PO4)3. In the first compound, Li ions occupy M1 sites; however, in the second one Li occupy intermediate M1/2 sites. As the temperature increases, a first-order displacive transformation is detected in the triclinic phase, but a second-order/disorder transition is detected in the rhombohedral phase. From the temperature dependence of the 7Li NMR quadrupole constant (CQ) of the two compounds, the evolution of M1 and M1/2 sites occupancy in the Nasicon conduction network has been deduced. At high temperatures, analyzed phases tend toward a disordered rhombohedral phase, in which both M1 and M1/2 sites are equally populated and in which lithium mobility is favored by the existence of vacant M1 sites. According to this study, this phase can also be obtained by substituting Ti by Zr in the LiTi2-xZrx(PO4)3 series.     

Syntheses and X-ray diffraction, photochemical, and optical characterization of Cu2SixSn1-xS3 (0.4 < or = x < or = 0.6) for photovoltaic applications

The study of the pseudobinary system Cu(2)SnS(3-)Cu(2)SiS(3) shows that a solid solution (Cu(2)Si(x)Sn(1-x)S(3)) exists in the range 0.4 < or = Si/(Sn+Si) < or = 0.6. Based on diffuse reflectance and photoelectrochemical measurements these compounds show potential as absorber materials for photovoltaic devices. The compounds were prepared at 850 degrees C from copper sulfide, silicon, tin, and sulfur and were analyzed with single-crystal (for x approximately 0.40) and powder diffraction techniques. Optical band gaps of 1.25, 1.35, and 1.45 eV were observed for the three compositions x = 0.39, 0.48, and 0.61; cathodic photocurrent occurring is significant.     

A phosphorus supported multisite coordinating tris hydrazone P(S)[N(Me)N=CH-C6H4-o-OH]3 as an efficient ligand for the assembly of trinuclear metal complexes: synthesis, structure, and magnetism

A phosphorus supported multisite coordinating ligand P(S)[N(Me)N=CH-C(6)H(4)-o-OH](3) (2) was prepared by the condensation of the phosphorus tris hydrazide P(S)[N(Me)NH(2)](3) (1) with o-hydroxybenzaldehyde. The reaction of 2 with M(OAc)(2).xH(2)O (M = Mn, Co, Ni, x = 4; M = Zn, x = 2) afforded neutral trinuclear complexes [P(S)[N(Me)N=CH-C(6)H(4)-o-O](3)](2)M(3) [M = Mn (3), Co (4), Ni (5), and Zn (6)]. The X-ray crystal structures of compounds 2-6 have been determined. The structures of 3-6 reveal that the trinculear metal assemblies are nearly linear. The two terminal metal ions in a given assembly have an N(3)O(3) ligand environment in a distorted octahedral geometry while the central metal ion has an O(6) ligand environment also in a slightly distorted octahedral geometry. In all the complexes, ligand 2 coordinates to the metal ions through three imino nitrogens and three phenolate oxygens; the latter act as bridging ligands to connect the terminal and central metal ions. The compounds 2-6 also show intermolecular C-H...S=P contacts in the solid-state which lead to the formation of polymeric supramolecular architectures. The observed magnetic data for the (s = 5/2)3 L(2)(Mn(II))(3) derivative, 3, show an antiferromagnetic nearest- and next-nearest-neighbor exchange (J = -4.0 K and J' = -0.15 K; using the spin Hamiltonian H(HDvV) = -2J(S(1)S(2) + S(2)S(3)) - 2J'S(1)S(3)). In contrast, the (s = 1)(3) L(2)(Ni(II))(3) derivative, 5, displays ferromagnetic nearest-neighbor and antiferromagnetic next-nearest-neighbor exchange interactions (J = 4.43 K and J' = -0.28 K; H = H(HDvV)+ S(1)DS(1) + S(2)DS(2)+ S(3)DS(3)). The magnetic behavior of the L(2)(Co(II))(3) derivative, 4, reveals only antiferromagnetic exchange analogous to 3 (J = -4.5, J' = -1.4; same Hamiltonian as for 3).     

Structure-property correlations in solid solutions of (CuI)8P12-xAsx, 2.4< or = x < or =6.6

A series of P/As mixed pnicogen phases of composition (CuI)(8)P(12-x)As(x), in which x = 2.4, 4.2, 4.8, 5.4, and 6.6, have been synthesized and characterized by X-ray single crystal and powder diffraction, solid-state NMR spectroscopy, thermal gravimetric analysis, and impedance spectroscopy. These materials are isostructural to (CuI)(8)P(12) and consist of neutral, tubular P/As mixed pnicogen chains associated with Cu(I) and I(-) ions. The As is distributed throughout the pnicogen chains; however, the "roof" sites of the [P8] cage show preferred occupation by As relative to the other sites. Accordingly, the change in cell volume is not a linear function of the As incorporation. Solid-state (31)P NMR spectroscopy of the 40 % As incorporated sample are consistent with the X-ray structural model, with extensive broadening due to (31)P-(75)As coupling and site disorder, and a change in the chemical shifts of the resonances due to the As substitution into the lattice. The degree of copper ion site disorder, probed by single-crystal X-ray diffraction, increases with increasing As content. Although very little change is observed in the copper ionic conductivity of polycrystalline samples, which ranges from 1.8-5.1 x 10(-6) S cm(-1) for (CuI)(8)P(12-x)As(x), x = 0, 4.2, 5.4; a single crystal (x = 4.8) measured along the needle axis has a conductivity of 1.7 x 10(-3) S cm(-1) at 128 degrees C. This represents an order of magnitude improvement in conductivity over (CuI)(8)P(12) at the same temperature.     

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)).     

Weak M(II)-azide-4,4'-bipy ferromagnets based on unusual diamondoid (M = Mn) and 2D arrays (M = Co, Ni)

Four compounds of general formula [M(4,4'bipy)(N(3))2](n) (M = Mn (1), Zn (2), Co (3), Ni (4)) have been synthesized and magnetostructurally characterized by means of X-ray diffraction analysis, IR and ESR spectroscopies, and measurements of the magnetic susceptibility and magnetization. Compound 1 (C(10)H(8)N(8)Mn) crystallizes in the tetragonal P4(3)2(1)2 space group, Z = 4, with a = 8.229(2), b = 8.229(2), and c = 16.915(2) A. It exhibits an acentric 3D structure where Mn(II) ions are linked through EE-azide groups resulting in a diamondoid network. The 4,4'bipy ligands are coordinated on the axial positions of the octahedral spheres reinforcing the intermetallic connections. Weak ferromagnetism arising from spin canting is observed for compound 1. Compounds 2, 3, and 4 are proposed to be isomorphous and would consist of a 2D array where alternating EO + EE/EO + EE/EO + EO azide-chains are linked by 4,4'bipy ligands resulting in pi-pi stacked pyridyl-columns. The azido ligand dispositions in compounds 3 and 4 make possible systems of type -AF-AF-F-, which would give rise to a topological ferromagnetic behavior.     

Coupled ion/electron hopping in Li(x)NiO2: a 7Li NMR study

Deintercalated "Li(x)NiO2" materials (x = 0.25, 0.33, 0.50, 0.58, and 0.65) were obtained using the electrochemical route from the Li0.985Ni1.015O2 and Li0.993Ni1.007O2 compounds. Refinements of X-ray diffraction data using the Rietveld method show a good agreement with the phase diagram of the Li(x)NiO2 system studied earlier in this laboratory. Electronic conductivity measurements show a thermally activated electron-hopping process for the deintercalated Li0.5NiO2 phase. In the Li(x)NiO2 materials investigated (x = 0.25, 0.33, 0.50, and 0.58), 7Li NMR shows mobility effects leading to an exchanged signal at room temperature. A clear tendency for Li to be surrounded mainly by Ni3+ ions with the 180 degree configuration is observed, particularly, for strongly deintercalated materials with smaller Li+ and Ni3+ contents, even upon heating, when this mobility becomes very fast in the NMR time scale. This suggests that Li/vacancy hopping does occur on the NMR time scale but that Ni3+/Ni4+ hopping does not occur independently. The position of Li seems to govern the oxidation state of the Ni around it at any time; the electrons follow the Li ions to satisfy local electroneutrality and minimal energy configuration. The observed NMR shifts are compatible with the Li/vacancy and Ni3+/Ni4+ ordering patterns calculated by Arroyo y de Dompablo et al. for x = 0.25 and x = 0.50, but not for x = 0.33 and x = 0.58.     

Novel Zn1-xMnxSe (x = 0.1-0.4) one-dimensional nanostructures: nanowires, zigzagged nanobelts, and toothed nanosaws

Novel Zn1-xMnxSe one-dimensional nanostructures-straight nanowires (x = 0.1 and 0.3), zigzagged nanobelts (x = 0.4), and toothed nanosaws (x = 0.4)-were synthesized using the chemical vapor deposition method. They all consisted of single-crystalline wurtzite ZnSe crystals, irrespective of the Mn content. In particular, the nanosaws have a unique structure in which double-sided teeth are rooted in the nanowire core and bent so as to align as two parallel rows. The long axis is parallel to the [010] direction, and all of the teeth have the [0001] growth direction. The X-ray diffraction pattern confirms the formation of wurtzite ZnSe crystal and the decrease of the lattice constant owing to Mn doping. The Mn2+ emission at 2.1 eV (appeared below 100 K), originating from the d-d (4T1 --> 6A1) transition, proves the effective substitution of Mn2+ ions at the tetrahedral coordinate sites.     

Nature of copper(II)-lanthanide(III) magnetic interactions and generation of a large magnetic moment with magnetic anisotropy of 3d-4f cyclic cylindrical tetranuclear complexes [CuIILLnIII(hfac)2]2, (H3L = 1-(2-hydroxybenzamido)-2-(2-hydroxy-3-methoxybenzylideneamino)ethane and Hhfac = hexafluoroacetylacetone,LnIII = Eu,Gd, Tb,Dy)

A cyclic cylindrical 3d-4f tetranuclear structure, in which the 3d and 4f magnetic ions are arrayed alternately, has been found to be a suitable molecular design to produce a large magnetic moment and large magnetic anisotropy. Complexes 3-10 with the chemical formula [MLLn(hfac)2]2 ((MII, LnIII) = (Cu, Eu) (3), (Cu, Gd) (4), (Cu, Tb) (5), (Cu, Dy) (6), (Ni, Eu) (7), (Ni, Gd) (8), (Ni, Tb) (9), (Ni, Dy) (10)) have been synthesized, where H3L = 1-(2-hydroxybenzamido)-2-(2-hydroxy-3-methoxybenzylideneamino)ethane and Hhfac = hexafluoroacetylacetone. The powder X-ray diffractions and FAB-mass spectra demonstrated that these complexes assume a similar tetranuclear structure. The crystal structures of 4 and 5 showed that each complex has a cyclic cylindrical tetranuclear CuII2LnIII2 structure, in which the CuII complex functions as a "bridging ligand-complex" to two adjacent LnIII ions. The temperature-dependent magnetic susceptibilities from 2 to 300 K and the field-dependent magnetizations at 2 K from 0 to 5 T have been measured for four pairs of CuII2LnIII2 and NiII2LnIII2, in which compound NiII2LnIII2 containing diamagnetic NiII ion was used as the reference complex to evaluate the CuII-LnIII magnetic interaction. Comparison of the magnetic properties of the CuII2LnIII2 complex with those of the corresponding NiII2LnIII2 complex showed that the magnetic interaction between CuII and EuIII ions is weakly ferromagnetic and that between CuII and either of GdIII, TbIII, and DyIII ions is ferromagnetic. Complex CuII2GdIII2, 4, has an S = 8 spin ground state, due to the ferromagnetic spin coupling between SGd = 7/2 and SCu = 1/2 with coupling constants of J1 = +3.1 cm-1 and J2 = +1.2 cm-1. The magnetic measurements showed that compounds 5 and 6, CuII2LnIII2 (LnIII = Tb, Dy), exhibit large magnetic moments and large magnetic anisotropy due to the LnIII ion.