A series of 3d-4f binuclear complexes, [M(3-MeOsaltn)(MeOH)(x)(ac)Ln(hfac)(2)] (x = 0 for M = Cu-II, Zn-II; x = 1 for M = Co-II, Ni-II; Ln Gd-III, Dy-III, La-III), have been synthesized and characterized, where 3-MeOsaltn, ac, and hfac denote N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propane-diaminato, acetato, and hexafluoroacetylacetonato, respectively. The X-ray analyses demonstrated that all the complexes have an acetato- and diphenolato-bridged M-II-Ln(III) binuclear structure. The Cu-II-Ln(III) and Zn-II-Ln(III) complexes are crystallized in an isomorphous triclinic space group PT, where the Cu-II or Zn-II ion has square pyramidal coordination geometry with N2O2 donor atoms of 3-MeOsaltn at the equatorial coordination sites and one oxygen atom of the bridging acetato ion at the axial site. The Co-II-Ln(III) and Ni-II-Ln(III) complexes are crystallized in an isomorphous monoclinic space group P2(1)/c, where the Co-II or Ni-II ion at the high-spin state has an octahedral coordination environment with N2O2 donor atoms of 3-MeOsaltn at the equatorial sites, and one oxygen atom of the bridged acetato and a methanol oxygen atom at the two axial sites. Each Ln(III) ion for all the complexes is coordinated by four oxygen atoms of two phenolato and two methoxy oxygen atoms of "ligand-complex" M(3-MeOsaltn), four oxygen atoms of two hfac(-), and one oxygen atom of the bridging acetato ion; thus, the coordination number is nine. The temperature dependent magnetic susceptibilities from 1.9 to 300 K and the field-dependent magnetization up to 5 T at 1.9 K were measured. Due to the important orbital contributions of the Li-III (Tb-III, Dy-III) and to a lesser extent the M-II (N-III, Co-II) components, the magnetic interaction between M-II and Ln(III) ions were investigated by an empirical approach based on a comparison of the magnetic properties of the M-II-Ln(III), Zn-II-Ln(III), and complexes. The differences of chi T-M and M(H) values for the M-II-Ln(III), Zn-II-Ln(III) and those for the M-II-La-III complexes, that is, Delta(T) = (chi T-M)(MLn) - (chi T-M)(znLn)-(chi T-M)(MLa) = J(MLn)(T) and Delta(H) = M-MLn(H) - M-ZnLn(H) - M-MLa(H) = J(MLn)(H), give the information of 3d-4f magnetic interaction. The magnetic interactions are ferromagnetic if M-II = (Cu-II, Ni-II, and Co-II) and Ln = (Gd-III, Tb-III, and Dy-III) The magnitudes of the ferromagnetic interaction, J(MLn)(T) and J(Mln)(H), are in the order Cu-II-Gd-III > Cu-II-Dy-III > Cu-II-Tb-III, while those are in the order of M-II-Gd-III approximate to M-II-Tb-III > M-II-Dy-III for M-II = Ni-II and Co".Alternating current (ac) susceptibility measurements demonstrated that the Ni-II-Dy-III and Co-II-Tb-III complexes showed out-of-phase signal with frequency-dependence and the Ni-II-Dy-III and Co-II-Dy-II complexes showed small frequency-dependence. The energy barrier for the spin flipping was estimated from the Arrhenius plot to be 14.9(6) and 17.0(4) K for the (NiII-TbIII) and Co-II-Tb-III complexes, respectively, under a dc bias field of 1000 Oe.

Copper(II) complexes with tridentate ligands H2LR (R = H, 2-Me, and 5-Me) derived from 1:1 condensation products of DL-phenylalanine and imidazole-4-carbaldehyde derivatives (imidazole-4-carbaldehyde, 2-methylimidazole-4-carbaldehyde, and 5-methylimidazole-4-carbaldehyde), [CuClHLH] (1), [CuClHL2-Me] (2), [CuClHL5-Me]-MeOH (3), [CuBrHLH] (4a and 4b), and [CuBrHL2-Me] (5), were prepared. Two types of crystals in the reaction vessel, 4a and 4b, were obtained in the reaction between CuBr2 and H2LH. Their assembled structures were determined by single-crystal analysis. Except for 4b, the complexes assumed a homochiral chain structure constructed by intrachain imidazole-carboxylato hydrogen bonds between the adjacent two molecules, and the adjacent chains are linked by interchain Cu-X (X = Cl or Br) interactions. 3 exhibited a shorter interchain Cu-X distance and crystallized in the acentrosymmetric space group C222(1) representing a spontaneous resolution (conglomerate), while 1, 2, 4a, and 5 gave a stacking of the adjacent chains with opposite chiralities to give racemic crystals. 4b assumed a homochiral chain structure constructed by a coordination bond between a copper(II) ion and an oxygen atom of the carboxyl group of the adjacent complex. A zinc(II) complex, [ZnClHLH] (6), showed a similar racemic crystal to that of 4b.

A mononuclear copper(II) complex, [2-ethoxy-6-{[3-(2-methyl-4-imidazolylmethyleneamino)propyl]iminomethyl}-phenolato]copper(II) perchlorate [CuHL]ClO4 and its deprotonated complex at the imidazole moiety, [CuL](n), were prepared. The structure of [CuHL]ClO4 Consists of a cation [CuHL](+) exhibiting a four-coordinated square-planar geometry and an anion ClO4-, while [CuL](n) assumes an imidazolato-bridged zigzag-chain structure, in which the copper(II) ion is coordinated by the imidazolato nitrogen atom of the adjacent Molecule with Cu-N = 2.258(5) A and the two adjacent CuL units assumes a perpendicular orientation. The temperature-dependent magnetic susceptibilities from 2.0 to 300K and field-dependent magnetization at 2.0 K demonstrate that [CuHL]ClO4 is a magnetically isolated copper(II) molecule while [CuL](n) is a ferromagnetic chain. The magnetic susceptibility data of [CuL](n) were analyzed by Baker's model based on H = -2J Sigma SAjSAj+1 for chain of equally spaced copper(II) ions to give the best-fit parameters of g = 2.08 and J = +0.63 cm(-1).

The polymeric isomorphous hybrid inorganic-organic vanadium oxide compounds: [M(Im)4V2O6], M = Mn(I), Co(II), Ni(III), Im = imidazole, were investigated between 100 (2) and 295 (2) K by single crystal X-ray diffraction. The compounds contain 2-D sheets packed perpendicular to c* and undergo a reversible order-disorder phase transitions. The room temperature P42/n disordered phase (Z = 8) is reversibly transformed to the I41/a ordered phase (Z = 32) below 281 (2) K for I and 175 (2) K for II, requiring a change of the hydrogen bond connectivity for two of the eight imidazoles per asymmetric unit of the I41/a structure. The structure of I has a well defined phase transition but II shows a large hysteresis and it was necessary to include stacking faults in the modelling of II at low temperatures. The structure of III was shown to be partially twinned but ordered in space group P2/n (Z = 8) at 100 (2) K, with two different localised regions each containing four pairs of inversion related imidazoles hydrogen bonding to framework oxygen atoms involving eight imidazoles in one region and six imidazoles in the other. Models for the phase transition mechanisms are considered.

Sessions 7 1In the case of the bipyridyl ligand (5MeCONHbpy) possessing -NHC(O)Me at 5,5'-positions, of which the orientation is different from -C(O)NH t Bu, the structures of [Ru(5MeCONHbpy)3] 2+ drastically depend on the counter ion.The hexafluorophosphate salt, [Ru(5MeCONHbpy)3](PF6)2, yield a bundle structure of onedimensional chains in which the amide groups connect together with each other via hydrogen bonds.On the other hand, the chloride salt, [Ru(5MeCONHbpy)3]Cl2, give layer structures, where the layer of ruthenium complexes link with the chloride layer.Here, the differences in photophysical properties of the ruthenium complexes with amide groups having different orientation will be presented.

Three tetranuclear copper(II)-lanthanide(III) complexes, [{Cu(II)LLn(III) (o-van)(CH3COO)(MeOH)}(2)]center dot 2H(2)O (Ln(III) = Gd-III, Tb-III, and Dy-III), were synthesized and characterized, where H3L is 1-(2-hydroxybenzamido)-2-(2-hydroxy-3-methoxybenzylideneamino)ethane and o-van is 3-methoxysalicylaldehydato. These compounds are isomorphous to each other and consist of a cyclic tetranuclear Cu(2)(II)Ln(2)(III) structure, in which the Cu-II and Ln(III) ions are alternately arrayed and the Cu-II component complex. [(CuL)-L-II](-) unit functions as a "bridging ligand-complex" between two adjacent Ln(III) ions through the phenolato and methoxy oxygen atoms at one side and the amido oxygen atom at the another side. The temperature-dependent magnetic susceptibilities from 2.0 to 300.0 K and the field-dependent magnetizations at 2.0 K from 0 to 5 T showed that the magnetic interaction between Cu-II and each of the lanthanide ions is ferromagnetic. The magnetic susceptibilities of [{(CuLGdIII)-L-II (o-van)(CH3COO)(MeOH)}(2)]center dot 2H(2)O were analyzed by using a spin-only Hamiltonian H = -2J(1) (S-Cul S-Gd1 + SCu2SGd2) - 2J(2)(SCu1SGd2 + SCu2SGd1) based on a cyclic tetranuclear structure and gave the best-fit parameters of g = 1.97, J(1) = +3.8 cm(-1), J(2) = +0.7 cm(-1), and zJ' = -0.01 cm(-1). The magnetization data at 2.0 K of [(Cu-II LGdIII (o-van)(CH3COO)(MeOH))(2)]center dot 2H(2)O were well reproduced by using a Brillouin function with an S = 8 spin ground state due to the ferromagnetic interactions between Cu-II and Gd-III ions and g = 1.97. The ac magnetic susceptibilities of [(Cu(II)LLn(III)(o-van)(CH3COO)(MeOH))(2)]center dot 2H(2)O (Ln(III) = Tb-III and Dy-III) in the temperature range 1.8-10.0 K with a 3 G ac field oscillating in the range 1-1000 Hz showed a frequency dependence characteristic of SMMS.

An extensive series of tetranuclear CuII2LnIII2 complexes [CuIILLnIII(hfac)2]2 (with LnIII being all lanthanide(III) ions except for the radioactive PmIII) has been prepared in order to investigate the nature of the CuII-LnIII magnetic interactions and to try to answer the following question: What makes the CuII2TbIII2 and CuII2DyIII2 complexes single molecule magnets while the other complexes are not? All the complexes within this series possess a similar cyclic tetranuclear structure, in which the CuII and LnIII ions are arrayed alternately via bridges of ligand complex (CuIIL). Regular SQUID magnetometry measurements have been performed on the series. The temperature-dependent magnetic susceptibilities from 2 to 300 K and the field-dependent magnetizations from 0 to 5 T at 2 K have been measured for the CuII2LnIII2 and NiII2LnIII2 complexes, with the NiII2LnIII2 complex containing diamagnetic NiII ions being used as a reference for the evaluation of the CuII-LnIII magnetic interactions. These measurements have revealed that the interactions between CuII and LnIII ions are very weakly antiferromagnetic if Ln=Ce, Nd, Sm, Yb, ferromagnetic if Ln=Gd, Tb, Dy, Ho, Er, Tm, and negligible if Ln=La, Eu, Pr, Lu. With the same goal of better understanding the evolution of the intramolecular magnetic interactions, X-ray magnetic circular dichroism (XMCD) has also been measured on CuII2TbIII2, CuII2DyIII2, and NiII2TbIII2 complexes, either at the L- and M-edges of the metal ions or at the K-edge of the N and O atoms. Last, the CuII2TbIII2 complex exhibiting SMM behavior has received a closer examination of its low temperature magnetic properties down to 0.1 K. These particular measurements have revealed the unusual very slow setting-up of a 3D order below 0.6 K.

A 3d-4f complex with the formula of {Na[(CuL)(4)Gd]}(1 infinity) was prepared, where (CuL)(-) is a "ligand-complex," [N-(4-methyl-6-oxo-3-azahept-4-enyl)oxamato]copper(II). The structure consists of a pin-wheel-like CU4Gd core and Na+ ion as a connector to give a one-dimensional chain. The magnetic data and their analyses demonstrated an intramolecular ferromagnetic interaction within a CU4Gd core and an intercore antiferromagnetic interaction operating through Na+ ion with the coupling parameters of J = +1.09cm(-1), zJ' = -0.07 cm(-1); S-Cu = 1/2, S-Gd = 7/2).