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Single crystals of the title compounds are prepared by slow diffusion of diethyl ether into MeCN solutions of [NBu4]3[W(CN)8], Ln(NO3)3 (Ln: Eu, Tb), and Ln′(NO3)3 (Ln′: Tb, Gd, Sm).

Crystals of Er(H2O)4[M(CN)8] (M: W, Mo) are prepared by slow diffusion of diethyl ether into an acetonitrile solution of [NBu4]3[M(CN)8] and [Er(H2O)5](NO3)3.

The title compound is prepared in 76% yield by slow diffusion of Et2O into a MeCN solution of (NBu4)3[Mo(CN)8] and Eu(NO3)3.

Slow diffusion of aqueous solutions containing K4[MoIII(CN)7]·2H2O and a MnII salt, respectively, affords well shaped single crystals of two cyano-bridged bimetallic phases ordering ferromagnetically with a pronounced magnetic anisotropy in the magnetically-ordered phase.

The title compound has been synthesized by slow diffusion of aqueous solutions containing K4[Mo(CN)7]·2H2O and [Mn(H2O)6](NO3)2, respectively. The compound crystallizes in the monoclinic system, space group P21/c. The Mo site is surrounded by seven −C−N−Mn linkages in a distorted pentagonal bipyramid fashion. There are two distorted octahedral Mn sites, one with four and the other with three Mn−N−C−Mo linkages. The structure is three-dimensional and of low symmetry. It consists of ladders made of edge-sharing lozenge motifs (MoCNMnNC)2 running along the a direction. These ladders are linked further along the b and c directions. Both temperature dependences of the magnetic susceptibility and field dependences of the magnetization have been investigated along the three crystallographic directions, a, b, and c*. The angular dependence of the magnetization in the ab plane as a function of the external field has also been measured. These single crystal magnetic measurements have revealed that the compound orde...

A survey on the synthesis of cyano-bridged coordination polymer nanoparticles (CPNs) performed in our group and on the study of their related magnetic properties is given. Two synthetic approaches consisting in the one-pot synthesis of soluble CPNs and in the sequential growth of CPNs onto appropriate matrices are reviewed. A special emphasis is placed on the magnetic properties of CPNs and the determination of the magnetic regime in these systems, which strongly depends on various factors. We show that the size of the nanoparticles, the magnetostatic interparticles and/or the NP–matrix interactions provide significant modification of the superparamagnetic relaxation regime.

A new family of cyano-bridged coordination polymers Ln(H2O)5[M(CN)8] (Ln = Eu, Tb, Sm, Gd; M = Mo, W) were obtained and characterized by X-ray diffraction, photoluminescence spectroscopy, and magnetic analyses. These compounds are isomorphous and crystallize in the tetragonal system P4/nmm, forming two-dimensional gridlike networks. The Eu- and Tb-containing coordination polymers are room-temperature optically active emitters displaying the characteristic 5D0 → 7F0-4 (Eu3+) and 5D4 → 7F6−2 (Tb3+) transitions. All of the coordination polymers except Eu(H2O)5[M(CN)8] present long-range magnetic ordering at low temperatures. The coexistence of luminescence with ferromagnetic ordering for Tb(H2O)5[M(CN)8] (M = Mo, W) suggests that these compounds may be considered as bifunctional magneto-luminescent coordination polymers exhibiting diverse physical responses when subjected to various external stimuli.

A new cyano-bridged coordination polymer network Tb(H2O)5-[Mo(CN)8] was obtained and characterized. This compound has a two-dimensional layered structure and presents luminescence along with a magnetic transition at low temperature.

Two coordination polymers [MII(H2O)2]2[MoIV(CN)8]·4H2O [MII = Co (1), Mn (2)] were prepared as monocrystals and structurally characterised. These compounds crystallise in the tetragonal systems I4/m (1) and I4/mcm (2) and form three-dimensional networks containing channels occupied by two types of water molecules, i.e. coordinated to MII and crystallised ones. The dehydration of these materials occurs topochemically to give [MII(H2O)]2[MoIV(CN)8] compounds having an open metal coordination site on the MII ions that may be accessible to coordination by other species and serve as a reaction site. The intercalation of water, ammonia and amines has been studied. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)