Design of chiral magnets: Cyanide-bridged bimetallic assemblies based on cyclohexane-1,2-diamine

Abstract Four magnetic compounds based on chiral ligands trans-(1S,2S)-chxn and trans-(1R,2R)-chxn (chxn: cyclohexane-1,2-diamine), [Ni(trans-(1S,2S)-chxn)2]3[Fe(CN)6]2·2H2O (1), [Ni(trans-(1R,2R)-chxn)2]3[Fe(CN)6]2·2H2O (2), [Cu(trans-(1S,2S)-chxn)2]3[Fe(CN)6]2·4.5H2O (3) and [Cu(trans-(1R,2R)-chxn)2]3[Fe(CN)6]2·4.5H2O (4), are reported. The four compounds are chiral, as confirmed by X-ray analyses and circular dichroism measurements. From the magnetic point of view, 1 and 2 behave as ferromagnets, whereas 3 and 4 show a paramagnetic behavior.

Magnetic properties of Cd–Mg–Tb quasicrystal

Abstract The magnetic properties of an icosahedral Cd–Mg–Tb quasicrystal were studied by dc magnetization and thermoremanent magnetization time decay measurements. An unusual temperature dependence of the susceptibility below freezing temperature can be attributed to the inhomogeneous sample structure. In addition to the quasicrystalline portion which exhibits a spin-glass transition at 12.5 K a part of the sample behaves like a paramagnet. During aging of the sample in air the spin-glass part transforms into the paramagnetic one. The linear M ∝ H dependence of the thermoremanent magnetization time decay on magnetic field is quite different as compared to canonical spin glasses.

Hybrid materials containing organometallic cations and 3-D anionic metal dicyanamide networks of type [Cp*2M][M′(dca)3]

A new series of hybrid materials of type [Cp*2M][M′(dca)3] has been prepared by cation templation and structurally characterised (M = Fe(III), Co(III); M′ = Mn(II), Fe(II), Co(II), Ni(II), Cd(II); dca− = N(CN)2−). The crystallographic analysis of [Cp*2Fe][Cd(dca)3] showed that the [Cd(dca)3]− anionic framework is of a symmetrical 3-D α-polonium type, containing octahedral Cd nodes and μ1,5-dca bridging ligands. The [Cp*2Fe]+ cations occupy the cube-like cavities within the framework. The cationic and anionic-framework sublattices remain magnetically independent and display susceptibilities, over the range 300 to 2 K, of a Curie–Weiss nature obtained by adding a S = 1/2 (Cp*2Fe+) or a S = 0 …

Tuning the magnetic properties in the layered molecular based magnets A[FeIIRuxIIIM1−xIII(ox)3] (MIII=Cr or Fe; ox=oxalate; A=organic or organometallic cation)

Abstract The magnetic properties of the family of layered molecular magnets A[FeIIMIII(ox)3] (MIII=Cr, Fe, Ru; ox=oxalate; A+=[NBu4]+, [ CoCp 2 ∗ ] + ) are reported. In particular, a detailed magnetic study of the solid solutions FeII(RuIIICrIII) and FeII(RuIIIFeIII) has been undertaken. We show that in these magnets both, transition temperatures and coercive fields, can be easily tuned by changing the chemical composition of the material, i.e. the ratio RuIII/MIII (MIII=Cr, Fe) within the magnetic layers and the type of cation A+ inserted in between the layers. Coercive fields as high as 2.2 T have been reached in this way.

Magnetic properties of MoS 2 nanotubes doped with lithium

DC magnetization measurements of lithium-doped molybdenum sulfide nanotubes (LixMoS2, 2.2 10 kOe, the nonlinear part in H<5 kOe with saturation at approximately 10 kOe can be observed. This suggests a formation of ferromagnetic clusters even at room temperature. No magnetic phase transition between 2 and 300 K has been detected.

Unusual Magnetic State in Lithium-DopedMoS2Nanotubes

We report on the very peculiar magnetic properties of an ensemble of very weakly coupled lithium-doped MoS2 nanotubes. The magnetic susceptibility chi of the system is nearly 3 orders of magnitude greater than in typical Pauli metals, yet there is no evidence for any instability which would alleviate this highly frustrated state. Instead, the material exhibits peculiar paramagnetic stability down to very low temperatures, with no evidence of a quantum critical point as T-->0 in spite of clear evidence for strongly correlated electron behavior. The exceptionally weak intertube interactions appear to lead to a realization of a near-ideal one-dimensional state in which fluctuations prevent the…

Increasing the Coercivity in Layered Molecular-based Magnets A[MIIMIII(ox)3] (MII = Mn, Fe, Co, Ni, Cu; MIII = Cr, Fe; ox = oxalate; A = organic or organometallic cation)

Discrete Dinuclear Complexes and Two‐Dimensional Architectures from Bridging Polynitrile and Bipyrimidine (bpym) Ligands: Syntheses, Structures and Magnetic Properties of [M 2 (bpym)(dcne) 4 (H 2 O) 2 ] (M = Mn II , Co II ) and [M 2 (bpym)(dcne) 4 (H 2 O) 4 ]·2H 2 O (M = Fe II , Cu II ) (dcne − = [(CN) 2 CC(O)OEt)] − )

One-pot reactions in aqueous solutions of the polynitrile anion dcne− {2,2-dicyano-1-ethoxyethenolate = [(CN)2CC(O)OEt)]−] with the MII ions (M = Mn, Fe, Co, Cu) in the presence of bpym (2,2′-bipyrimidine) afford the first mixed dcne/bpym compounds [M2(bpym)(dcne)4(H2O)2] (1: M = Mn; 2: M = Co) and [M2(bpym)(dcne)4(H2O)4]·2H2O (3: M = Fe; 4: M = Cu). The new compounds have been characterized by IR spectroscopy and X-ray crystallography. Compounds 1 and 2 are isostructural, with each metal ion being located in an MN5O pseudo-octahedral environment with three N atoms coming from three dcne− ligands, two nitrogen atoms from bpym and one oxygen atom from a water molecule. The extended structure…

Magnetic properties of hybrid molecular materials based on oxalato complexes

Abstract The use of [MIII(ox)3]3− (MIII=Ru, Rh) complexes as building blocks for hybrid molecular materials is highlighted with two different synthetic approaches. The first strategy is the combination of organic donors and [RuIII(ox)3]3− units, resulting in the radical salt of formula TTF3[Ru(ox)3]·0.5EtOH·4H2O (1) which shows coexistence of paramagnetism and semiconducting properties. The second approach is the synthesis of extended 2D bimetallic oxalato-bridged networks of general formula [FeCp2 *][MIIRh(ox)3] in which paramagnetic layers of decamethylferricinium cations are alternated with paramagnetic bimetallic layers.

Layered Molecule-Based Magnets Formed by Decamethylmetallocenium Cations and Two-Dimensional Bimetallic Complexes [MIIRuIII(ox)3]−(MII=;Mn, Fe, Co, Cu and Zn; ox=oxalate)

Abstract A new series of hybrid organometallic-inorganic layered magnets with formula [Z III Cp * 2 ] [M II Ru III (ox) 3 ] ( Z III =Co and Fe; M II =Mn, Fe, Co, Cu, and Zn; ox=oxalate: Cp * =pentamethylcyclopentadienyl) has been prepared. All of these compounds are isostructural to the previously reported [ Z III Cp * 2 ] [ M II M III (ox) 3 ] ( M III =Cr, Fe) series and crystallize in the monoclinic space group C 2/ m , as found by powder X-ray diffraction analysis. They are novel examples of magnetic materials formed by bimetallic oxalate-based extended layers separated by layers of organometallic cations. The magnetic properties of all these compounds have been investigated (ac and dc m…

Mn 12 single-molecule magnets incorporated into mesoporous MCM-41 silica

Abstract The incorporation of four Mn12 derivatives, namely [Mn12O12(O2CR)16(H2O)4] (R=CH3 (1), CH3CH2 (2), C6H5 (3), C6F5 (4)), into the hexagonal channels of the MCM-41 mesoporous silica have been studied. Only the smallest clusters 1 and 2 that are those with compatible size with the pores of MCM-41 could be incorporated into the mesoporous silica. Powder X-ray diffraction (XRD) analysis and N2 adsorption–desorption isotherm experiments show that the well-ordered hexagonal structure of MCM-41 is preserved and that the Mn12 clusters are inside the pores. The magnetic properties of the MCM-41/1 nanocomposite material indicate that the structure of the cluster is maintained after incorporat…

Synthesis, structure and magnetic properties of iron (II), cobalt (II) and nickel (II) complexes of 2,6-bis(pyrazol-3-yl)pyridine and paramagnetic counterions

Abstract Iron (II), cobalt (II) and nickel (II) complexes of 2,6-bis(pyrazol-3-yl)pyridine (bpp) with [Cr(C2O4)3]3− have been prepared. They were characterised by single-crystal X-ray diffraction, magnetic susceptibility measurements and thermal gravimetric analyses. All three compounds are isostructural and they are formed by isolated [MII(bpp)2]2+ and [Cr(C2O4)3]3− complexes and free ClO4 −. As expected, only the salt [Fe(bpp)2]2[Cr(C2O4)3]ClO4·5H2O shows a thermal spin transition with transition temperature (T1/2) around 375 K that is correlated to the loss of water molecules.

Molecule-Based Magnets Formed by Bimetallic Three-Dimensional Oxalate Networks and Chiral Tris(bipyridyl) Complex Cations. The Series [ZII(bpy)3][ClO4][MIICrIII(ox)3] (ZII = Ru, Fe, Co, and Ni; MII = Mn, Fe, Co, Ni, Cu, and Zn; ox = Oxalate Dianion)

The synthesis, structure, and physical properties of the series of molecular magnets formulated as [ZII(bpy)3][ClO4][MIICrIII(ox)3] (ZII = Ru, Fe, Co, and Ni; MII = Mn, Fe, Co, Ni, Cu, and Zn; ox = oxalate dianion) are presented. All the compounds are isostructural to the [Ru(bpy)3][ClO4][MnCr(ox)3] member whose structure (cubic space group P4(1)32 with a = 15.506(2) A, Z = 4) consists of a three-dimensional bimetallic network formed by alternating MII and CrIII ions connected by oxalate anions. The identical chirality (lambda in the solved crystal) of all the metallic centers determines the 3D chiral structure adopted by these compounds. The anionic 3D sublattice leaves some holes where th…