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The lanthanide-tuned structural and magnetic characterization of magnetic materials based on the use of 2,2':6',2'-terpyridine (terpy) as a blocking ligand at the [Ln.sup.III] center which forms isomorphous cyano-bridged compounds is demonstrated.

[Mn(super III)(salen)(H2O)(super +1)[salen = the N,N' -ethylenebis(salicylideneaminato) dianion], which has a high-spin ground state (S = 2), as a building block is studied. Results suggest the possibility of design and construction of single molecule magnets or high-spin molecules based on Schiff-base cationic precursors and octacyanometalates.

The self-assembly of [NbIV(CN)8]4- with different 3d metal cenfers in an aqueous solution and an escess of pyrazole resulted in the formation of four 3D isostructural compounds {[MII(pyrazole)4]2[NbIV(CN)8] · 4H2O}n, where MII = Mn, Fe, Co, and Ni for 1-4, respectively. All four assemblies crystallize in the same I41/a space group and show identical cyanido-bridged structures decorated with pyrazole molecules coordinated to MII centers. All four compounds show also long-range magnetic ordering below 24, 6, 6, and 13 K, respectively. A thorough analysis of the structural and magnetic data utilizing the molecular field model has allowed for an estimation of the values of coupling constants JM-Nb attributed to the one type of MII-NC-NbIV linkage existing in 1-4. The JM-Nb values increase monotonically from -6.6 for 1 through -3.1 for 2 and +3.5 for 3, to +8.1 cm-1 for 4 and are strongly correlated with the number of unpaired electrons on the MII metal center. Average orbital contributions to the total exchange coupling constants JM-Nb have also been identified and calculated: antiferromagnetic JAF = -21.6 cm-1 originating from the dxy, dxz, and dyz orbitals of MII and ferromagnetic JF = +15.4 cm-1 originating from dz2 and dx2-y2 orbitals of MII. Antiferromagnetic interaction is successively weakened in the 1-4 row with each additional electron on the t2g level, which results in a change of the sign of JM-Nb and the nature of long-range magnetic ordering from ferrimagnetic in 1 and 2 to ferromagnetic in 3 and 4. [ABSTRACT FROM AUTHOR]

The reaction of cetium(lll) nitrate, sodium octacyanotungstate(V), and 2,2'-bipyrimidine (bpm) under vanous conditions leads to the formation of three new compounds: ionic [Ce2(bpm)(dmf)6(H2O)8][W(CN)5]2∙3H2O (1; dmf = N,N- dimethylforrnamide), tetranuclear molecules [Ce2(bpm)(dmso)8(H2O)4][W(CN)8]2∙4H2O (2; dmso = dimethyl sulfoxide), and a two-dimensional inorganic-organic hybrid coordination polymer ([Ce2(bpm)(dmf)8(H2O)2][W(CN)5]2)n-2nH2O (3), allot which contain the subunit [Ce2(u-bpm)] within the structure. These systems were characterized by single-crystal X-ray diffractometry, FTIR spectroscopy, and thermogravimetric analysis. Magnetic susceptibility measurements for 1-3 were performed on polycrystalline samples ot the compounds. Magnetic behavior was interpreted in terms of the ligand-field splitting parameters and the exchange interaction between lanthanide centers and a d-electron spin carrier. The msufts confirmed the ferromagnetic cyano-mediated (Ce-NC-W) interaction kew = 1.7 (2) and 1.4(3) cm-1 (3) compared to the antiferromagnetic (Ce-bpm-Ce) interaction JCeCe = -1.1 cm-1 (1 and 2). [ABSTRACT FROM AUTHOR]

Review: 56 refs. [ABSTRACT FROM AUTHOR]

The novel tetranuclear copper (II) cluster namely (C 5 H 7 N 2 ) 2 [Cu 4 (µ 4 -O)(µ 3 -SO 4 ) 4 (C 5 H 6 N 2 ) 4 ] (1) was obtained by the hydrothermal reaction of copper (II) sulfate and the monodentate 4-aminopyridine ligand. Single-crystal X-ray diffraction indicated that compound 1 crystallizes in the monoclinic system, space group C2/c, a = 25.827 (5) Å, b = 10.657 (5) Å, c = 19.838 (5) Å, β = 121.195 (5)°, V = 4671 (3) Å 3 and Z = 4. The discrete [Cu 4 (µ 4 -O)(µ 3 -SO 4 ) 4 (C 5 H 6 N 2 ) 4 ] 2− anion present in (1) contains Cu 4 (µ 4 -O) tetrahedra with the copper centres held together by four sulfate groups in two different coordinated modes: η 1 .η 1 .η 1 .μ 3 :3.1110 and η 2 .η 1 .μ 3 :3.2100 (Harris notation). Again, the structural arrangement and the intermolecular interactions such as hydrogen-bonding are discussed from which supramolecular assembly was formed. The thermal behavior of the compound, studied by TG-DSC, showed that the successive decomposition stages of precursor lead to the formation of intermediate phases during heating giving rise to the copper oxide as a final product at 700 °C. Characteristic IR bands are discussed in terms of the known structure of (1). The magnetic properties of (1) have been studied by variable temperature dc magnetic susceptibility techniques. Using an idealized geometry of the tetranuclear cluster the magnitude of exchange coupling constants is examined. The calculations within the simplified model reveal a relatively strong superexchange interaction between the Cu(II) ions (on the order of a 100 cm −1 ) indicating a substantial anisotropy with the apical coupling being ferromagnetic while the equatorial coupling favoring an antiferromagnetic arrangement of the spin components. [ABSTRACT FROM AUTHOR]

Graphical abstract A combination of dinuclear Fe O Fe and tetranuclear Co CN Fe O Fe NC Co units with strong intramolecular antiferromagnetic coupling. Abstract The synthesis, characterization, structure and magnetic properties of a hexametallic mixed-metal iron(III)–cobalt(III) compound are described. The compound has been characterized by standard spectroscopic and analytical methods to determine its composition. Single-crystal X-ray diffraction has shown that the asymmetric unit consists of discrete dinuclear dicationic units of {(µ-oxido-µ-[sulfato- O1 , O2 ])bis[tris(2-pyridyl-methyl)amineiron(III)]}2+, herein designated as Fe12, and two half-dinuclear dianionic units of {(µ-oxido)bis[(µ-cyanido- κN -pentacyanidocobaltato(III))(tris(2-pyridyl-methyl)-amine)iron(III)]}2− units, herein designated as Fe33a and Fe44b, generating the overall composition Co 2 Fe 4 O 2 (CN) 12 (tpa) 4 , 1 , where tpa is tris(2-pyridyl-methyl)amine. X-ray structural results and thermogravimetric and differential scanning calorimetry measurements also indicate that the compound, depending upon its history, may contain up to nine interstitial waters of hydration, herein designated as 1 (H 2 O) 9. In the dinuclear dicationic unit, the bridging Fe O Fe bond in Fe12 is bent and there is also an Fe O S O Fe sulfato-based bridge with an angle of 132.8°. In contrast, in the two dinuclear dianionic units, Fe33a and Fe44b, the Fe O Fe bond angle is crystallographically constrained to be 180°. The Co CN Fe bonds are almost co-linear, with Co C N angles of 176° and C N Fe angles of 169°. In each species the tpa ligand is tripodal tetradentate with the tertiary amine trans to the sulfato ligand or to the cyanide ligand in the dianions or the bridged oxido ligand in the dications. Bond lengths and angles are all in the typical range for Fe(III) and Co(III) compounds. The magnetic behavior of 1 (H 2 O) 9 , obtained upon cooling from 300 to 2 K, reveals a strong antiferromagnetic interaction between the Fe(III) ions in each dinuclear unit. Attempts to discriminate between the two Fe(III) dinuclear units in 1 (H 2 O) 9 have in all cases led to two very different Heisenberg isotropic exchange coupling constants, namely J = −220(2) and −716(32) cm−1 for 1 (H 2 O) 9 ; i.e. one of the dinuclear units, probably the Fe12 unit, is so strongly antiferromagnetically coupled that it is close to diamagnetic between 2 and ca. 250 K and has a Heisenberg S = 0 ground state. [ABSTRACT FROM AUTHOR]

A novel two-dimensional cyanide-bridged polymer [CuII(tren)]{CuI[W(V)(CN)8]} . 1.5H2O (tren = tris(2-aminoethyl)amine) formed via the simultaneous in situ metal-ligand redox reaction of [Cu(tren)(OH2)]2+ and self-assembly with [W(V)(CN)8]3- consists of a {CuI[W(V)(CN)8]} square grid built of CuI centres of tetrahedral geometry coordinatively saturated by CN bridges and [W(V)(CN)8]3- capped by [CuII(tren)]2+ moieties; it exhibits ferromagnetic coupling J1 = +5.8(1) cm(-1) within the CuII-W(V) dinuclear subunits and weak antiferromagnetic coupling J2 = -0.03(1) cm(-1) between them through diamagnetic CuI spacers.