How can [Mo(IV)(CN)6](2-), an apparently octahedral (d)(2) complex, be diamagnetic? Insights from quantum chemical calculations and magnetic susceptibility measurements.

Quantum chemical calculations are employed to elucidate the origin of a puzzling diamagnetism for a hexacyanomolybdate(IV) anion, [Mo(CN)6](2-), which was previously reported by Szklarzewicz et al. [Inorg. Chem., 2007, 46, 9531-9533]. The diamagnetism is surprising because for the octahedral (d)(2) complex one would rather expect a (paramagnetic) triplet ground state, clearly favored over a (diamagnetic) singlet state by an exchange interaction between two d electrons in the t2g orbitals. Nevertheless, the present calculations reveal that the minimum energy structure of isolated [Mo(CN)6](2-) is not an octahedron, but a trigonal prism; the latter geometry allows maximization of a σ-donation from the cyanides to the electron-deficient Mo(iv) center. Unlike for the octahedron, for the trigonal prism structure the singlet and triplet spin states are close in energy to within a few kcal mol(-1). Although the actual relative energy of the two spin states turns out to be method-dependent, the complete active space calculations (CASPT2; with the appropriate choice of the IPEA shift parameter) can reproduce the singlet ground state, in agreement with the experimentally observed diamagnetism. Moreover, magnetic measurements reveal a slight increase of the magnetic susceptibility with the increase of temperature from 100 to 300 K, suggesting an admixture of a thermally induced paramagnetism (possibly due to Boltzmann population of the low-energy triplet state) on top of the dominant diamagnetism. Our prediction that the geometry of [Mo(CN)6](2-) should significantly deviate from the ideal octahedron, not only in the gas phase, but also in a periodic DFT model of the crystalline phase, as well as the experimentally confirmed diamagnetic properties, does not agree with the previously reported ideal octahedral structure. We suggest that this crystal structure might have been determined incorrectly (e.g., due to overlooked merohedral twinning or superstructure properties) and it should be re-investigated.

Magnetocaloric effect and critical behaviour in Mn2-pyridazine-[Nb(CN)8] molecular compound under press.

A comprehensive study of magnetocaloric effect (MCE) and critical behaviour in the ferrimagnetic Mn2­pyridazine­[Nb(CN)8] molecular magnet under hydrostatic pressure is reported. The pressure-induced structural changes provoke the strengthening of magnetic interaction between Mn and Nb centres. Consequently, an increase of critical temperature Tc is observed from 43 K for a sample at ambient pressure (A) to 52.5 K for a sample under a pressure of 1.19 GPa (AHP). The magnetocaloric effect was determined by the magnetization measurements. The application of a hydrostatic pressure of 1.19 GPa causes a decrease in the maximum value of magnetic entropy change ΔS, which for AHP is equal to 4.63 J mol−1 K−1 (7.73 J kg−1 K−1) at µ0ΔH = 5 T, while for A it is 5.36 J mol−1 K−1 (8.95 J kg−1 K−1) for the same magnetic field change. The temperature-dependent parameter n obtained for AHP, describing the field dependence of MCE, is consistent with other critical exponents determined from magnetization measurements. The critical exponents allow us to classify AHP to the 3D Heisenberg universality class, similar to the case of the non-pressurized sample.

A water sensitive ferromagnetic [Ni(cyclam)]2[Nb(CN)8] network.

Reaction between [Ni(cyclam)](2+) and [W(CN)(8)](4-) leads to the formation of a 3D diamond-like network [Ni(cyclam)](2)[W(CN)(8)]·3.5H(2)O (1). The structure is characterised by a network of intersecting channels of 3-4 Å in diameter, filled with crystallisation water, most of which is released upon drying in air, causing the crystals to collapse. Analogous compound [Ni(cyclam)](2)[Nb(CN)(8)]·3.5H(2)O (2), based on paramagnetic Nb(IV), could only be obtained as a powder, due to the decomposition of the [Nb(CN)(8)](4-) complex under slow diffusion conditions. It shows long-range magnetic ordering with T(C) = 11.8 K and magnetic hysteresis at 2 K. These properties are lost upon drying in air. After rehydration differently shaped hysteresis appears, which together with AC susceptibility measurements suggests the formation of a multiphase system. Subsequent dehydration-rehydration experiments show partial reversibility.

Magnetocaloric effect in M-pyrazole-[Nb(CN)(8)] (M = Ni, Mn) molecular compounds.

We report a study of magnetocaloric effect (MCE) in cyanido-bridged {[M(II)(pyrazole)(4)](2)[Nb(IV)(CN)(8)]·4H(2)O}(n) molecular compounds where M = Ni, Mn, pyrazole = C(3)H(4)N(2). The substances show a sharp phase transition to a long range magnetically ordered state, with ferromagnetic coupling between M and Nb sublattices in the case of the Ni-based sample 1 (T(c) = 13.4 K) and ferrimagnetic coupling for the Mn-based sample 2 (T(c) = 23.8 K). The magnetic entropy change ΔS due to applied field change ΔH as a function of temperature was determined by the magnetization and heat capacity measurements. The maximum value of ΔS at µ(0)ΔH = 5 T is 6.1 J mol(-1) K(-1) (5.9 J kg(-1) K(-1)) for 1 at T = 14 K and 6.7 J mol(-1) K(-1) (6.5 J kg(-1) K(-1)) for 2 at T = 25 K. MCE data at different applied fields have been presented as one universal curve, which confirms magnetic transitions in 1 and 2 to be of second order. The temperature dependences of the n exponent characterizing the dependence of ΔS on ΔH have been obtained. The n(T(c)) values, consistent with the shape of the magnetization curves, pointed to the 3D Heisenberg behaviour for 2 and some anisotropy, probably of the XY type, for 1. The (H/T(c))(2/3) dependence of the maximum entropy change has been tested in the ferrimagnetic Mn(2)-L-[Nb(CN)(8)] (L = C(3)H(4)N(2), C(4)H(4)N(2)) series.

The role of carboxylate ligands in two novel cyanido-bridged 2D coordination networks Cu(II)-W(V) and Mn(II)-Nb(IV).

We report on the synthesis, molecular structure and magnetic properties of two novel coordination polymers: [{Cu(II)(4)(pic)(2)(H(2)O)(2)(MeOH)}{W(V)(CN)(8)}(2)]·MeOH·4H(2)O (1) and [{Mn(II)(3)(HCOO)(2)(H(2)O)(4)}{Mn(II)(H(2)O)(3)(HCONH(2))}(2){Nb(IV)(CN)(8)}(2)]·4HCONH(2)·2H(2)O (2). The single-crystal X-ray diffraction analysis of 1 shows that its molecular structure can be interpreted as a cyanido bridged (3,4,7)-connected 2D bilayer built of two different subnets sharing the tungsten centers. The magnetic measurements suggest that the system reveals long-range ferromagnetic ordering between Cu(II) and W(V) centers below 13.4 K. The molecular structure of (2) reveals a 2D topology of layers built of cyanido and formato bridging ligands. The system reveals ferrimagnetic behavior with a critical temperature at 17.8 K.

Microporous {[Ni(cyclam)]3[W(CN)8]2}n affording reversible structural and magnetic conversions.

Methanol adsorption into the porous 2D bimetallic coordination network {[Ni(cyclam)](3)[W(CN)(8)](2)}(n) (cyclam = 1,4,8,11-tetraazacyclotetradecane) causes significant modification of its structure and magnetic properties. Fully reversible transformations between the three states of the network: anhydrous, hydrated and methanol-modified are observed with the transition to the magnetic ordered state at T(c) equal to 4.9 K, 8.3 K and 11.4 K respectively. All three phases have a metamagnetic character but the methanol-modified one most easily turns to ferromagnetic and shows a hysteresis loop with coercivity field of 250 Oe. The differences in magnetic behaviour of the anhydrous and guest-induced forms of the compound are discussed in terms of changes in the structure: CN-bridge geometry and distance between the layers.

Nature of magnetic interactions in 3D {[M(II)(pyrazole)4]2[Nb(IV)(CN)8].4H2O}n (M = Mn, Fe, Co, Ni) molecular magnets.

The self-assembly of [Nb(IV)(CN)(8)](4-) with different 3d metal centers in an aqueous solution and an excess of pyrazole resulted in the formation of four 3D isostructural compounds {[M(II)(pyrazole)(4)](2)[Nb(IV)(CN)(8)].4H(2)O}(n), where M(II) = Mn, Fe, Co, and Ni for 1-4, respectively. All four assemblies crystallize in the same I4(1)/a space group and show identical cyanido-bridged structures decorated with pyrazole molecules coordinated to M(II) centers. All four compounds show also long-range magnetic ordering below 24, 8, 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 J(M-Nb) attributed to the one type of M(II)-NC-Nb(IV) linkage existing in 1-4. The J(M-Nb) values increase monotonically from -6.8 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 M(II) metal center. Average orbital contributions to the total exchange coupling constants J(M-Nb) have also been identified and calculated: antiferromagnetic J(AF) = -21.6 cm(-1) originating from the d(xy), d(xz), and d(yz) orbitals of M(II) and ferromagnetic J(F) = +15.4 cm(-1) originating from d(z(2)) and d(x(2)-y(2)) orbitals of M(II). Antiferromagnetic interaction is successively weakened in the 1-4 row with each additional electron on the t(2g) level, which results in a change of the sign of J(M-Nb) and the nature of long-range magnetic ordering from ferrimagnetic in 1 and 2 to ferromagnetic in 3 and 4.

Iron(II)-octacyanoniobate(IV) ferromagnet with T(C) 43 K.

We have synthesized the octacyanoniobate-based cyano-bridged 3D ferromagnet {[Fe(II)(H(2)O)(2)](2)[Nb(IV)(CN)(8)].4H(2)O}(n) and characterized structurally, spectroscopically (XANES/EXAFS, IR, UV-Vis, Resonance Raman, (57)Fe Mössbauer spectroscopy) and magnetically. crystallizes in the tetragonal system, space group I4/m, a = 11.989(5) A, c = 13.237(5) A, V = 1902.6(13) A(3). 3D coordination architecture comprises two types of Nb(IV)-C-N-Fe(II)(HS) (HS = high spin) linkages with Fe-N-C angles of 154.5 degrees and 167.5 degrees . The XANES/EXAFS spectra at Fe:K and Nb:K lines confirm the presence of Nb(IV)-C-N-Fe(II) linkages. Magnetic measurements reveal ferromagnetic ordering below T(c) = 43 K with some non-collinearity of Nb(IV) (S = 1/2) and Fe(II) (S = 2) magnetic moments. The molecular field model simulation reproduces well the M(T) curve and T(c) value with one average exchange coupling constant J(FeNb) = + 8.1 cm(-1).

Magnetic spongelike behavior of 3D ferrimagnetic {[Mn(II)(imH)]2[Nb(IV)(CN)8]}n with Tc = 62 K.

Fully reversible room temperature dehydration of 3D {Mn(II)2(imH)2(H2O)4[Nb(IV)(CN)8] x 4 H2O}n (1; imH = imidazole) of Tc = 25 K results in the formation of 3D ferrimagnet {[Mn(II)(imH)]2[Nb(IV)(CN)8]}n (2), with Tc = 62 K, the highest ever known for octacyanometalate-based compounds. The dramatic magnetostructural modifications in 2 provide the first example of magnetic spongelike behavior in an octacyanometallate-based assembly.

Cobalt(II) octacyanotungstate(V) organic-inorganic hybrid ferromagnetic materials with pyrazine and 4,4'-bipyridine.

Two new ferromagnetic organic-inorganic hybrid materials [Co(II)3(H2O)6(pyz)3[W(V)(CN)8]2].3.5H2O (1) and [Co(II)3(H2O)4(4,4'-bpy)3[W(V)(CN)8]2].1.5(4,4'-bpy).6H2O (2) have been synthesised and characterised. The structure of the compounds have been investigated combining EXAFS (extended X-ray absorption fine structure), ES-MS (electrospray mass spectrometry), IR (infrared spectroscopy), UV-VIS electronic spectroscopy and TGA (thermogravimetric analysis) coupled with QMS (quadrupole mass spectrometer) experiments. The studies reveal that both compounds consist of Co(II)-NC-W(V) and Co(II)-L-Co(II) linkages (L = pyrazine (1) or 4,4-bipyridine (2)). Both networks are created by cyano-bridged Co(II)3W(V)2 chains joined by organic linkers into a 2D architecture. A difference of cobalt coordination numbers in both compounds derived from EXAFS study is consistent with the ES-MS conclusion. The ac magnetic characterisation exhibits the transition to the ferromagnetic phase at T(C) = 26 K (1) and to the spin glass-like phase at T(G) = 16 K (2). The frequency dependent chi'(T) and chi''(T) signals indicate the presence of some disorder in spin alignment below ordering temperatures. Both networks are also characterised a by magnetic hysteresis loop of coercive field H(c) = 750 Oe (1) and 1200 Oe (2) at T = 4.2 K.

[Ln(terpy)]3+ (Ln = Sm, Gd) entity forms isolated magnetic chains with [W(CN)8]3-.

The reaction between Ln(NO3)3*xH2O, Cs3[W(V)(CN)8]*H2O and 2,2':6',2''-terpyridine (terpy) leads to the original isomorphous cyano-bridged [Ln(III)(terpy)(DMF)4][W(V)(CN)8] *6H2O [Ln = Gd (1), Sm (2)] 1-D chains. The crystal structures of {Ln(III)W(V)} chains and consist of alternating {[W(CN)8]} and {[Ln(terpy)]} building blocks. The neighbouring 1-D chains are weakly linked through pi-pi stacking interactions of the aromatic rings leading to 2-D supramolecular layers. The layers are linked through hydrogen bonds between H2O molecules and terminal cyano ligands. Magnetic studies revealed a weak antiferromagnetic coupling (J = -2.3(2) K) within the {Gd(III)W(V)} chains in . The positive effective coupling constant J = +2.0(5) K between the total angular momentum of the Sm(III) centre and the spin of the W(v) ion is equivalent to an antiferromagnetic character of the spin coupling between both centres in the {Sm(III)W(V)} chains of 2. The magnetic measurements suggest that they display an isolated magnetic chain behaviour.

An unprecedented copper(I,II)-octacyanotungstate(V) 2-D network: crystal structure and magnetism of [CuII(tren)]{CuI[W(V)(CN)8]} . 1.5H2O.

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.

Crystal structures and magnetic properties of two low-dimensional materials constructed from [Mn(III)(salen)H2O]+ and [M(CN)8](3-/4-) (M = Mo or W) precursors.

The syntheses, X-ray structures, and magnetic behaviors of two new cyano-bridged assemblies, the molecular [Mn(III)(salen)H2O]3[W(V)(CN)8].H2O (1) and one-dimensional [Mn(salen)(H2O)2]2[[Mn(salen)(H2O)][Mn(salen)]2[Mo(CN)(8)]].0.5ClO4.0.5OH.4.5H2O (2), are presented. Compound 1 crystallizes in the monoclinic system, has space group P2(1)/c, and has unit cell constants a = 13.7210(2) A, b = 20.6840(4) A, c = 20.6370(2) A, and Z = 4. Compound 2 crystallizes in the triclinic system, has space group P, and has unit cell dimensions a = 18.428(4) A, b = 18.521(3) A, c = 18.567(4) A, and Z = 2. The structure of 1 consists of the asymmetric V-shaped Mn-NC-W-NC-Mn-O(phenolate)-Mn molecules, where W(V) coordinates with [Mn(salen)H2O] and singly phenolate-bridged [Mn(salen)H2O]2 moieties through the neighboring cyano bridges. The [W(V)(CN)8]3- ion displays distorted square-antiprism geometry. The structure of 2 consists of the cyano-bridged [Mn3(III)Mo(IV)]n- repeating units linked by double phenolate bridges into one-dimensional zigzag chains. The Mn(III) centers are bound to Mo(IV) of square-antiprism geometry through the neighboring cyano bridges. The magnetic studies of 1 reveal the antiferromagnetic intramolecular interactions through the CN and phenolate bridges and the relatively weak intermolecular interactions. Compound 1 becomes antiferromagnetically ordered below TN = 4.6 K. The presence of the magnetic anisotropy is documented with the MH measurements carried out for both polycrystalline and single-crystal samples. At T = 1.9 K, the spin-flop transition is observed in the field of 18 kOe applied parallel to the bc plane, which is the easy plane of magnetization. Field dependence of magnetization of 1 shows field-induced metamagnetic behavior from the antiferromagnetic ground state of ST = 3/2 to the state of ST = 5/2. The magnetic properties of 2 indicate a weak antiferromagnetic interaction between Mn(III) centers in double-phenolate-bridged [Mn(III)(salen)]2 dinuclear subunits and a very weak ferromagnetic interaction between them through the diamagnetic [Mo(IV)(CN)8]4- spacer.

2-D soft ferromagnet based on [Wv(CN)8]3- and CuII with a Tc of 34 K.

Self-assembly of [Cu(tetren)]2+ (tetren = tetraethylenepentamine) and [W(CN)8]3- in acidic aqueous solution yields the double-layered square grid cyanide-bridged polymer of ((tetrenH5)0.8CuII4[Wv(CN)8](4).7.2H2O)n with Cu(II) centres of square pyramidal geometry coordinatively saturated solely by CN bridges supplied by five [W(CN)8]3- ions; it exhibits soft ferromagnetic behaviour with an ordering temperature Tc of 34 K.