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.

The design and construction of switchable materials attracts tremendous interest owing to the potential in information storing and processing or molecular sensing. [1][2][3][4] The archetypal examples involve a diversity of Fe II -, [5,6] Fe III - [7] or Co IIbased [8][9][10] spin-crossover (SCO) compounds, Co III/II -catecholate/semiquinone systems, [1,11] as well as d-d bimetallic and sd-d trimetallic cyanide-bridged systems revealing chargetransfer-induced spin transitions (CTIST). [12][13][14][15][16][17][18] Some of these compounds, for example Prussian blue analogues, are particularly promising from the point of view of photoswitching between nonmagnetic and magnetized (that is, T B , T C ) states, owing to magnetic coupling through molecular bridges in discrete species [14,15] and extended networks. [17,18] Such bistability also emerged in the magnetochemistry of octacyanidometalates, exploiting metal-to-metal electron transfer in HS Co II L[W V (CN) 8 ] 3À (L = pyrimidine, 4-methylpyridine) [19,20] or canonical SCO in Fe II L[Nb IV (CN) 8 ] 4À extended networks [21] (L = 4-pyridinealdoxime). A magnetic hysteresis loop with a coercivity of 1-3 T were observed in an optically excited low-temperature metastable phase.

Precisely controlled stoichiometric mixtures of Co(2+) and Fe(2+) metal ions were combined with the [W(V)(CN)8](3-) metalloligand in a methanolic solution to produce a series of trimetallic cyanido-bridged {Fe(9-x)Co(x)[W(CN)8]6(MeOH)24}·12MeOH (x = 0, 1, ..., 8, 9; compounds 0, 1, ..., 8, 9) clusters. All the compounds, 0-9, are isostructural, and consist of pentadecanuclear clusters of a six-capped body-centered cube topology, capped by methanol molecules which are coordinated to 3d metal centers. Thus, they can be considered as a unique type of a cluster-based molecular solid solution in which different Co/Fe metal ratios can be introduced while preserving the coordination skeleton and the overall molecular architecture. Depending on the Co/Fe ratio, 0-9 exhibit an unprecedented tuning of magnetic functionalities which relate to charge transfer assisted phase transition effects and slow magnetic relaxation effects. The iron rich 0-5 phases exhibit thermally induced reversible structural phase transitions in the 180-220 K range with the critical temperatures being linearly dependent on the value of x. The phase transition in 0 is accompanied by (HS)Fe(II) W(V) ↔ (HS)Fe(III) W(IV) charge transfer (CT) and the additional minor contribution of a Fe-based spin crossover (SCO) effect. The Co-containing 1-5 phases reveal two simultaneous electron transfer processes which explore (HS)Fe(II) W(V) ↔ (HS)Fe(III) W(IV) CT and the more complex (HS)Co(II) W(V) ↔ (LS)Co(III) W(IV) charge transfer induced spin transition (CTIST). Detailed structural, spectroscopic, and magnetic studies help explain the specific role of both types of CN(-)-bridged moieties: the Fe-NC-W linkages activate the molecular network toward a phase transition, while the subsequent Co-W CTIST enhances structural changes and enlarges thermal hysteresis of the magnetic susceptibility. On the second side of the 0-9 series, the vanishing phase transition in the cobalt rich 6-9 phases results in the high-spin ground state, and in the occurrence of a slow magnetic relaxation process at low temperatures. The energy barrier of the magnetic relaxation gradually increases with the increasing value of x, reaching up to ΔE/kB = 22.3(3) K for compound 9.