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Diverse functional potential of heterometallic systems based on octacyanidometallates places them at the forefront of research into modern molecule-based materials.

Planar honeycomb-like coordination network {[Ni(cyclam)]3[W(CN)8]2}n (cyclam = 1,4,8,11-tetraazacyclotetradecane) was obtained in the self-assembly reaction of [Ni(cyclam)]2+ and [W(CN)]83-. Its structure is characterized by void channels along the a axis. The compound shows reversible water adsorption in the temperature range of 25-40 degrees C with the formation of {[Ni(cyclam)]3[W(CN)8]2}n.16nH2O, accompanied by single-crystal-to-single-crystal transformation. The structural transformation significantly changes the character of intraplane magnetic exchange interactions.

The aim and the scope of this review is to show the results of ten years of research following the first reports on magnetic and photomagnetic assemblies constructed from. It is illustrated on the basis of our own work as well as a wide range of studies carried out in numerous laboratories around the world. The diversity and evolution of topological and structural patterns is discussed alongside synthetic strategies, which led to the establishment of regular magnetostructural correlations in selected 3D systems. Different types of functionality observed in solid phases are presented with special attention devoted to tuning of magnetic

A complete review of all known octacyanide-based clusters with an extensive discussion of their structures, magnetic properties and multifunctionality.

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.

We present an overview of very recent advances in the engineering of magnetic networks based on octacyanometalates. The selected magnetic networks of Cu II W V , Ni II W V and Mn II LNb IV (L -organic bridging linker) illustrate the possible strategies for tuning of the magnetic characteristics. The combination of magnetic ordering for 2D (two-dimensional) and 3D (threedimensional) networks together with the solvent sensitivity of a cyano-bridged framework resulted in the development of a novel 3D {[Mn II (imH)] 2 [Nb IV (CN) 8 ]} assembly with magnetic sponge character, characterized by T c of 62 K, the highest ever observed for octacyanometalate-based networks.

An alternating bimetallic {(H3O)[Ni(III)(cyclam)][Fe(II)(CN)6]·5H2O}n chain undergoes reversible dehydration at 40 °C accompanied by electron transfer which leads to Ni(II)-Fe(III) in about 50% of metal centres. The hydrated dark blue form is a paramagnet while the dehydrated yellowish-green form shows ferromagnetic coupling between neighbouring Ni(II) and Fe(III).