We present an overview of very recent advances in the engineering of magnetic networks based on octacyanometalates. The selected magnetic networks of Cu^IIW^V, Ni^IIW^V and Mn^IILNb^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 (three-dimensional) 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.

The magnetocaloriceffect is considered as an energy-efficient and environmentally friendly technique which can take cooling technology to the next level. Apart from its commercial application at room temperature, magnetic refrigeration is an up-and-coming solution for the cryogenic regime, especially as an alternative to He³ systems. Molecular magnets reveal advantageous features for ultra-low cooling which are competitive with intermetallic and lanthanide alloys. Here, we present a guide to the current status of magnetocaloric effect research of molecular magnets with a theoretical background focused on the inverse magnetocaloric effect and an overview of recent results and developments, including the rotating magnetocaloric effect.

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^IIIW^V} chains 1 and 2 consist of alternating {[W(CN)₈]} and {[Ln(terpy)]} building blocks. The neighbouring 1-D chains are weakly linked through π–π 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^IIIW^V} chains in 1. 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^IIIW^V} chains of 2. The magnetic measurements suggest that they display an isolated magnetic chain behaviour.