Humidity-Induced Switching between Two Magnetic and Structural Phases in a Co^II -[W^V (CN)₈ ] Molecular Magnet

The self-assembly of cobalt(II) with purine and octacyanidotungstate(V) results in the formation of the three-dimensional Co₃ [W(CN)₈ ]₂ (purine)₂ ⋅8.5H₂ O (1) coordination polymer. This compound exhibits humidity-induced variation of the number of water molecules of crystallisation leading to a reversible structural phase transition and the alternation of the long-range ferromagnetic ordering temperature from T_C =29 K for the pristine assembly (1) to T_C =49 K for the sample stored in a low-humidity atmosphere (1-deh). This phenomenon can be attributed to a reversible change in the hydrogen-bonding network resulting in the modification of the local geometries of cobalt(II) as well as the cyanido bridges.