Novel 'anti-Prussian blue' structure based on Zn2+ nodes and [Re3Mo3S8(CN)(6)](6-) heterometallic cluster spacers and its rearrangement to Prussian blue

摘要

The reaction between ZnCl2 and an aqueous solution of CaK4[Re3Mo3S8(CN)(6)]center dot 8H(2)O is controlled by the concentration of NH3. High concentration of NH3 favors the formation of [Zn(NH3)(4)](8){Zn[Re3Mo3S8(CN)(6)](3)}center dot 9H(2)O with an ideal primitive cubic 3D network of Zn2+ cations joined by cyanocluster anions acting as unprecedented bulky linear spacers. The low concentration of NH3 leads to the formation of the usual Prussian blue structure [Zn(NH3)(4)](2)[ZnRe3Mo3S8(CN)(6)]center dot 2H(2)O with alternating octahedral Zn2+ and cyanocluster nodes. Both compounds contain a paramagnetic cluster anion with g = 2.279 and 2.280, respectively. Powder diffraction studies prove that the former compound transforms into the latter after the exposure of a polycrystalline sample to air.