The reaction of VIII( THF)(3)Cl-3 with NEt4CN in acetonitrile ( MeCN) forms ( NEt4)(3)[ VIII( CN)(6)]center dot 4MeCN ( 1), which after characterization was used as a molecular building block toward the synthesis of Prussian blue structured magnets. The reaction of 1 with [ Cr-II( NCMe)(4)]( BF4)(2) forms (Cr0.5CrIII)-Cr-II[ V-II( CN)(6)]center dot zMeCN via internal electron transfer, whose structure and magnetic properties are dependent on the degree of solvation, z. When solvated, (Cr0.5CrIII)-Cr-II[ VII( CN)(6)]center dot 1.2MeCN ( 2) is a mixture of crystalline and amorphous fractions that yield a material with two magnetic phases: bulk ferrimagnetic phase/crystalline [ faced-centered-cubic lattice with a = 10.55( 2) angstrom] and cluster-glass phase/amorphous. The bulk ferrimagnetic phase exhibits a critical temperature, T c, of 110 K, while the amorphous cluster-glass phase exhibits a freezing temperature, T-f, of similar to 25 K. Amorphous (Cr0.5CrIII)-Cr-II[ V-II( CN)(6)]center dot 0.1MeCN ( 3) was determined to be the pure cluster-glass phase. This is an overall enhancement of 85 K ( 350%) in the magnetic ordering temperature via solvation, z. The coercivity was also increased 4-fold from 890 ( 2) and 3900 Oe ( 3) via desolvation.