The kinetic inertness of the hexaaquachromium(III) (k(H2O)= 2.4 x 10(-6) s(-1)) has led to challenges with respect to incorporating Cr-III ions into Prussian blue-type materials; however, hexakis(acetonitrile)chromium(III) was shown to be substantially more labile (similar to 10(4) times) and enables a new synthetic route for the synthesis of these materials via nonaqueous solvents. The synthesis, spectroscopic, and physical properties of Cr[M(CN)(6)] (M = V, Cr, Mn, Fe) Prussian blue analogues synthesized from [Cr-III(NCMe)(6)](3+) and the corresponding [M-III(CN)(6)](3-) are described. All these compounds {(NEt4)(0.02)Cr-III[V-III(CN)(6)](0.98)(BF4)(0.08)center dot 0.10MeCN (1), Cr-III[Cr-III(CN)(6)]center dot 0.16MeCN (2), Cr-III[Mn-III(CN)(6)]center dot 0.10MeCN (3), and (NEt4)(0.04)(Cr0.64Cr0.40IV)-Cr-III[Fe-III(CN)(6)](0.40)[Fe-III(CN)(6)]( 0.60)(BF4)(0.16)center dot 1.02MeCN (4)} are ferrimagnets exhibiting cluster-glass behavior. Strong antiferromagnetic coupling was observed for M = V, Cr, and Mn with Weiss constants (theta) ranging from -132 to -524 K; and in 2, where the strongest coupling is observed (0 = -524 K), the highest T, (110 K) value was observed. Weak antiferromagnetic coupling was observed for M = Fe (theta = -12 K) leading to the lowest T-c (3 K) value in this series. Weak coupling and the low T-c value observed in 4 were additionally contributed by the presence of both [Fe-II(CN)(6)](4-) and [Fe-III(CN)(6)](3-) as confirmed by Fe-57-Mossbauer spectroscopy.