Two novel low-dimensional molecular magnetic materials were prepared by the self-assembly of 3d- and 5d-metal complexes. These are the first neutral heterobimetallic cyanobridged compounds involving one anisotropic Mn(III) Schiff base complex and one octacyanotungstate(V) per molecular unit. A slow diffusion of the constituents’ solutions leads to the formation of the 0D crystalline complex 1
, due to coordination of a water molecule to the Mn center, which prevents polymer formation. A rapid mixing of reagents results in the precipitation of the microcrystalline powder of complex 2
, which based on the totality of experimental data, possesses a 1D polymeric structure. The magnetic studies have shown that antiferromagnetic exchange interactions prevail in 1
= −13.1(7) K, D
= −3.0(1.3) K, zJ'
= −0.16(20) K and gav
= 2.00(1)); while the presence of the significant intramolecular Mn(III)–W(V) ferromagnetic coupling through cyanide bridge is characteristic for 2
46.1(5) K, gMn
= 2.11(3), fixed gW
= 2.0). Due to the weak interchain interactions, zJ
= −0.8(2) K, and compound 2
is a metamagnet with the Néel temperature of 9.5 K undergoing a spin-flip transition at 2 kOe. The slow magnetization dynamics of 2
were investigated at a DC field of 0 and 2 kOe, giving the values of τ0
32(15) and 36(15) ps, respectively, well within the range typical for single-chain magnets (SCMs). The respective ∆τ
values were 48.4(1.2) and 44.9(1.0) K.