Three new heterobimetallic cyanide-bridged complexes, {[Ni(L 1)][Ag(CN) 2 ]}[Ag(CN) 2 ] • 2H 2 O (2), {[Mn(L 2)][Ag(CN) 2 ]} • 1.5H 2 O (3) and {[Mn(L 3)(H 2 O)] 2 [Ag(CN) 2 ]}ClO 4 • 2H 2 O (4) (L 1 = 2,7,12-trimethyl-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),13,15-triene; L 2 = N,N'-1,3-propylenebis(5-chlorosalicylideneiminate); L 3 = N,N'-1,2-propylene-bis(5-bromosalicylideneiminate)), have been assembled using for the first time a new polyaza macrocycle nickel(II) compound [Ni(L 1)](ClO 4) 2 (1), or Schiff-base manganese(III) compounds and K[Ag(CN) 2 ]. Single crystal X-ray diffraction analysis reveals that complexes 2 and 3 can be characterized as one-dimensional cationic and neutral single chain structure, respectively. Complex 3 forms a three-dimensional network via weak inter-chain Ag…Ag interactions. Complex 4 belongs to a cyanide-bridged bimetallic sandwich-like cationic trinuclear structure containing Mn 2 Ag core with free ClO − 4 as a counter anion, indicating that the Schiff-base ligand has an obvious influence on the structure of the cyanide-bridged complexes formed. Investigation of the magnetic susceptibilities of the cyanide-bridged Ag-Ni(II)/Mn(III) complexes showed the weak anti-ferromagnetic interaction between neighboring paramagnetic Ni(II) or Mn(III) ions bridged by the long NC-Ag-CN unit. From the best-fit of the magnetic susceptibility data of complexes 2 and 4 the magnetic coupling constant was determined to be J = −0.51 and −0.78 cm −1 , respectively.