On the basis of high-spin metal-cyanide clusters of (Mn6MIII)-M-III (M = Cr, Fe, Co), three one-dimensional (1D) chain complexes, [Mn(salen)](6)[Cr(CN)(6)](2)center dot 6CH(3)OH center dot H2O (1), [Mn(5-CH3)salen)](6)[Fe(CN)(6)](2)center dot 2CH(3)CN center dot 10H(2)O (2), and [Mn(5-CH3)salen)](6)[Co(CN)(6)](2)center dot 2CH(3)CN center dot 10H(2)O (3) [salen = N,N'-ethylenebis(salicylideneiminato) dianion], have been synthesized and characterized structurally as well as magnetically. Complexes 2 and 3 are isomorphic but slightly different from complex 1. All three complexes contain a 1D chain structure which is comprised of alternating high-spin metal-cyanide clusters of [Mn6M](3+) and a bridging group [M(CN)(6)](3-) in the trans mode. Furthermore, the three complexes all exhibit extended 3D supramolecular networks originating from short intermolecular contacts. Magnetic investigation indicates that the coupling mechanisms are intrachain antiferromagnetic interactions for 1 and ferromagnetic interactions for 2, respectively. Complex 3 is a magnetic dilute system due to the diamagnetic nature of Co-III. Further magnetic investigations show that complexes 1 and 2 are dominated by the 3D antiferromagnetic ordering with T-N = 7.2 K for 1 and 9.5 K for 2. It is worth noting that the weak frequency-dependent phenomenon of AC susceptibilities was observed in the low-temperature region in both 1 and 2, suggesting the presence of slow magnetic relaxations.