Abstract: | Two tetranuclear cyanide‐bridged FeIII2NiII2 compounds Ni2(L1)4Fe2(μ‐CN)4(CN)2(L2)2] · 2ClO4 · CH3OH · 4H2O ( 1 ) and Ni2(L1)4Fe2(μ‐CN)4(CN)2(L3)2] · 2ClO4 ( 2 ) L1 = 4,4′‐dichloro‐2,2′‐bipyridine; L2 = hydrotris(pyrazolyl)borate; L3 = tetrakis(pyrazolyl)borate] were synthesized. Magnetic measurements indicated that both two compounds showed single‐molecule magnet (SMM) behaviors with the relaxation energy barrier of Δ/kB = 68.9(8) K for 1 and 12.6(1) K for 2 . Magneto‐structural analysis indicated that the intermolecular interactions played an important part in the slow magnetic relaxation behaviors. |