The successful introduction of azide ions as secondary bridges into the Fe-III-Ni-II cyanide system afforded two clusters and one unique 4(3),2-ribbon chain: [(bpzpy)(2)Ni-2(mu(2)-1,1-N-3)(2){(pzTp)Fe(CN)(3)}(2)]center dot 3H(2)O [1; bpzpy = 2,6-bis(pyrazol-1-yl)pyridine, and pzTp = tetrakis(pyrazolyl)borate], [(L-1)(2)Ni-4( mu(3)1,1,1-OCH3)(2)(mu(2)-1,1-N-3)(2)(H2O)(2){(Tp)Fe(CN)(3)}(2)]center dot 2CH(3)OH center dot H2O [2; Tp = hydrotris(pyrazolyl)borate, and HL1 = 2,6-bis{(2-hydroxypropylimino)methyl}4-methylphenol], and [(L-2)(2)Ni-3(mu(2)-1,1-N-3)(4){(pzTp)Fe(CN)(3)}(2)](n) (3; L2 = 2-{[phenyl(pyridin-2-yl)methylene]amino}ethan-1-amine). Both 1 and 2 feature the centrosymmetric {Fe-III-Ni-2(II)-Fe-III} and {Fe-III-Ni-4(II)-Fe-III} rodlike structures in which the two peripheral [(Tp(R))Fe(CN)(3)](-) anions act as monodentate ligands via one cyanide group to link the central azide-bridged [Ni-2] and [Ni-4] subunit, respectively, while 3 displays an extended structure of the double-zigzag (4,2-ribbon) chain in which the double end-on azide-bridged trinuclear [Ni-3] subunits serve as the 4-connected nodes. Magnetic study revealed that intramolecular ferromagnetic coupling is dominated by the azide or cyanide bridges in all of the complexes. Remarkably, complex 1 behaves as a single-molecule magnet with an effective energy barrier of 16.5 cm(-1) at zero dc field, while complex 3 exhibits metamagnetism with a hidden spin canting property below 12 K.