Self-Assembly from Discrete Clusters to 2D Network Based on [Fe(phen)(CN)4]- and [Fe(bipy)(CN)4]-: Synthesis, Structures and Magnetic Properties

A series of cyanido‐bridged complexes {[FeIII(phen) (CN)4]2[NiL1]}·4H2O (1), {[FeIII(bipy)(CN)4]2[NiL1]}·4H2O (2), [FeIII(bipy)(CN)4]2[NiL2] (3), {[FeIII(phen)(CN)4]2[CuL3]}·5H2O (4), {[FeII(phen)(CN)4][Ni(ea)2]}2·2H2O (5), {[FeII(phen)(CN)4] [NiL2]·2H2O}n (6), {[FeIII(bipy)(CN)4]2[Ni(H2O)2]}·6.5H2O}n (7) and {[FeII(bipy)(CN)4][Ni(ea)2]·H2O}n (8) were synthesized using H[Fe(phen)(CN)4]·2H2O and H[Fe(bipy)(CN)4]·2H2O as precursors [L1 = 5,5,7,12,12,14‐hexamethyl‐1,4,8,11‐tetraazacyclotetradecane, L2 = 3,10‐bis(2‐phenylethyl)‐1,3,5,8, 10,12‐hexaazacyclotetradecane, L3 = 3,10‐bis(2‐hydroxyethyl)‐1,3,5,8,10,12‐hexaazacyclotetradecane, phen = 1,10‐phenanthroline, bipy = 2,2′‐bipyridine, ea = ethanolamine). Complexes 1–4 are trinuclear clusters, and 5 is a tetranuclear square. In 6, the [FeII(phen)(CN)4]2– anions alternately bridge the [NiL2]2+ cations to generate a 1D wavy chain. The structure of 7 possesses a 4,2‐ribbonlike chain, which contains a NiII2(CN)4FeIII2 square with each NiII atom shared by two adjacent squares. Each FeII and NiII atom in 8 acts as a three‐connected node through the cyanido‐bridges to generate a 2D network with a 4,82 topological net. Ferromagnetic couplings are found between the low‐spin FeIII ions and the NiII ions through the cyanido groups in 1–3 and 7, and a metamagnetic behavior and a frequency dependence of the out‐of‐phase ac susceptibility are observed in 7. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) Eight cyanido‐bridged complexes, from clusters to 2D networks, were synthesized with H[Fe(phen)(CN)4]·2H2O and H[Fe(bipy)(CN)4]·2H2O as precursors. Ferromagnetic couplings are found between the low‐spin FeIII ions and NiII ions through the cyanido groups in the complexes and a metamagnetic behavior and a frequency dependence of the out‐of‐phase ac susceptibility are observed in one complex.