Cyano-Bridged FeIII2CuII3 and FeIII4NiII4 Complexes:  Syntheses, Structures, and Magnetic Properties

Two tricyanometallate precursors, (Bu4N)[(Tp4Bo)Fe(CN)3]·H2O·2MeCN (1) and (Bu4N)[(pzTp)Fe(CN)3] (2) [Bu4N+ = tetrabutylammonium cation; Tp4Bo = tris(indazolyl)hydroborate; pzTp = tetrakis(pyrazolyl)borate], with a low-spin FeIII center have been synthesized and characterized. The reactions of 1 or 2 with [Cu(Me3tacn)(H2O)2](ClO4)2 (Me3tacn = N,N‘,N‘ ‘-trimethyl-1,4,7-triazacyclononane) afford two pentanuclear cyano-bridged clusters, [(Tp4Bo)2(Me3tacn)3Cu3Fe2(CN)6](ClO4)4·5H2O (3) and [(pzTp)2(Me3tacn)3Cu3Fe2(CN)6](ClO4)4·4H2O (4), respectively. Assembly reactions between 2 and [Ni(phen)(CH3OH)4](ClO4)2 (phen = 1,10-phenanthroline) or Zn(OAc)2·2H2O afford a molecular box [(pzTp)4(phen)4Ni4Fe4(CH3OH)4(CN)12](ClO4)4·4H2O (5) and a rectangular cluster [(pzTp)2Zn2Fe2(OAc)2(H2O)2(CN)6] (6). Their molecular structures were determined by single-crystal X-ray diffraction. In complexes 1 and 2, the central FeIII ions are coordinated by three cyanide carbon atoms and three nitrogen atoms of Tp4Bo- or pzTp-. Both complexes 3 and 4 show a trigonal-bipyramidal geometry, in which [(L)Fe(CN)3]- units occupy the apical positions and are linked through cyanide to [Cu(Me3tacn)]2+ units situated in the equatorial plane. Complex 5 possesses a cubic arrangement of eight metal irons linked through edge-spanning cyanide bridges, while complex 6 shows Zn2Fe2(CN)4 rectangular structure, in which FeIII and ZnII ions are alternately bridged by the cyanide groups. Intramolecular ferromagnetic couplings are observed for complexes 35, and they have S = 5/2, 5/2, and 6 ground states and appreciable magnetic anisotropies with negative D values equal to −0.49, −2.39, and −0.39 cm-1, respectively.