Ferromagnetic coupling between low- and high-spin iron(III) ions in the tetranuclear complex fac-[[FeIII[HB(pz)3](CN)2(mu-CN)]3FeIII(H2O)3]* 6H2O ([HB(pz)3]- = hydrotris(1-pyrazolyl)borate).
The novel mononuclear PPh4-fac-[FeIII[HB(pz)3](CN)3]*H2O (1) [PPh4+= tetraphenylphosphonium cation; (HB(pz)3)- = hydrotris(1-pyrazolyl)borate] and tetranuclear fac-[[FeIII[HB(pz)3](CN)2(mu-CN)]3FeIII(H2O)3]*6H2O (2) have been prepared and characterized by X-ray diffraction analysis. Crystal data for compound 1: monoclinic, space group P21/c, a = 9.575(3) A, b = 21.984(4) A, c = 16.863(3) A, beta = 100.34(2) degrees, U = 3486(1) A3, Z = 4. Crystal data for compound 2: orthorhombic, space group Pnam, a = 14.084(3) A, b = 14.799(4) A, c = 25.725(5) A, U = 5362(2) A3, Z = 4. Compound 1 is a low-spin iron(III) compound with three cyanide ligands in fac arrangement and a tridentate pyrazolylborate ligand building a distorted octahedral environment around the iron atom. Compound 2 is the first example of a molecular species containing three peripheral low-spin iron(III) ions linked to a central high-spin iron(III) cation by single cyanide bridges, the anion of 1 acting as a monodentate ligand in 2. Variable-temperature magnetic susceptibility measurements of 2 reveal the occurrence of a significant ferromagnetic coupling between the three peripheral low-spin iron(III) centers and the central high-spin iron(III) ion cations leading to a low-lying nonet spin state.
Lescouëzec
Rodrigue
R
Departament de Química Inorgànica/Instituto de Ciencia Molecular, Facultat de Química de la Universitat de València, Dr. Moliner 50, 46100-Burjassot, València, Spain.
Vaissermann
Jacqueline
J
Lloret
Francesc
F
Julve
Miguel
M
Verdaguer
Michel
M