Enhancing the magnetic anisotropy of cyano-ligated chromium(II) and chromium(III) complexes via heavy halide ligand effects.
A method of increasing the axial zero-field splitting parameter for transition metal complexes of utility in the assembly of magnetic clusters is demonstrated through the use of heavy atoms as auxiliary ligands. The octahedral complexes [Cr(dmpe)(2)(CN)X](+) (dmpe = 1,2-bis(dimethylphosphino)ethane, X = Cl, Br, I) and Cr(dmpe)(2)(CN)X (X = Cl, I) are synthesized and structurally characterized. Variable-field magnetization measurements show the magnitude of D for these complexes to increase significantly as the halide ligand varies from chloride to iodide, ranging from 0.11 cm(-1) for [Cr(dmpe)(2)(CN)Cl](+) to 6.26 cm(-1) for Cr(dmpe)(2)(CN)I.
Karunadasa
Hemamala I
HI
Department of Chemistry, University of California, Berkeley, California 94720-1460, USA.
Arquero
Kristine D
KD
Berben
Louise A
LA
Long
Jeffrey R
JR
D016880:Anisotropy; D002857:Chromium / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003486:Cyanides / Q000737:chemistry*; D006219:Halogens / Q000737:chemistry*; D008024:Ligands; D008280:Magnetics; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013696:Temperature
D003486:Cyanides; D006219:Halogens; D008024:Ligands; D009942:Organometallic Compounds; D002857:Chromium