TY - JOUR
T1 - Structures, magnetic properties, and XPS of cyanide-bridged Nd III/SmIII/GdIII-CrIII complexes
AU - Akitsu, Takashiro
AU - Einaga, Yasuaki
PY - 2006/3/20
Y1 - 2006/3/20
N2 - Synthesis, structural characterization, and spectroscopic and magnetic properties of three new cyano-bridged 3d-4f bimetallic complexes, Ln III(DMF)4(H2O)3CrIII (CN)6·nH2O (Ln = Nd, Sm, Gd), have been described. The Nd-Cr complex crystallizes in the monoclinic P21/n space group with the following unit cell parameters: a = 20.063(7) Å, b = 8.967(4) Å, c = 18.023(6) Å, b = 96.12(3)°, V = 3224(2) Å3, and Z = 4. The neodymium (III) ion, which adopts anti-prism eight-coordination environment, is linked to the [CrIII(CN) 6]3- moiety through a bridging cyanide ligand with Nd-N = 2.550(4) Å and Nd-N-C = 164.4(4)°. The variable-temperature (0.5 T at 2-300 K) and variable-field (0-5 T at 2 and 5 K) magnetic measurements reveal that the weak interaction of Gd-Cr complexes differs from that of Nd-Cr and Sm-Cr ones mainly because of the lack of orbital angular momentum. The XPS and diffuse reflectance electronic spectra were also measured to discuss charge transfer transitions concerning π-backdonation from the viewpoint of magneto-optical functions.
AB - Synthesis, structural characterization, and spectroscopic and magnetic properties of three new cyano-bridged 3d-4f bimetallic complexes, Ln III(DMF)4(H2O)3CrIII (CN)6·nH2O (Ln = Nd, Sm, Gd), have been described. The Nd-Cr complex crystallizes in the monoclinic P21/n space group with the following unit cell parameters: a = 20.063(7) Å, b = 8.967(4) Å, c = 18.023(6) Å, b = 96.12(3)°, V = 3224(2) Å3, and Z = 4. The neodymium (III) ion, which adopts anti-prism eight-coordination environment, is linked to the [CrIII(CN) 6]3- moiety through a bridging cyanide ligand with Nd-N = 2.550(4) Å and Nd-N-C = 164.4(4)°. The variable-temperature (0.5 T at 2-300 K) and variable-field (0-5 T at 2 and 5 K) magnetic measurements reveal that the weak interaction of Gd-Cr complexes differs from that of Nd-Cr and Sm-Cr ones mainly because of the lack of orbital angular momentum. The XPS and diffuse reflectance electronic spectra were also measured to discuss charge transfer transitions concerning π-backdonation from the viewpoint of magneto-optical functions.
KW - Chromium(III)
KW - Cyano-bridged
KW - Lanthanide(III)
KW - Magnetic properties
KW - XPS
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U2 - 10.1016/j.ica.2005.12.004
DO - 10.1016/j.ica.2005.12.004
M3 - Article
AN - SCOPUS:33644798902
VL - 359
SP - 1421
EP - 1426
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
SN - 0020-1693
IS - 5
ER -