TY - JOUR
T1 - Structures, magnetic properties, and XPS of cyanide-bridged Nd III/SmIII/GdIII-CrIII complexes
AU - Akitsu, Takashiro
AU - Einaga, Yasuaki
N1 - Funding Information:
This work was supported by Grant-in-Aid for the 21st Century COE program ‘KEIO Life Conjugate Chemistry’ form the Ministry of Education, Culture, Sports, Science, and Technology, Research Foundation for Opto-Sceince and Technology, and Japan and Mizuho Foundation for the Promotion of Science. The authors are grateful to Prof. Tohru Yamada and Dr Taketo Ikeno (Keio University) for the use of the differential scanning calorimetry apparatus, and Dr Motoko Akita-Tanaka (Institute for Molecular Science) for the use of SQUID.
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 -