Structures, magnetic properties, and XPS of cyanide-bridged Nd III/SmIII/GdIII-CrIII complexes

Takashiro Akitsu, Yasuaki Einaga

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)1421-1426
Number of pages6
JournalInorganica Chimica Acta
Volume359
Issue number5
DOIs
Publication statusPublished - 2006 Mar 20

Fingerprint

Neodymium
Angular momentum
Magnetic variables measurement
Cyanides
cyanides
Prisms
Charge transfer
Magnetic properties
X ray photoelectron spectroscopy
Ligands
Ions
magnetic properties
Temperature
neodymium
electronic spectra
prisms
magnetic measurement
angular momentum
charge transfer
reflectance

Keywords

  • Chromium(III)
  • Cyano-bridged
  • Lanthanide(III)
  • Magnetic properties
  • XPS

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Structures, magnetic properties, and XPS of cyanide-bridged Nd III/SmIII/GdIII-CrIII complexes. / Akitsu, Takashiro; Einaga, Yasuaki.

In: Inorganica Chimica Acta, Vol. 359, No. 5, 20.03.2006, p. 1421-1426.

Research output: Contribution to journalArticle

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abstract = "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) {\AA}, b = 8.967(4) {\AA}, c = 18.023(6) {\AA}, b = 96.12(3)°, V = 3224(2) {\AA}3, 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) {\AA} 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.",
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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.

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