Structures and XPS studies of several 3d-4f cyano-bridged LnIII-FeIII/CoIII heterometallic complexes

Takashiro Akitsu, Yasuaki Einaga

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

Characterization and crystal structure determination of 3d-4f cyano-bridged bimetallic assemblies, Ln(DMF)4(H2O)3Co(CN)6 · H2O (DMF = N,N′-dimethylformamide, Ln = Tb, Dy, Ho and Er) have been newly carried out. We have observed their isostructural features and gradual decreasing cell constants and corresponding changes of local bond distances and angles around the cyano-bridges in accord with the ionic radii changes due to lanthanoid contraction. In order to elucidate the reasons that only Nd-Fe and Nd-Co complexes can exhibit photo-induced magnetic functions, we have also investigated the electronic properties for several analogous 3d-4f complexes, Ln(DMF)4(H2O)3M(CN)6 · H2O (Ln = Ce, Nd, Sm, Gd, Tb, Dy, Ho and Er; M = Co and Fe), by means of X-ray photoelectron spectroscopy (XPS). We found that the characteristic bent features of Nd-N-C bond angles and the slight shift of binding energies of Ln 4d3/2 peaks in the 3d-4f systems being closed to mixed-valence states might be the reasons for the novel functions.

Original languageEnglish
Pages (from-to)2655-2662
Number of pages8
JournalPolyhedron
Volume25
Issue number13
DOIs
Publication statusPublished - 2006 Sep 11

Keywords

  • 3d-4f Complexes
  • Crystal structures
  • Cyanide-bridged
  • Heterometallates
  • XPS

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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