Exchange couplings in one-dimensionally arrayed 4f-3d heterometallic [Ln2Cu2]n compounds: A chemical trend of the coupling parameter

Atsushi Okazawa, Kei Fujiwara, Ryo Watanabe, Norimichi Kojima, Shunsuke Yoshii, Hiroyuki Nojiri, Takayuki Ishida

Research output: Contribution to journalArticlepeer-review

21 Citations (Scopus)

Abstract

Heterometallic polymeric coordination compounds [{Ln(hfac) 2(CH3OH)}2{Cu(dmg)(Hdmg)}2] n (abbreviated as [Ln2Cu2]n) involving light lanthanoid ions, Pr, Nd, Sm, and Eu, were synthesized, where H2dmg and Hhfac stand for dimethylglyoxime and 1,1,1,5,5,5- hexafluoropentane-2,4-dione, respectively. The X-ray crystallographic analysis shows that their structures are isomorphous to those of the known heavy lanthanoid analogs. The exchange couplings were evaluated by high-frequency electron paramagnetic resonance and pulsed-field magnetization studies, giving ferromagnetic exchange parameters: JPr-Cu/kB = 0.039(1) K, JNd-Cu/kB = 0.38(1) K, JSm-Cu/kB = 0.95(2) K, and no interaction between Eu and Cu ions. A significant trend is found in the order of the periodic table. The ferro- and antiferromagnetic 4f-3d couplings were characterized for the light and heavy lanthanoid derivatives, respectively. The magnitude of JLn-Cu decreases with a decrease of the 4f-spin portion, i.e., the number of unpaired electrons, whether the coupling is ferro- or antiferromagnetic.

Original languageEnglish
Pages (from-to)3121-3126
Number of pages6
JournalPolyhedron
Volume30
Issue number18
DOIs
Publication statusPublished - 2011 Nov 28

Keywords

  • EPR
  • ESR
  • Exchange interaction
  • Lanthanide
  • Lanthanoid
  • Rare earth metal
  • Single-molecule magnet

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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