Structural tailoring effects on the magnetic behavior of symmetric and asymmetric cubane-type Ni complexes

Alexey N. Ponomaryov, Namseok Kim, Jaewon Hwang, Hiroyuki Nojiri, Johan Van Tol, Andrew Ozarowski, Jena Park, Zeehoon Jang, Byoungjin Suh, Sungho Yoon, Kwang Yong Choi

Research output: Contribution to journalArticlepeer-review

11 Citations (Scopus)

Abstract

Using two kinds of carboxylate ligands with small but significant differences in steric size, symmetric and asymmetric FeII and Ni II cubanes have been synthesized in a controlled fashion. Fast sweeping pulsed field measurements showed magnetization hysteresis loops for two cubane-type molecular complexes, [Ni4(μ-OMe)4(O 2CAr4F-Ph)4(HOMe)8] and [Ni 4(μ-OMe)4(O2CArTol) 4(HOMe)6], thus suggesting single-molecule magnet behavior. To differentiate the magnetic properties between the symmetric and asymmetric cubanes, detailed electron paramagnetic resonance (EPR) measurements were performed. From the EPR data, taken at various frequencies and temperatures, zero-field splitting parameters D, E, and other higher-order parameters for both cubane samples were extracted. Compared to the symmetric N-cubane, the asymmetric one shows an increase in the D and E values by about 20 %, thereby suggesting structural engineering effects on the magnetic properties. By using the magnetic parameters determined by EPR, a static magnetization curve at 2 K and a temperature dependence of the magnetic susceptibility were simulated. A good agreement between theoretical and experimental data confirms the validity of the values obtained from EPR measurements.

Original languageEnglish
Pages (from-to)1152-1159
Number of pages8
JournalChemistry - An Asian Journal
Volume8
Issue number6
DOIs
Publication statusPublished - 2013 Jun

Keywords

  • EPR spectroscopy
  • N-cubanes
  • carboxylate ligands
  • magnetic properties
  • steric hindrance

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry

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