Syntheses, structures, and electrochemical and magnetic properties of rectangular heterobimetallic clusters based on tricyanometallic building blocks

Cai Feng Wang, Wei Liu, You Song, Xin Hui Zhou, Jing Lin Zuo, Xiao Zeng You

Research output: Contribution to journalArticlepeer-review

46 Scopus citations

Abstract

Three tricyanometalate precursors, (Bu4N)[(PhTp)Fe(CN) 3]· H2O (1), (Bu4N)[(MeTp)Fe(CN) 3] (2), and (Bu4N)[(iBuTp)-Fe(CN)3] (3) [Bu4N+ = tetrabutylammonium cation; PhTp = tris(pyrazolyl)phenylborate; MeTp = methyltris(pyrazolyl)-borate; iBuTp = 2-methylpropyltris(pyrazolyl)borate], were successfully synthesized. By using 1-3 as building blocks, four rectangular clusters, [(PhTp)Fe(CN) 3Cu(bpy)(H2O)-(ClO4)]2· 2H2O (4; bpy = 2,2′-bipyridine), [(PhTp)Fe(CN) 3Ni-(tren)]2(ClO4)2 [5; tren = tris(2-amino)ethylamine], [(MeTp)-Fe(CN)3Ni(tren)] 2(ClO4)2·2H2O (6), and [(iBuTp)Fe(CN)3Ni-(tren)]2(ClO4) 2·2H2O·2CH3OH (7), were prepared in parallel and structurally characterized. All clusters show similar square structures, where FeIII and MII (M = CuII or NiII) ions are alternatively located on the rectangle corners. The cyclic voltammograms of FeIII2NiII2 clusters 5-7 reveal two quasi-reversible iron-centered reduction processes and two quasi-reversible nickel-centered oxidation processes. Magnetic studies show intramolecular ferromagnetic coupling and appreciable magnetic anisotropy in clusters 4-7. Complexes 5-7 show obvious frequency dependence in the alternating current magnetic susceptibility data, which indicates single-molecule magnet behavior with preexponential factors of τ0 = 4.5 × 10 -8 s (5), 6.1 × 10-8 s (6), and 5.0 × 10 -8 s (7) and the effective spin-reversal barriers of Ueff = 17.5K (5), 20.6 K (6), and 20.8 K (7).

Original languageEnglish
Pages (from-to)717-727
Number of pages11
JournalEuropean Journal of Inorganic Chemistry
Issue number5
DOIs
StatePublished - Feb 2008
Externally publishedYes

Keywords

  • Crystal structures
  • Cyanometalates
  • Magnetic properties
  • Polynuclear complexes
  • Single-molecule magnets

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