Properties of Prussian blue materials manifested in molecular complexes: observation of cyanide linkage isomerism and spin-crossover behavior in pentanuclear cyanide clusters. Academic Article uri icon


  • Pentanuclear, cyanide-bridged clusters [M(tmphen)2]3[M'(CN)6]2 (M/M' = Zn/Cr (1), Zn/Fe (2), Fe/Fe (3), Fe/Co (4), and Fe/Cr (5); tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline) were prepared by combining [M'III(CN)6]3- anions with mononuclear complexes of MII ions with two capping tmphen ligands. The clusters consist of a trigonal bipyramidal (TBP) core with three MII ions in the equatorial positions and two M'III ions in the axial positions. Compounds 1-4 are isostructural and crystallize in the monoclinic space group P21/c. Complex 5 crystallizes in the enantiomorphic space group P3221. The magnetic properties of compounds 1 and 2 reflect the contributions of the individual [CrIII(CN)6]3- and [FeIII(CN)6]3- ions. The FeII ions in compounds 3 and 4 exhibit a gradual, temperature-induced spin transition between high spin (HS) and low spin (LS), as determined by the combination of Mssbauer spectroscopy, magnetic measurements, and single-crystal X-ray studies. The investigation of compound 5 by these methods and by IR spectroscopy indicates that cyanide linkage isomerism occurs during cluster formation. The magnetic behavior of 5 is determined by weak ferromagnetic coupling between the axial CrIII centers mediated by the equatorial diamagnetic FeII ions. Mssbauer spectra collected in the presence of a high applied field have allowed, for the first time, the direct experimental observation of uncompensated spin density at diamagnetic metal ions that bridge paramagnetic metal ions.

published proceedings

  • J Am Chem Soc

altmetric score

  • 125

author list (cited authors)

  • Shatruk, M., Dragulescu-Andrasi, A., Chambers, K. E., Stoian, S. A., Bominaar, E. L., Achim, C., & Dunbar, K. R.

citation count

  • 191

complete list of authors

  • Shatruk, Mikhail||Dragulescu-Andrasi, Alina||Chambers, Kristen E||Stoian, Sebastian A||Bominaar, Emile L||Achim, Catalina||Dunbar, Kim R

publication date

  • May 2007