Highly anisotropic exchange interactions in a trigonal bipyramidal cyanide-bridged Ni 11 3Os 11 2 Cluster

Andrei V. Palii, Oleg S. Reu, Sergei M. Ostrovsky, Sophia I. Klokishner, Boris S. Tsukerblat, Matthew Hilfiger, Michael Shatruk, Andrey Prosvirin, Kim R. Dunbar

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17 Scopus citations


This article is a part of our efforts to control the magnetic anisotropy in cyanide-based exchange-coupled systems with the eventual goal to obtain single-molecule magnets with higher blocking temperatures. We give the theoretical interpretation of the magnetic properties of the new pentanuclear complex {[Ni II(tmphen) 2] 3[Os III(CN) 6] 2} -6CH 3CN (Ni II 3Os III 2 cluster). Because the system contains the heavy Os III ions, spin-orbit coupling considerably exceeds the contributions from the low-symmetry crystal field and exchange coupling. The magnetic properties of the Ni II 3Os III 2 cluster are described in the framework of a highly anisotropic pseudo-spin Hamiltonian that corresponds to the limit of strong spin-orbital coupling and takes into account the complex molecular structure. The model provides a good fit to the experimental data and allows the conclusion that the trigonal axis of the bipyramidal Ni II 3Os III 2 cluster is a hard axis of magnetization. This explains the fact that in contrast with the isostructural trigonal bipyramidal Mn III 2Mn II 3 cluster, the Ni II 3Os III 2 system does not exhibit the single-molecule magnetic behavior.

Original languageEnglish
Pages (from-to)6886-6890
Number of pages5
JournalJournal of Physical Chemistry A
Issue number25
StatePublished - 25 Jun 2009

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry


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