Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 16, Issue 45, Pages 13458-13464Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201001259
Keywords
anisotropy; magnetic properties; manganese; osmium; single-molecule magnets
Categories
Funding
- Swiss National Science Foundation [IZ73ZO-128078/1]
- Supreme Council for Science and Technological Development of Moldova
- Danish Neutron Scattering Society (DANSCATT)
- Danish Chemical Society
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We report the first singlemolecule magnet (SMM) to incorporate the [Os(CN)(6)](3-) moiety. The compound (1) has a trimeric, cyanidebridged MnIII-OsIII-MnIII skeleton in which Mn(III) designates a [Mn(5Brsalen)(MeOH)](+) unit (5-Brsalen=N,N'-ethylenebis(5-bromosalicylideneiminato)). X-ray crystallographic experiments reveal that 1 is isostructural with the Mn(III)-Fe(III)-Mn(III) analogue (2). Both compounds exhibit a frequency-dependent out-of-phase chi ''(T) alternating current (ac) susceptibility signal that is suggestive of SMM behaviour. From the Arrhenius expression, the effective barrier for 1 is found to be Delta eff/k(B)=19 K (tau(0)=5.0x10(-7) s; k(B)=Boltzmann constant), whereas only the onset (1.5 kHz, 1.8 K) of chi ''(T) is observed for 2, thus indicating a higher blocking temperature for 1. The strong spin-orbit coupling present in Os(III) isolates the E'(1g(1/2))(O(h)*) Kramers doublet that exhibits orbital contributions to the single-ion anisotropy. Magnetic susceptibility and inelastic neutron-scattering measurements reveal that substitution of [Fe(CN)(6)](3-) by the [Os(CN)(6)](3-) anion results in larger ferromagnetic, anisotropic exchange interactions going from quasi-Ising exchange interactions in 2 to pure Ising exchange for 1 with J(parallel to)(MnOs)=-30.6 cm(-1). The combination of diffuse magnetic orbitals and the Ising-type exchange interaction effectively contributes to a higher blocking temperature. This result is in accordance with theoretical predictions and paves the way for the design of a new generation of SMMs with enhanced SMM properties.
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