TY - JOUR
T1 - Enhancing the blocking temperature in single-molecule magnets by incorporating 3d-5d exchange interactions
AU - Pedersen, Kasper Søndergaard
AU - Schau-Magnussen, Magnus
AU - Bendix, Jesper
AU - Weihe, Høgni
AU - Palii, Andrei V
AU - Klokishner, Sophia I
AU - Ostrovsky, Serghei
AU - Reu, Oleg S
AU - Mutka, Hannu
AU - Tregenna-Piggott, Philip L W
PY - 2010/12/3
Y1 - 2010/12/3
N2 - We report the first single-molecule magnet (SMM) to incorporate the [Os(CN)6]3- moiety. The compound (1) has a trimeric, cyanide-bridged MnIII-OsIII-MnIII skeleton in which MnIII designates a [Mn(5-Brsalen)(MeOH)]+ unit (5-Brsalen=N,N′-ethylenebis(5-bromosalicylideneiminato)). X-ray crystallographic experiments reveal that 1 is isostructural with the Mn III-FeIII-MnIII analogue (2). Both compounds exhibit a frequency-dependent out-of-phase π″(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 Δeff/kB=19a K (τ0=5.0× 10 -7a s; kB=Boltzmann constant), whereas only the onset (1.5a kHz, 1.8a K) of π″(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)(Oh*) 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∥MnOs = -30.6a 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. The iron age to the osmium age: Introduction of [Os(CN) 6]3- in single-molecule magnets instead of [Fe(CN) 6]3- leads to an increase in the blocking temperature due to stronger exchange interactions and orbital contributions that arise from the unquenched orbital angular momentum of the octahedral OsIII ion (see figure).
AB - We report the first single-molecule magnet (SMM) to incorporate the [Os(CN)6]3- moiety. The compound (1) has a trimeric, cyanide-bridged MnIII-OsIII-MnIII skeleton in which MnIII designates a [Mn(5-Brsalen)(MeOH)]+ unit (5-Brsalen=N,N′-ethylenebis(5-bromosalicylideneiminato)). X-ray crystallographic experiments reveal that 1 is isostructural with the Mn III-FeIII-MnIII analogue (2). Both compounds exhibit a frequency-dependent out-of-phase π″(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 Δeff/kB=19a K (τ0=5.0× 10 -7a s; kB=Boltzmann constant), whereas only the onset (1.5a kHz, 1.8a K) of π″(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)(Oh*) 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∥MnOs = -30.6a 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. The iron age to the osmium age: Introduction of [Os(CN) 6]3- in single-molecule magnets instead of [Fe(CN) 6]3- leads to an increase in the blocking temperature due to stronger exchange interactions and orbital contributions that arise from the unquenched orbital angular momentum of the octahedral OsIII ion (see figure).
U2 - 10.1002/chem.201001259
DO - 10.1002/chem.201001259
M3 - Journal article
C2 - 20938935
SN - 0947-6539
VL - 16
SP - 13458
EP - 13464
JO - Chemistry: A European Journal
JF - Chemistry: A European Journal
IS - 45
ER -