TY - JOUR
T1 - Structure, magnetism and theory of a family of nonanuclear CuII5LnIII4-triethanolamine clusters displaying single-molecule magnet behaviour
AU - Langley, Stuart
AU - Ungur, Liviu
AU - Chilton, Nicholas
AU - Moubaraki, Boujemaa
AU - Chibotaru, Liviu
AU - Murray, Keith
PY - 2011
Y1 - 2011
N2 - Synthesis, crystal structures and magnetic studies are reported for four new heterometallic CuIIa??LnIII clusters. The reaction of Cu(NO3)23H2O with triethanolamine (teaH3), pivalic acid, triethylamine and Ln(NO3)36H2O (Ln=Gd, Tb, Dy and Ho) results in the formation of four isostructural nonanuclear complexes of general formula [CuII5LnIII4O2(teaH)4 O2CC(CH3)3 2(NO3)4(OMe)4]2MeOH2Et2O [Ln=Gd (1), Tb (2), Dy (3) and Ho (4)]. The metal core of each cluster is made up of four face- and vertex-sharing tetrahedral units. Solid-state DC magnetic susceptibility studies reveal competing anti- and ferromagnetic interactions within each cluster leading to large-spin ground states for 1a??4. Solid-state AC magnetic susceptibility studies show frequency-dependent out-of-phase () signals for 2a??4 below 4a??K, suggestive of single-molecule magnet behaviour. Ab initio calculations on one of the anisotropic examples (3) provided a rare set of J values for Dya??Cu and Cua??Cu exchange interactions (Dya??Dy zero), some ferro- and some antiferromagnetic in character, that explain its magnetic behaviour.
AB - Synthesis, crystal structures and magnetic studies are reported for four new heterometallic CuIIa??LnIII clusters. The reaction of Cu(NO3)23H2O with triethanolamine (teaH3), pivalic acid, triethylamine and Ln(NO3)36H2O (Ln=Gd, Tb, Dy and Ho) results in the formation of four isostructural nonanuclear complexes of general formula [CuII5LnIII4O2(teaH)4 O2CC(CH3)3 2(NO3)4(OMe)4]2MeOH2Et2O [Ln=Gd (1), Tb (2), Dy (3) and Ho (4)]. The metal core of each cluster is made up of four face- and vertex-sharing tetrahedral units. Solid-state DC magnetic susceptibility studies reveal competing anti- and ferromagnetic interactions within each cluster leading to large-spin ground states for 1a??4. Solid-state AC magnetic susceptibility studies show frequency-dependent out-of-phase () signals for 2a??4 below 4a??K, suggestive of single-molecule magnet behaviour. Ab initio calculations on one of the anisotropic examples (3) provided a rare set of J values for Dya??Cu and Cua??Cu exchange interactions (Dya??Dy zero), some ferro- and some antiferromagnetic in character, that explain its magnetic behaviour.
UR - http://onlinelibrary.wiley.com.ezproxy.lib.monash.edu.au/doi/10.1002/chem.201100218/pdf
U2 - 10.1002/chem.201100218
DO - 10.1002/chem.201100218
M3 - Article
SN - 0947-6539
VL - 17
SP - 9209
EP - 9218
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 33
ER -