TY - JOUR
T1 - Metallacrowns as Templates for Diabolo‐like LnCu $_8$ Complexes with Nearly Perfect Square Antiprismatic Geometry
AU - Zhou, Guo‐Jun
AU - Han, Tian
AU - Ding, You‐Song
AU - Chilton, Nicholas F.
AU - Zheng, Yan‐Zhen
PY - 2017/9/15
Y1 - 2017/9/15
N2 - A series of diabolo‐like nonanuclear {LnIIICuII8} (Ln=Tb, Dy, Ho, Er, Tm, Yb, and Y) clusters were prepared in which the LnIII ion is capped by two 8‐MC‐4 metallacrown ligands to form a nearly ideal square antiprismatic (SAP) coordination geometry with D4d symmetry. Despite the lack of crystallographic symmetry, these molecules engender the lanthanide ions with highly axial mJ states. The axial/equatorial nature of the crystal field in environments close to ideal SAP geometry is very subtle and influenced by the nature of the ligand lone pairs. Slow magnetic relaxation behaviour was observed for the DyIII, ErIII, TmIII, and YbIII analogues, and the obtained effective energy barriers are not consistent with excitations on the LnIII ion, suggesting a more nuanced situation.
AB - A series of diabolo‐like nonanuclear {LnIIICuII8} (Ln=Tb, Dy, Ho, Er, Tm, Yb, and Y) clusters were prepared in which the LnIII ion is capped by two 8‐MC‐4 metallacrown ligands to form a nearly ideal square antiprismatic (SAP) coordination geometry with D4d symmetry. Despite the lack of crystallographic symmetry, these molecules engender the lanthanide ions with highly axial mJ states. The axial/equatorial nature of the crystal field in environments close to ideal SAP geometry is very subtle and influenced by the nature of the ligand lone pairs. Slow magnetic relaxation behaviour was observed for the DyIII, ErIII, TmIII, and YbIII analogues, and the obtained effective energy barriers are not consistent with excitations on the LnIII ion, suggesting a more nuanced situation.
U2 - 10.1002/chem.201703830
DO - 10.1002/chem.201703830
M3 - Article
SN - 0947-6539
VL - 23
SP - 15617
EP - 15622
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 62
ER -