Metallacrowns as templates for diabolo-like {LnCu8} complexes with nearly perfect square antiprismatic geometry

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A series of diabolo-like nonanuclear {LnIIICuII8} (Ln = Tb, Dy, Ho, Er, Tm, Yb and Y) clusters 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 have been prepared. Despite the lack of crystallographic symmetry these molecules engender the lanthanide ions with highly axial mJ states. We observe that 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. We find slow magnetic relaxation behaviour for the DyIII, ErIII, TmIII and YbIII analogues, and show that the obtained effective energy barriers are not consistent with excitations on the LnIII ion, suggesting a more nuanced situation.

Bibliographical metadata

Original languageEnglish
JournalChemistry: A European Journal
Early online date15 Sep 2017
Publication statusPublished - 2017

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