Twists to the Spin Structure of the Ln9-diabolo Motif Exemplified in Two {Zn2Ln2}[Ln9]{Zn2} Coordination Clusters.

ABSTRACT

Two pentadecanuclear Zn4Ln11 [with Ln = Gd(1) or Dy(2)] coordination clusters, best formulated as {Zn2Ln2}[Ln9]{Zn2}, are presented. The central {Ln9} diabolo core has a {Zn2Ln2} handle motif pulling at two outer Ln ions of the central core via two {ZnLn} units, which also invest the system with C2 point symmetry. The resulting cluster motif is supported on two Zn "feet", corresponding to the {Zn2} unit in the formula. A thorough investigation of the magnetic properties in the light of the properties of previously reported {Ln9} diabolo compounds was undertaken. Up to now, the spin structure of such diabolo motifs usually proves ambiguous. Our magnetic studies show that the orientation of the central spin in the {Gd9} diabolo plays a decisive role. In stabilizing the core by attachment of the {Zn}2+ "feet" and using the C2 symmetry related {ZnGd}5+ handles to influence the spin direction of the central Gd of the {Gd9} diabolo, we can understand why the "naked" {Gd9} diabolo shows ambiguous spin structure. This then allowed us to elucidate the single-molecule magnetic (SMM) properties of the Dy-based compound 2 through disentangling the magnetic properties of the isostructural Gd-based compound 1.