Twists to the Spin Structure of the Ln<sub>9</sub>‑diabolo Motif Exemplified in Two {Zn<sub>2</sub>Ln<sub>2</sub>}[Ln<sub>9</sub>]{Zn<sub>2</sub>} Coordination Clusters

Two pentadecanuclear Zn<sub>4</sub>Ln<sub>11</sub> [with Ln = Gd­(<b>1</b>) or Dy­(<b>2</b>)] coordination clusters, best formulated as {Zn<sub>2</sub>Ln<sub>2</sub>}­[Ln<sub>9</sub>]­{Zn<sub>2</sub>}, are presented. The central {Ln<sub>9</sub>} diabolo core has a {Zn<sub>2</sub>Ln<sub>2</sub>} handle motif pulling at two outer Ln ions of the central core via two {ZnLn} units, which also invest the system with <i>C</i><sub>2</sub> point symmetry. The resulting cluster motif is supported on two Zn “feet”, corresponding to the {Zn<sub>2</sub>} unit in the formula. A thorough investigation of the magnetic properties in the light of the properties of previously reported {Ln<sub>9</sub>} 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 {Gd<sub>9</sub>} diabolo plays a decisive role. In stabilizing the core by attachment of the {Zn}<sup>2+</sup> “feet” and using the <i>C<sub>2</sub></i> symmetry related {ZnGd}<sup>5+</sup> handles to influence the spin direction of the central Gd of the {Gd<sub>9</sub>} diabolo, we can understand why the “naked” {Gd<sub>9</sub>} diabolo shows ambiguous spin structure. This then allowed us to elucidate the single-molecule magnetic (SMM) properties of the Dy-based compound <b>2</b> through disentangling the magnetic properties of the isostructural Gd-based compound <b>1</b>.