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Two pentadecanuclear Zn 4 Ln 11 [with Ln = Gd(1) or Dy(2)] coordination clusters, best formulated as {Zn 2 Ln 2 }[Ln 9 ]{Zn 2 }, are presented. The central {Ln 9 } diabolo core has a {Zn 2 Ln 2 } handle motif pulling at two outer Ln ions of the central core via two {ZnLn} units, which also invest the system with C 2 point symmetry. The resulting cluster motif is supported on two Zn "feet", corresponding to the {Zn 2 } unit in the formula. A thorough investigation of the magnetic properties in the light of the properties of previously reported {Ln 9 } 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 9 } diabolo plays a decisive role. In stabilizing the core by attachment of the {Zn} 2+ "feet" and using the C 2 symmetry related {ZnGd} 5+ handles to influence the spin direction of the central Gd of the {Gd 9 } diabolo, we can understand why the "naked" {Gd 9 } 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.

inorganic chemistry

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