Inorganic Chemistry, Vol.58, No.4, 2483-2490, 2019
Twists to the Spin Structure of the Ln(9)-diabolo Motif Exemplified in Two {Zn(2)Ln(2)}[Ln(9)]{Zn-2} Coordination Clusters
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" {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.