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

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  • Kieran Griffiths
  • Irina A. Kühne
  • Graham J. Tizzard
  • Simon J. Coles
  • George E. Kostakis
  • Annie K. Powell
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<mark>Journal publication date</mark>18/02/2019
<mark>Journal</mark>Inorganic Chemistry
Issue number4
Volume58
Number of pages8
Pages (from-to)2483-2490
Publication statusPublished
Early online date31/01/19
Original languageEnglish

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 Gdbased compound 1.