Mixed d-f Block Single-Molecule Toroics

Single Molecule Toroics pp 15–66Cite as Mixed d-f Block Single-Molecule Toroics Keith S. Murray, Stuart K. Langley, Kuduva R. Vignesh, Gopalan Rajaraman, Kieran Hymas & Alessandro Soncini Chapter First Online: 24 November 2022 3 Accesses Abstract In this chapter, we focus on the single-molecule toroidal (SMT) behaviour of a family of “double dysprosium triangle” heptanuclear species which contain a bridging d-block M(III) or a p-block M(III) ion. They are of general formula [MIIIDyIII 6(OH)8(o-tol)12(NO3)(MeOH)5]∙3MeOH, labelled MDy 6, where o-tol = o-toluate. The parent compound has M = Cr, with subsequent family members having M = Mn, Fe, Co and Al, the latter two having diamagnetic M(III) centres. This heptanuclear family could also be made using chloride as counter-anion rather than nitrate, the molecular structures being similar to the nitrates though the unit cells are different. The LnIII ion could also be varied to include Tb, Ho and Er and, thus, allow exploration of SMT behaviour in non-Dy analogues. The syntheses, structures and magnetic and EPR properties are described, starting with the parent CrDy 6. Theoretical calculations are described in detail, with MOLCAS methods employed to determine anisotropy directions, blocking barriers and relaxation effects and a newly developed model used to calculate magnetically coupled toroidal states and the role of these states in spin dynamics. The direct simulation of the micro-Squid magnetic hysteresis loops of all family members is described as well as that of the original Dy 3 material. Toroido-structural correlations are presented with strategies developed to optimize the important ferrotoroidic coupling between Dy3 triangles in these heptanuclear toroidal species. Finally, we give a brief summary of SMT behaviour in ring-shaped 3d-4f toroidal species.