Attaining record-high magnetic exchange, magnetic anisotropy and blocking barriers in dilanthanofullerenes.

While the blocking barrier ( ) and blocking temperature ( ) for "Dysprocenium" SIMs have been increased beyond liquid N temperature, device fabrication of these molecules remains a challenge as low-coordinate Ln complexes are very unstable. Encapsulating the lanthanide ion inside a cage such as a fullerene (called endohedral metallofullerene or EMF) opens up a new avenue leading to several Ln@EMF SMMs. The CASSCF calculations play a pivotal role in identifying target metal ions and suitable cages in this area.

Exploiting host-guest chemistry to manipulate magnetic interactions in metallosupramolecular ML tetrahedral cages.

Reaction of Ni(OTf) with the bisbidentate quaterpyridine ligand results in the self-assembly of a tetrahedral, paramagnetic cage [Ni ]. By selectively exchanging the bound triflate from [OTf⊂Ni ](OTf) (), we have been able to prepare a series of host-guest complexes that feature an encapsulated paramagnetic tetrahalometallate ion inside this paramagnetic host giving [MX⊂Ni ](OTf), where MX = MnCl (), CoCl (), CoBr (), NiCl (), and CuBr () or [MX⊂Ni ](OTf), where MX = FeCl () and FeBr (). Triflate-to-tetrahalometallate exchange occurs in solution and can also be accomplished through single-crystal-to-single-crystal transformations.

Modulating magnetic anisotropy in Ln(iii) single-ion magnets using an external electric field.

Single-molecule magnets have potential uses in several nanotechnology applications, including high-density information storage devices, the realisation of which lies in enhancing the barrier height for magnetisation reversal ( ). However, Ln(iii) single-ion magnets (SIMs) that have been reported recently reveal that the maximum value of values that can be obtained by modulating the ligand fields has already been achieved. Here, we have explored, using a combination of DFT and CASSCF calculations, a unique way to enhance the magnetisation reversal barrier using an oriented external electric field in three well-known Ln(iii) single-ion magnets: [Dy(Py)(O Bu)] (), [Er{N(SiMe)}Cl] () and [Dy(Cp)Cl] ().