Utility of all-pyrazole heteroscorpionates in f-element chemistry

Since their discovery in 1966, scorpionate ligands have been utilized to make coordination compounds for a variety of applications such as: studying organometallic reactions, biomimetic complexes, light-emitting materials and single-ion magnets. The recent development of a solvent-free pyrazole substitution chemistry has yielded the quantitative synthesis of asymmetrically functionalized all-pyrazole heteroscorpionate ligands. In this frontier article, we highlight the utility of all-pyrazole heteroscorpionates, specifically, nitro-trispyrazolylborates, in f-element chemistry. They offer great versatility in coordinating ability, donor strength, steric bulk and even optical charge transfer properties, all of which can be used to tune the properties of resultant complexes with metal ions. We show how they can impart structural diversity, sensitize Ln³⁺ luminescence and engender magnetic anisotropy and slow magnetic relaxation in the ion they coordinate. Additionally, we comment on the future of functionalized trispyrazolyl scorpionates, which includes enabling post-synthetic modifications of f-element complexes and becoming a platform to study the electronic properties of low oxidation state actinides.