Exchange-bias quantum tunnelling in a CO₂-based Dy₄-single molecule magnet

Carbamate formation in green-plants through the RuBisCO enzyme continuously plays a pivotal role in the conversion of CO₂ from the atmosphere into biomass. With this in mind, carbamate formation from CO₂ by a lanthanide source in the presence of a secondary amine is herein explored leading to a lanthanide–carbamate cage with the formula [Dy4(O₂CNiPr₂)$_{12}$]. Magnetic studies show slow relaxation leading to the observation of hysteresis loops; the tetranuclear cage being a single molecule magnet. Detailed interpretation of the data reveals: (i) the presence of two different exchange interactions, ferromagnetic and antiferromagnetic and (ii) the observation of exchange-bias quantum tunnelling with two distinct sets of loops, attributable to ferromagnetic interactions between dysprosium ions at longer distances and antiferromagnetic exchange between dysprosium ions at shorter distances. The results clearly demonstrate that the [Dy4(O₂CNiPr₂)$_{12}$] cage acts as a quantum magnet which in turn could be at the heart of hybrid spintronic devices after having implemented CO₂ as a feedstock.