Incorporation of expanded organic cations in dysprosium(III) borohydrides for achieving luminescent molecular nanomagnets

Luminescent single-molecule magnets (SMMs) constitute a class of molecular materials offering optical insight into magnetic anisotropy, magnetic switching of emission, and magnetic luminescent thermometry. They are accessible using lanthanide(III) complexes with advanced organic ligands or metalloligands. We present a simple route to luminescent SMMs realized by the insertion of well-known organic cations, tetrabutylammonium and tetraphenylphosphonium, into dysprosium(III) borohydrides, the representatives of metal borohydrides investigated due to their hydrogen storage properties. We report two novel compounds, [n-Bu4N][DyIII(BH4)4] (1) and [Ph4P][DyIII(BH4)4] (2), involving DyIII centers surrounded by four pseudo-tetrahedrally arranged BH4– ions. While 2 has higher symmetry and adopts a tetragonal unit cell (I41/a), 1 crystallizes in a less symmetric monoclinic unit cell (P21/c). They exhibit yellow room-temperature photoluminescence related to the f–f electronic transitions. Moreover, they reveal DyIII-centered magnetic anisotropy generated by the distorted arrangement of four borohydride anions. It leads to field-induced slow magnetic relaxation, well-observed for the magnetically diluted samples, [n-Bu4N][YIII0.9DyIII0.1(BH4)4] (1@Y) and [Ph4P][YIII0.9DyIII0.1(BH4)4] (2@Y). 1@Y exhibits an Orbach-type relaxation with an energy barrier of 26.4(5) K while only the onset of SMM features was found in 2@Y. The more pronounced single-ion anisotropy of DyIII complexes of 1 was confirmed by the results of the ab initio calculations performed for both 1–2 and the highly symmetrical inorganic DyIII borohydrides, α/β-Dy(BH4)3, 3 and 4. The magneto-luminescent character was achieved by the implementation of large organic cations that lower the symmetry of DyIII centers inducing single-ion anisotropy and separate them in the crystal lattice enabling the emission property. These findings are supported by the comparison with 3 and 4, crystalizing in cubic unit cells, which are not emissive and do not exhibit SMM behavior.