Axial Ligand as a Critical Factor for High-Performance Pentagonal Bipyramidal Dy(III) Single-Ion Magnets.

The choice of axial ligands is of great importance for the construction of high-performance Dy-based single-molecule magnets (SMMs). Here, combining axial ligands Ph 3 SiO - (anion of triphenylsilanol) and 2,6-dichloro-4-nitro-PhO - (the anion of 2,6-dichloro-4-nitrophenol) with a neutral macrocyclic ligand 2,14-dimethyl-3,6,10,13,19-pentaazabicyclo[13.3.1]nonadeca-1(19),2,13,15,17-pentaene (L 2 N5 ) generates two new pentagonal bipyramidal Dy(III) complexes [Dy III (L 2 N5 ) (X) 2 ](BPh 4 ) (X = Ph 3 SiO - , 1 ; 2,6-dichloro-4-nitro-PhO - , 2 ) with strong axial ligand fields. Magnetic characterizations show that 1 possesses a large energy barrier above 1000 K and a magnetic hysteresis up to 9 K, whereas 2 only displays field-induced peaks of alternating-current susceptibilities without the hysteresis loop, even though 2 has a similar coordination geometry with 1 . Detailed Ab initio calculations indicate an apparent difference in the axial negative charge between both complexes, which is caused by the diverse electron-donating properties of the axial ligands. The present work provides an efficient strategy to enhance the SMMs' properties, which highlights that the electron-donating property of the axial ligands is especially important for constructing the high-performance Dy-based SMMs.