Trityl-Based Lanthanide-Supramolecular Assemblies Exhibiting Slow Magnetic Relaxation

The triphenylmethane (trityl) group has been recognized as a supramolecular synthon in crystal engineering, molecular machine rotors and stereochemical chirality inductors in materials science. Herein we demonstrate for the first time how it can be utilized in the domain of molecular magnetic materials through shaping of single molecule magnet (SMM) properties within the lanthanide complexes in tandem with other non-covalent interactions. Trityl-appended mono- (HL¹ ) and bis-compartmental (HL² ) hydrazone ligands were synthesized and complexated with Dy(III) and Er(III) triflate and nitrate salts to generate four monometallic (1-4) and two bimetallic (5, 6) complexes. The static and dynamic magnetic properties of 1-6 were investigated, revealing that only ligand HL¹ induces assemblies (1-4) capable of showing SMM behaviour, with Dy(III) congeners (1, 2) able to exhibit the phenomenon also under zero field conditions. Theoretical ab initio studies helped in determination of Dy(III) energetic levels, magnetic anisotropic axes and corroborated magnetic relaxation mechanisms to be a combination of Raman and quantum tunnelling in zero dc field, the latter being cancelled in the optimum non-zero dc field. Our work represents the first study of magneto-structural correlations within the trityl Ln-SMMs, leading to generation of slowly relaxing zero-field dysprosium complexes within the hydrogen-bonded assemblies.