Lanthanoid (III) diphthalocyanine (LnPc2) double decker complexes have been intensely studied due to their unique properties, in particular their magnetism. The terbium complex, TbPc2, in particular, has shown to be an effective single-molecule magnet, with a blocking temperature between 30 and 50 K, and has since become the most studied of molecular qubit candidates. Since the discovery of the TbPc2 properties, significant research has gone into synthesizing and characterizing various double decker complexes in an effort to better understand the impact of geometric and electronic structure on the magnetic relaxation process. We present here our investigation of the structure and magnetism of four distinct polymorphs of LnPc2 complexes, which we were able to selectively and reproducibly prepare with multiple metal centers. With the help of density functional theory calculations, we will show how controlled crystallization allows for fine-tuning the molecular geometry, intermolecular interactions, and their impact on the resulting magnetism. In order to investigate the impact of the ligand's electronic properties, we have also synthesized and characterized well-defined halogenated complexes, which have been largely unexplored thus far, and will present the study of how the position of the halogen substituents affects magnetic properties.

Fine control of the structure of lanthanoid (III) diphthalocyanine complexes allows for a detailed study of their structure-property relationships

ACS Fall 2021

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