Lanthanide Single Molecule Magnets

Molecular single-ion magnets based on lanthanides and actinides: Design considerations and new advances in the context of quantum technologies

“…Over the last fifteen years or so, the field of molecular magnetism has undergone a shift of focus away from polynuclear complexes towards SIMs, and in particular toward those containing f-block elements [32][33][34][35][36][37][38][39][40]. This change in direction was largely driven by research progress, being realised that the parameters defining the magnetic relaxation barrier of SMMs, the total spin (S) and the axial anisotropy (D), are not easily achievable by simply scaling molecules to contain more spin-bearing atoms.…”

Revisiting the One-Step Synthesis of Heteroleptic Lanthanide(III) (Porphyrinato)(Phthalocyaninates): Opportunities and Limitations

“…In contrast, in the case of application of dimethoxyphthalonitrile in the synthesis (entry 3), the corresponding triple-decker complex was isolated with only 6 % yield, while octamethoxyphthalocyanine [30] was found to be the main product of the reaction. Presumably, low solubility of the free-base (MeO) 8 PcH 2 and its precipitation from the reaction mixture facilitated its formation resulting in efficient removal of the phthalonitrile from the reaction medium. Thus, the presence of electron-donating groups in the phthalocyanine macrocycle was found to be crucial for the formation of the triple-decker [Por]Ln[Pc]Ln[Por] complexes and was testified by the application of unsubstituted phthalonitrile in the synthesis (entry 4).…”

“…Further increase of the bulkiness of the porphyrin meso-substituents was performed by the introduction of mesityl groups (entry 9). This modification has switched the selectivity of the reaction to the formation of the homoleptic lanthanum diphthalocyaninate La[(BuO) 8 Pc] 2 as a redox mixture.…”

“…[5,6] Complexes with various functional tetrapyrrolic ligands have revealed single molecule magnet properties. [1,[7][8][9][10][11] Non-linear optics, [12] and two-photon absorption [13] have also been shown to be the strengths of heteroleptic lanthanide (porphyrinato)(phthalocyaninates). Hence, the targeted synthesis of heteroleptic sandwichtype complexes with desired arrangement of tetrapyrrolic ligands remains an actual task.…”

Six-Coordinate Ln(III) Complexes with Various Coordination Geometries Showing Distinct Magnetic Properties

“…Single-molecule magnets (SMMs), with the individual molecules acting as tiny magnets, are the most appealing candidates to develop memory devices with ultra-high density and spintronic devices [1][2][3][4][5][6]. The realization of those potential applications firstly depends on the high magnetic blocking temperature (T B ) and large effective energy barrier (U eff ), which have attracted the interests of chemists, physicists, and theorists [7][8][9].…”