Sandwich-Type Mixed Tetrapyrrole Rare-Earth Triple-Decker Compounds. Effect of the Coordination Geometry on the Single-Molecule-Magnet Nature

Employment of the raise-by-one step method starting from M(TClPP)(acac) (acac = monoanion of acetylacetone) and [Pc(OPh)(8)]-M'[Pc(OPh)(8)] led to the isolation and free modulation of the two rare-earth ions in the series of four mixed tetrapyrrole dysprosium sandwich complexes {(TClPP)M[Pc(OPh)(8)]M'[Pc(OPh)(8)]} [1-4; TClPP = dianion of meso-tetrakis(4-chlorophenyl)porphyrin; Pc(OPh)(8) = dianion of 2,3,9,10,16,17,23,24-octa(phenoxyl)phthalocyanine; M M' = Dy-Dy, Y-Dy, Dy-Y, and Y-Y]. Single-crystal X-ray diffraction analysis reveals different octacoordination geometries for the two metal ions in terms of the twist angle (defined as the rotation angle of one coordination square away from the eclipsed conformation with the other) between the two neighboring tetrapyrrole rings for the three dysprosium-containing isostructural triple-decker compounds, with the metal ion locating between an inner phthalocyanine ligand and an outer porphyrin ligand with a twist angle of 9.64-9.90 degrees and the one between two phthalocyanine ligands of 25.12-25.30 degrees. Systematic and comparative studies over the magnetic properties reveal magnetic-field-induced single-molecule magnet (SMM), SMM, and non-SMM nature for 1-3, respectively, indicating the dominant effect of the coordination geometry of the spin carrier, instead of the f-f interaction, on the magnetic properties. The present result will be helpful for the future design and synthesis of tetrapyrrole lanthanide SMMs with sandwich molecular structures.