Syntheses, Structures, and Magnetic Properties of seven-coordinate Lanthanide Porphyrinate or Phthalocyaninate Complexes with Kläui’s Tripodal Ligand

A series of seven-coordinate mononuclear lanthanide(III) complexes of the general formula [(TPP)Ln(L(OEt))]·0.25H2O and [(Pc)Ln(L(OEt))] (Ln(3+) = Dy(3+), Tb(3+), Ho(3+), and Gd(3+); TPP = 5,10,15,20-tetraphenylporphyrinate; Pc = phthalocyaninate; L(OEt)(-) = [(η(5)-C5H5)Co(P(=O)(OEt)2)3](-)) are synthesized on the basis of the tripodal ligand L(OEt)(-) and either porphyrin or phthalocyanine ligands. All of the complexes are characterized by X-ray crystallography and by static and dynamic magnetic measurements. The Dy and Tb complexes show the field-induced slow relaxation of magnetization, and they are interesting seven-coordinate single-lanthanide-based SMMs. The magnetic relaxation properties of these double-decker sandwich complexes are influenced by the local molecular symmetry and are sensitive to subtle distortions of the coordination geometry of the paramagnetic lanthanide ions, such as metal-to-plane distances, plane center distances, and bending angles.