State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, PR China.
Inorg Chem. 2013 Jun 3;52(11):6407-16. doi: 10.1021/ic400245n. Epub 2013 May 21.
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.
基于三齿配体 L(OEt)(-)和卟啉或酞菁配体，合成了通式为[(TPP)Ln(L(OEt))]·0.25H2O 和 [(Pc)Ln(L(OEt))] 的一系列七配位单核镧系(III)配合物，Ln(3+) = Dy(3+)、Tb(3+)、Ho(3+) 和 Gd(3+)；TPP = 5,10,15,20-四苯基卟啉；Pc = 酞菁；L(OEt)(-) = (η(5)-C5H5)Co(P(=O)(OEt)2)3。所有配合物均通过 X 射线晶体学和静态和动态磁测量进行了表征。Dy 和 Tb 配合物表现出磁场诱导的磁化缓慢弛豫，它们是有趣的七配位单核镧系 SMM。这些双层夹心配合物的磁弛豫性质受局部分子对称性的影响，并对顺磁镧系离子配位几何形状的细微扭曲敏感，例如金属-平面距离、平面中心距离和弯曲角度。
