Structural Trends in a 3 d‐4 f System: Ln(NO3)3−Cu(2,2‐bipyridine)2(NO3)2 (Ln=La−Nd, Sm−Yb)

Abstract

AbstractA series of thirteen complexes which may be formally considered as assembled from Cu(bpy)2(NO3)2 and Ln(NO3)3 (Ln=La−Yb excluding Pm, bpy=2,2’‐bipyridine) have been characterized. The crystals may be grouped into four classes: A, [Cu2(bpy)4(μ‐NO3)][Ln(NO3)6] (Ln=La−Nd); B, [Cu(bpy)2(NO3)]2[Ln(NO3)4(OH2)2](NO3) (Ln=Sm−Dy); C, [Cu(bpy)2(NO3)]2[Ln(NO3)5] (Ln=Ho−Tm); D, [Cu(bpy)2(NO3)]2 [Ln(NO3)3(OH2)3](NO3)2⋅2H2O (Ln=Yb). The coordination numbers of the nitrato or aquonitrato lanthanide anions range from 9 to 12. The dinuclear cation in Class A having a linear monoatomic nitrate bridge is new and is seen to produce weak antiferromagnetic coupling in these compounds. The other classes contain distortion isomers of [Cu(bpy)2NO3]+. The structural trends are analysed in terms of lanthanide contraction and non‐covalent interactions in the crystals. EPR and electronic spectral characteristics are discussed for the four classes of compounds.