Syntheses and Properties of Three Types of 3,4‐Dichlorobenzoate‐based Ni(II)‐Ln(III) Heterometallic Clusters

Abstract

The solvothermal reactions of NiCl2⋅6H2O, Ln(NO3)3⋅nH2O, 3,4‐dichlorobenzoic acid (3,4‐HDCB), and 2,2′‐bipyridine (2,2′‐bpy) yielded eight zero‐dimensional (0D) Ni(II)‐Ln(III) heterometallic complexes NdNi2(3,4‐DCB)7(2,2′‐bpy)2 (1) and Ln2Ni2(3,4‐DCB)10(2,2′‐bpy)2 [Ln=Sm (2), Eu (3), Gd (4), Tb (5), Dy (6), Er (7), and Yb (8)]. Complexes 1–8 display three types of linear heterometallic clusters. Complex 1 is a trinuclear cluster, whereas complexes 2–8 are tetranuclear clusters. Complexes 2–8 posssess the same formula, but the coordination number of Ln(III) in 2–6 is different from that in 7 and 8. In 1–8, the adjacent polynuclear clusters are linked by the π–π interactions into a one‐dimensional (1D) supramolecular chain. The size of Ln(III) ions and the position of halogen substituents have important effects on the formation and structures of 1–8. The properties of photoluminescence and magnetism of 1–8 were investigated.