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

The solvothermal reactions of NiCl 2 ⋅6H 2 O, Ln(NO 3 ) 3 ⋅ n H 2 O, 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 NdNi 2 (3,4‐DCB) 7 (2,2′‐bpy) 2 ( 1 ) and Ln 2 Ni 2 (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.