One homo-trinuclear 3d and five novel windmill-type hetero-pentanuclear 3d-4f complexes [Zn₃(L)(OAc)₂(H₂O)]·CH₂Cl₂ (1), [Zn₄(L)₂Sm(NO₃)₂(EtOH)₂]NO₃·H₂O·2CHCl₃ (2), [Zn₄(L)₂Eu(NO₃)₂(EtOH)₂]NO₃·C₂H₅OH·2CHCl₃ (3), [Zn₄(L)₂Gd(NO₃)₂(EtOH)₂]NO₃·C₂H₅OH·2CHCl₃ (4), [Zn₄(L)₂Tb(NO₃)₂(EtOH)₂]NO₃·C₂H₅OH (5) and [Zn₄(L)₂Dy(NO₃)₂(EtOH)₂]NO₃·C₂H₅OH·2CHCl₃ (6) were synthesized by the reactions of a new bis(Salamo)-based tetraoxime ligand (H₄L) with Zn(OAc)₂·2H₂O and Ln(NO₃)₃·6H₂O (Ln = Sm, Eu, Gd, Tb and Dy), respectively. The structures of complexes 1–6 were characterized via elemental analyses, FT-IR spectroscopy, UV-Vis spectroscopy and single crystal X-ray crystallography, and their fluorescence properties, catalytic activities and Hirshfeld surface analyses were studied.

Through the self-assembly of a Salamo-type ligand H₂L (H₂L = 1,2-bis(3-methoxysalicylideneaminooxy)ethane) with Ni(OAc)₂·4H₂O, Ln(NO₃)₃·6H₂O (Ln(III) = La(III), Gd(III), Tb(III) and Dy(III)) and Py (Py = pyridine) or 4,4′-bipy (4,4′-bipy = 4,4′-bipyridine) or H₂bdc (H₂bdc = terephthalic acid), nine new Ni(II)–Ln(III) heterometallic complexes [Ni(L)La(OAc)(NO₃)₂(Py)(CH₃OH)]·CH₃OH (1), [Ni(L)Dy(OAc)(NO₃)₂(Py)] (2), ¹ _∞[Ni(L)La(NO₃)₃(4,4′-bipy)(CH₃OH)] (3), ¹ _∞[Ni(L)Tb(NO₃)₃(4,4′-bipy)] (4), [Ni(L)Dy(OAc)(NO₃)₂(4,4′-bipy)] (5), [{Ni(L)Ln(NO₃)₂(DMF)(CH₃OH)}₂(bdc)] (Ln = La (6) and Gd (7)) and [{Ni(L)Ln(NO₃)₂(DMF)}₂(bdc)] (Ln = Tb (8) and Dy (9)) were obtained, respectively. The acetato ligand bridges the Ni(II) and Ln(III) (Ln = La (1) and Dy (2)) atoms in a μ₂ fashion and the Py coordinates to the apical position by a nitrogen atom in the heterobimetallic complexes 1 and 2. Complexes 3 and 4 are 1D coordination polymers constructed from heterobimetallic [Ni(L)Ln] (Ln = La (3) and Tb (4)) units which are connected by the exo-dentate ligand 4,4′-bipy bearing nitrogen-donor atoms, but complex 5 is a heterobimetallic Ni(II)–Dy(III) complex which is prepared under the same reaction conditions as complexes 3 and 4. Four heterotetranuclear dimers were constructed from heterobimetallic [Ni(L)Ln] (Ln = La (6), Gd (7)), Tb (8) and Dy (9) units which are connected by the exo-dentate H₂bdc ligand with oxygen-donor atoms. Magnetic measurements were performed on the Gd(III), Tb(III) and Dy(III) complexes.

A series of [Zn ^II Ln ^III ] complexes (Ln = Sm, Eu, Tb and Dy) are synthesized by Salamo-type ligand H ₂ L. Only [Zn ^II Sm ^III ] shows the characteristic transitions of Sm ³⁺ ion, indicating the effective energy transfer between the ligand and Sm ³⁺ ion.