Eight new Zn(II) and Cd(II) complexes based on the aromatic multicarboxylate and N-donor mixed ligands, namely Zn2(TCOPM)(2,2′-bipy)(OH)·1.25DMF (TCOPM = tris(p-carboxyphenyl)methane; 2,2′-bipy = 2,2′-bipyridine; DMF = N,N′-dimethylformamide) (1), Zn2(αOH-TCOPM)(phen)(OH)·DMF (αOH-TCOPM = tris(p-carboxyphenyl)methanol; phen = 1,10-phenanthroline) (2), Zn2(αOH-TCOPM)(tpy)(OH)(H2O) (tpy = 2,2′:6′,2′′-terpyridine) (3), Zn3(αOH-TCOPM)2(dpe)·2H2O (dpe = 4,4′-vinylenedipyridine) (4), Cd3(TCOPM)2(DMF)2(H2O)2 (5), Cd3(TCOPM)2(4,4′-bipy) (6), Cd3(TCOPM)2(dpe) (7), and Cd3(αOH-TCOPM)2(2,2′-bipy)2·2DMF (8) were synthesized through a solvothermal reaction. The αOH-TCOPM ligand is generated in situ by the nucleophilic addition of the TCOPM ligand. X-ray crystallographic analysis reveals that complexes 1–3, 5, and 8 exhibit a two-dimensional (2D) layered structure, while 4, 6, and 7 possess a 3D open framework. The coordination mode of TCOPM and the type of N-donors ligands have obvious effects on the final structures. The luminescence properties in the solid state of 1–4, 7, and 8 were also investigated.
