Four new complexes [Cu(L 1) 2 ] n (1), [Mn(L 1) 2 ] n (2), [Cu(L 2) 2 ] n (3), [Mn(L 2) 2 ] n (4, HL 1 = 2-(((4H-1,2,4-triazol-4-yl)imino)methyl)-4,6-dichlorophenol; HL 2 = 2-(((4H-1,2,4-triazol-4-yl)imino)methyl)-4,6-dibromophenol) were synthesized by microreaction bottle method. Complexes 1 and 3 and 2 and 4 are isomorphous heterostructures having the same molecular structure. The structures of 1-4 were characterized using single X-ray diffraction, Fouriertransform infrared spectroscopy, powder X-ray diffraction, and thermogravimetric analysis, and their potential applications were analyzed by detecting their fluorescence and electrochemical luminescence (ECL). Hirshfeld surface analysis indicates that X•••H (X = Br, Cl) interactions play a crucial role in stabilizing the self-assembly process of 1-4, which show highly intense ECL in N,N-dimethylformamide solution and high thermal stability.