Two tridentate N,N,O-donor ligands, HL 1 = 4-chloro-2-(((2-(methylamino)ethyl)amino)methyl)phenol and HL 2 = 4-chloro-2-(((2-(dimethylamino)ethyl)amino)methyl)phenol, have been used to synthesize phenolate-bridged dinuclear complexes [Zn 2 (L 1 ) 2 Cl 2 ] ( 1) and [Zn 2 (L 2 ) 2 (N 3 ) 2 ] (2). Single-crystal X-ray diffraction analysis confirmed their structures. Both complexes form assemblies in the solid state. Moreover, the existence of nonconventional spodium bonds in 1 and tetrel bonds in 2 has been explored using theoretical calculations, including MEP surface plots and QTAIM and NCIplot analyses.