Five isostructural complexes constructed with H 3 TTTA and 4,4′-bpy, namely Co(H 2 TTTA) 2 (4,4′-bpy) 2 (1), Ni(H 2 TTTA) 2 (4,4′-bpy) 2 (2), Mn(H 2 TTTA) 2 (4,4′-bpy) 2 (3), Cd(H 2 TTTA) 2 (4,4′-bpy) 2 (4) and Cu(H 2 TTTA) 2 (4,4′-bpy) 2 (5) (H 3 TTTA=2,2′, 2″-[1,3,5-triazine-2,4,6-triyltris(thio)] tris–acetic acid, 4,4′-bpy=4,4′-dipyridine), have been synthesized and characterized by elemental analysis, IR, XRD and single crystal X-ray diffraction. The strong O–H⋯N and O–H⋯O stacking interactions link the molecules into a 2D network. Moreover, these 2D networks are connected into 3D frameworks through C–H⋯O and C–H⋯N stacking interactions, which seem to be effective in stabilizing the crystal structures. Complexes 1–5 have been tested for their catalytic properties. The results indicate that all the complexes show good catalytic activities for the cyanosilylation of benzaldehyde, whilst the Mn complex (3) shows a much better conversion for the cyanosilylation of acetophenone than the other complexes. The fluorescence properties of the complexes have also been investigated in detail.