Metal-directed supramolecular assembly of metal(II) benzoates (M = Co, Ni, Cu, Zn, Mn, and Cd) with 4,4′-bipyridine: Effects of metal coordination modes and novel catalytic activities

Six polymeric metal(II)-benzoate complexes of formula [Co2(O2CPh)4(4,4′-bpy)2]n (1-Co), [Ni(O2CPh)4(H2O)2(4,4′-bpy)]n (2-Ni), [Cu2(O2CPh)4(4,4′-bpy)]n (3-Cu), [Zn2(O2CPh)2(OH)2(4,4′-bpy)2]n (4-Zn), [Zn3(O2CPh)4(μ-OH)2(4,4′-bpy)2]n (5-Zn), and [Cd2(O2CPh)4(4,4′-bpy)2]n (6-Cd) have been synthesized and characterized (4,4′-bpy = 4,4′-bipyridine). 1-Co and 6-Cd show ladder-type double chains, 2-Ni does a helical structure, 3-Cu does a one-dimensional chain containing paddle-wheel units, 4-Zn does a zigzag chain, and 5-Zn does two-dimensional sheets. Since different structures provide different coordination geometry of each metal ion, it is clear that selection of appropriate metal ions can control the coordination geometry of each metal ion to form different crystal structures. Reactivity study of the compounds 1–7 for the transesterification of a variety of esters has shown that 4-Zn and 5-Zn are very efficient and the best among them. The catalyst 6-Cd containing Cd ion, well known as an inert metal ion for the ligand substitution, also catalyzed efficiently the transesterification of a variety of esters, and its reactivity is comparable to 4-Zn and 5-Zn. Moreover, the redox-active metal-containing polymers, 1-Co, 3-Cu, and 7-Mn, have shown efficient catalytic reactivities for the transesterification reactions, while 2-Ni has displayed a very slow conversion. The reactivities of the compounds used in this study are in the order of 5-Zn > 4-Zn > 6-Cd > 7-Mn ∼ 3-Cu > 1-Co > 2-Ni, indicating that the non-redox metal-containing compounds (5-Zn, 4-Zn, and 6-Cd) show better activity than the redox-active metal-containing compounds (7-Mn, 3-Cu, 1-Co, and 2-Ni). These results suggest that it is possible to tune the catalytic activities by changing from Zn to those metals such as Cd, a kinetically inert metal, or Cu, Mn, and Co, the redox-active metals.

Graphical abstractWe have presented a systematic investigation on the coordination polymers assembled from metal benzoates and 4,4′-bpy. Since different structures provide different coordination geometry of each metal ion, it is clear that selection of appropriate metal ions can control the coordination geometry of each metal ion to form different crystal structures. Reactivity study of seven compounds for the transesterification of a variety of esters has shown that 4-Zn and 5-Zn are very efficient and the best among them. It can be possible to tune the catalytic activities by changing from Zn to those metals such as Cd, a kinetically inert metal, or Cu, Mn, and Co, the redox-active metals.Figure optionsDownload full-size imageDownload as PowerPoint slide