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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

Title
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
Authors
Song Y.J.Kwak H.Lee Y.M.Kim S.H.Lee S.H.Park B.K.Jun J.Y.Yu S.M.Kim C.Kim S.-J.Kim Y.
Ewha Authors
김성진김영미
SCOPUS Author ID
김성진scopus; 김영미scopus
Issue Date
2009
Journal Title
Polyhedron
ISSN
0277-5387JCR Link
Citation
vol. 28, no. 7, pp. 1241 - 1252
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
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. © 2009 Elsevier Ltd. All rights reserved.
DOI
10.1016/j.poly.2009.02.014
Appears in Collections:
자연과학대학 > 화학·나노과학전공 > Journal papers
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