TY - JOUR
T1 - Metal-directed supramolecular assembly of metal(II) benzoates (M = Co, Ni, Cu, Zn, Mn, and Cd) with 4,4′-bipyridine
T2 - Effects of metal coordination modes and novel catalytic activities
AU - Song, Young Joo
AU - Kwak, Han
AU - Lee, Young Min
AU - Kim, Soo Hyun
AU - Lee, Sun Hwa
AU - Park, Byeong Kwon
AU - Jun, Je Yeol
AU - Yu, Seung Man
AU - Kim, Cheal
AU - Kim, Sung Jin
AU - Kim, Youngmee
N1 - Funding Information:
Financial support from Korea Ministry Environment “ET – Human Resource Development Project”, the Korea Research Foundation (2007-314-C00159), the Korean Science and Engineering Foundation (R01-2008-000-20704-0), The SEOUL R&BD Program, and the SRC program of the Korea Science and Engineering Foundation (KOSEF) through the Center for Intelligent Nano-Bio Materials at Ewha Womans University (Grant R11-2005-008-00000-0) is gratefully acknowledged.
PY - 2009/5/12
Y1 - 2009/5/12
N2 - 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.
AB - 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.
KW - Catalytic activities
KW - Coordination polymers
KW - Metal benzoates
KW - Metal coordination modes
KW - Transesterification
UR - http://www.scopus.com/inward/record.url?scp=64549133339&partnerID=8YFLogxK
U2 - 10.1016/j.poly.2009.02.014
DO - 10.1016/j.poly.2009.02.014
M3 - Article
AN - SCOPUS:64549133339
SN - 0277-5387
VL - 28
SP - 1241
EP - 1252
JO - Polyhedron
JF - Polyhedron
IS - 7
ER -