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

Young Joo Song; Han Kwak; Young Min Lee; Soo Hyun Kim; Sun Hwa Lee; Byeong Kwon Park; Je Yeol Jun; Seung Man Yu; Cheal Kim; Sung Jin Kim; Youngmee Kim

doi:10.1016/j.poly.2009.02.014

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

Young Joo Song, Han Kwak, Young Min Lee, Soo Hyun Kim, Sun Hwa Lee, Byeong Kwon Park, Je Yeol Jun, Seung Man Yu, Cheal Kim, Sung Jin Kim, Youngmee Kim

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

69 Scopus citations

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.

Original language	English
Pages (from-to)	1241-1252
Number of pages	12
Journal	Polyhedron
Volume	28
Issue number	7
DOIs	https://doi.org/10.1016/j.poly.2009.02.014
State	Published - 12 May 2009

Bibliographical note

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.

Keywords

Catalytic activities
Coordination polymers
Metal benzoates
Metal coordination modes
Transesterification

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10.1016/j.poly.2009.02.014

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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. (2009). 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. Polyhedron, 28(7), 1241-1252. https://doi.org/10.1016/j.poly.2009.02.014

@article{22b6b9b307124c15acf1e4dc4bdd93b2,

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",

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.",

keywords = "Catalytic activities, Coordination polymers, Metal benzoates, Metal coordination modes, Transesterification",

author = "Song, {Young Joo} and Han Kwak and Lee, {Young Min} and Kim, {Soo Hyun} and Lee, {Sun Hwa} and Park, {Byeong Kwon} and Jun, {Je Yeol} and Yu, {Seung Man} and Cheal Kim and Kim, {Sung Jin} and Youngmee Kim",

note = "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. ",

year = "2009",

month = may,

day = "12",

doi = "10.1016/j.poly.2009.02.014",

language = "English",

volume = "28",

pages = "1241--1252",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier Ltd.",

number = "7",

}

Song, YJ, Kwak, H, Lee, YM, Kim, SH, Lee, SH, Park, BK, Jun, JY, Yu, SM, Kim, C, Kim, SJ & Kim, Y 2009, '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', Polyhedron, vol. 28, no. 7, pp. 1241-1252. https://doi.org/10.1016/j.poly.2009.02.014

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

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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 -

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

Abstract

Bibliographical note

Keywords

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