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Reagents for Metal Organic Framework (MOF) and Porous Coordination Polymer (PCP) Research

　Porous metal-organic frameworks (MOFs) (other name: porous coordination polymers (PCPs)) have attracted wide scientific attention for the potential application to gas storage, gas separation, catalysis and nanospace engineering.1) MOFs (PCPs) are constructed mainly by coordination bonds between metal cations and multidentate ligands. Their specificities depend on the pore shape, size, and chemical environments of the voids or channels. Kitagawa et al. have reported the first utilization of a MOF as an electrocatalyst for oxidation of ethanol to aldehyde, for which the potential was comparable with Pt-based catalysts.2)
　Recently, Kaneko, Kanoh, Kondo, Kajiro et al. have developed a quite unique Cu complex MOF [Cu(bpy)(BF4)2(H2O)2]bpy (bpy = 4,4’-bipyridine),3) named as pre-ELM-11 (ELM stands for Elastic Layer-Structured MOF). Upon heating and dehydration, pre-ELM-11 converts to an innovative and stable gas absorbent ELM-11 [Cu(bpy)2(BF4)2] (Figure 1). ELM-11 has structural flexibility, and its structural transformation occurs easier than traditional rigid MOFs. And the gate type adsorption isotherm on ELM-11, which has a predominantly rectangular shaped hysteresis, is quite unique (Figure 2).
Figure 1. Structure Transformation between pre-ELM-11 and ELM-11

　Pre-ELM-11 is easily converted to ELM-11 by an activation process (dehydration). Recommended conditions are 120℃ for 3 h in vacuo. ELM-11 is stable on drying at rt. ELM-11 rapidly absorbs moisture in atmospheric conditions and changes its structure to pre-ELM-11, but can be re-transformed.
Figure 2. Schematic representation of the gate adsorption of CO23a)

　Pre-ELM-11 is also utilized as a catalyst in organic synthesis for molecular oxygen-derived oxidation and epoxide alcoholysis (Scheme).4)
Scheme. Molecular oxygen-derived oxidation and epoxide alcoholysis using pre-ELM-11
pre-ELM-11
C2409
C2409
pre-ELM-11

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5-Aminoisophthalic Acid
A1290
2-Aminoterephthalic Acid
A1291
Pyromellitic Acid
B0039
1,3,5-Benzenetricarboxylic Acid
B0043
2,2'-Bipyridyl
B0468
4,4'-Bipyridyl
B0469
4,4'-Biphenyldicarboxylic Acid
B1191
Bromoterephthalic Acid
B1321
2,2'-Bipyridine-3,3'-dicarboxylic Acid
B3622
Copper(II) Tetrafluoroborate
C2410
1,4-Diazabicyclo[2.2.2]octane
D0134
1,2-Di(4-pyridyl)ethylene
D0276
1,3-Di(4-pyridyl)propane
D0938
1,2-Di(4-pyridyl)ethane
D3752
2,5-Dihydroxyterephthalic Acid
D3899
Dimethyl 5-Bromoisophthalate
D4068
5-Hydroxyisophthalic Acid
H0794
2-Hydroxyterephthalic Acid
H1385
Imidazole
I0001
1H-Imidazole-4,5-dicarboxylic Acid
I0003
Isophthalic Acid
I0155
2-Methylimidazole
M0345
5-Methoxyisophthalic Acid
M1835
Nitroterephthalic Acid
N0272
2,6-Naphthalenedicarboxylic Acid
N0377
5-Nitroisophthalic Acid
N0520
1,4-Naphthalenedicarboxylic Acid
N0606
1,10-Phenanthroline
P0221
Phthalic Acid
P0287
Pyrazine
P0544
2,3-Pyrazinedicarboxylic Acid
P0545
2,6-Pyridinedicarboxylic Acid
P0554
Terephthalic Acid
T0166
2,4,6-Tri(4-pyridyl)-1,3,5-triazine
T1937
1,3,5-Tris(4-carboxyphenyl)benzene
T2647
1,3,5-Triethynylbenzene
T2760
A1290
5-Aminoisophthalic Acid Hydrate
A1291
2-Aminoterephthalic Acid
B0039
Pyromellitic Acid
B0043
1,3,5-Benzenetricarboxylic Acid
B0468
2,2'-Bipyridyl
B0469
4,4'-Bipyridyl
B1191
4,4'-Biphenyldicarboxylic Acid
B1321
Bromoterephthalic Acid
B3622
2,2'-Bipyridine-3,3'-dicarboxylic Acid
C2410
Copper(II) Tetrafluoroborate (ca. 45% in Water)
D0134
1,4-Diazabicyclo[2.2.2]octane
D0276
1,2-Di(4-pyridyl)ethylene
D0938
1,3-Di(4-pyridyl)propane
D3752
1,2-Di(4-pyridyl)ethane
D3899
2,5-Dihydroxyterephthalic Acid
D4068
Dimethyl 5-Bromoisophthalate
H0794
5-Hydroxyisophthalic Acid
H1385
2-Hydroxyterephthalic Acid
I0001
Imidazole
I0003
1H-Imidazole-4,5-dicarboxylic Acid
I0155
Isophthalic Acid
M0345
2-Methylimidazole
M1835
5-Methoxyisophthalic Acid
N0272
Nitroterephthalic Acid
N0377
2,6-Naphthalenedicarboxylic Acid
N0520
5-Nitroisophthalic Acid
N0606
1,4-Naphthalenedicarboxylic Acid
P0221
1,10-Phenanthroline Monohydrate
P0287
Phthalic Acid
P0544
Pyrazine
P0545
2,3-Pyrazinedicarboxylic Acid
P0554
2,6-Pyridinedicarboxylic Acid
T0166
Terephthalic Acid
T1937
2,4,6-Tri(4-pyridyl)-1,3,5-triazine
T2647
1,3,5-Tris(4-carboxyphenyl)benzene
T2760
1,3,5-Triethynylbenzene

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Literature

  • 1)Reviews of metal-organic frameworks (MOFs / PCPs)
  • 2)Electrocatalyst for ethanol oxidation
  • 3)For gas storage and gas separation research of pre-ELM-11
    • a)D. Li, K. Kaneko, Chem. Phys. Lett. 2001, 335, 50.
    • b)A. Kondo, H. Noguchi, S. Ohnishi, H. Kajiro, A. Tohdoh, Y. Hattori, W.-C. Xu, H. Tanaka, H. Kanoh, K. Kaneko, Nano Lett. 2006, 6, 2581.
    • c)H. Noguchi, A. Kondo, Y. Hattori, H. Kajiro, H. Kanoh, K. Kaneko, J. Phys. Chem. C 2007, 111, 248.
    • d)H. Kanoh, A. Kondo, H. Noguchi, H. Kajiro, A. Tohdoh, Y. Hattori, W.-C. Xu, M. Inoue, T. Sugiura, K. Morita, H. Tanaka, T. Ohba, K. Kaneko, J. Colloid Interface Sci. 2009, 334, 1.
    • e)H. Kajiro, A. Kondo, K. Kaneko, H. Kanoh, Int. J. Mol. Sci. 2010, 11, 3803.
    • f)Nippon Steel Corporation, Nippon Steel Chemical Co., Ltd., Institute of Research and Innovation, Jpn. Kokai Tokkyo Koho 2005 162624, 2005; Nippon Steel Corporation, Nippon Steel Chemical Co., Ltd., Institute of Research and Innovation, Jpn. Kokai Tokkyo Koho 2005 162625, 2005; Nippon Steel Corporation, Institute of Research and Innovation, Jpn. Kokai Tokkyo Koho 2005 336129, 2005; Nippon Steel Corporation, Jpn. Kokai Tokkyo Koho 2005 232031, 2005.
  • 4)For catalysis research of pre-ELM-11

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