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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

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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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