Structural diversity of metal–organic frameworks via employment of azamacrocycles as a building block


Research on incorporating macrocycles into metal–organic frameworks (MOFs) has been performed intensively due to the opportunities afforded by merging a merit of macrocycles with MOF chemistry, which lead to novel hybrid materials for potential application. Among the numerous kinds of macrocycles, azamacrocycles are used as traditional and popular chelating agents in supramolecular coordination chemistry, because they are very easily functionalized by joining pendant arms and possess a strong propensity to complex metal cations, accounting for the amine functionalities. With this as background, many types of azamacrocyclic MOFs have been synthesized, granting compositionally and topologically new MOFs. The macrocyclic rings can serve as additional adsorption sites or catalytic sites, and the pendant arms on the macrocycles can also play versatile roles such as structure-directing agents, pore-decorating moieties, or rotatable molecular gates for opening/closing pores. In this review, we comprehensively discuss the syntheses, structures, and features of azamacrocyclic MOFs reported to date. Based on representative studies, advantages of these compounds are described, such as how the azamacrocycles increase the structural diversity and complexity of the MOFs and induce novel structural properties within the architectures.

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Reprinted with permission from ref [23]. Copyright 2008 from American Chemical Society

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Reprinted with permission from ref [29]. Copyright 2013 from American Chemical Society

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Reprinted with permission from ref [31]. Copyright 2018 from American Chemical Society

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Reprinted with permission from ref [33]. Copyright 2005 from Wiley-VCH

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Reprinted with permission from ref [34]. Copyright 1998 from American Chemical Society

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Reprinted with permission from ref [40]. Copyright 2010 from Wiley-VCH

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Reprinted with permission from ref [42]. Copyright 2009 from Wiley-VCH

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This work was supported by the National Research Foundation of Korea (NRF) Grant funded by the Ministry of Science and ICT (No. NRF-2016R1A5A1009405, and NRF-2017R1A2B4008757). J.H.L. acknowledges the Global Ph.D. Fellowship (NRF-2013H1A2A1033501).

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Lee, J.H., Moon, H.R. Structural diversity of metal–organic frameworks via employment of azamacrocycles as a building block. J Incl Phenom Macrocycl Chem 92, 237–249 (2018).

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  • Metal–organic frameworks
  • Azamacrocycles
  • Pendant arms
  • Structural control
  • Open metal sites
  • Flexibility