Structural diversity of metal–organic frameworks via employment of azamacrocycles as a building block
- 112 Downloads
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.
KeywordsMetal–organic frameworks Azamacrocycles Pendant arms Structural control Open metal sites Flexibility
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).
Compliance with Ethical Standards
Conflict of interest
The authors declare that they do not have any conflict of interest.
- 22.Rodríguez-Rodríguez, A., Esteban-Gómez, D., Tripier, R., Tircsó, G., Garda, Z., Tóth, I., de Blas, A., Rodríguez-Blas, T., Platas-Iglesias, C.: Lanthanide(III) complexes with a reinforced cyclam ligand show unprecedented kinetic inertness. J. Am. Chem. Soc. 136, 17954–17957 (2014)CrossRefGoogle Scholar
- 31.Zhu, J., Usov, P.M., Xu, W., Celis-Salazar, P.J., Lin, S., Kessinger, M.C., Landaverde-Alvarado, C., Cai, M., May, A.M., Slebodnick, C., Zhu, D., Senanayake, S.D., Morris, A.J.: A new class of metal-cyclam-based zirconium metal–organic frameworks for CO2 adsorption and chemical fixation. J. Am. Chem. Soc. 140, 993–1003 (2018)CrossRefGoogle Scholar