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.
This is a preview of subscription content, log in to check access.
Buy single article
Instant access to the full article PDF.
Tax calculation will be finalised during checkout.
Subscribe to journal
Immediate online access to all issues from 2019. Subscription will auto renew annually.
Tax calculation will be finalised during checkout.
Furukawa, H., Cordova, K.E., O’Keeffe, M., Yaghi, O.M.: The chemistry and applications of metal-organic frameworks. Science 341, 1230444 (2013)
Suh, M.P., Cheon, Y.E., Lee, E.Y.: Synthesis and functions of porous metallosupramolecular networks. Coord. Chem. Rev. 252, 1007–1026 (2008)
Li, B., Chrzanowski, M., Zhang, Y., Ma, S.: Applications of metal-organic frameworks featuring multi-functional sites. Coord. Chem. Rev. 307, 106–129 (2016)
Lee, K.J., Lee, J.H., Jeoung, S., Moon, H.R.: Transformation of metal–organic frameworks/coordination polymers into functional nanostructured materials: experimental approaches based on mechanistic insights. Acc. Chem. Res. 50, 2684–2692 (2017)
Lama, P., Aggarwal, H., Bezuidenhout, C.X., Barbour, L.J.: Giant hysteretic sorption of CO2: in situ crystallographic visualization of guest binding within a breathing framework at 298 K. Angew. Chem. Int. Ed. 55, 13271–13275 (2016)
Kim, J.Y., Balderas-Xicohténcatl, R., Zhang, L., Kang, S.G., Hirscher, M., Oh, H., Moon, H.R.: Exploiting diffusion barrier and chemical affinity of metal–organic frameworks for efficient hydrogen isotope separation. J. Am. Chem. Soc. 139, 15135–15141 (2017)
Kim, J.Y., Zhang, L., Balderas-Xicohténcatl, R., Pack, J., Hirscher, M., Moon, H.R., Oh, H.: Selective hydrogen isotope separation via breathing transition in MIL-53(Al). J. Am. Chem. Soc. 139, 17743–17746 (2018)
Kim, T.K., Lee, J.H., Moon, D., Moon, H.R.: Luminescent Li-based metal–organic framework tailored for the selective detection of explosive nitroaromatic compounds: direct observation of interaction sites. Inorg. Chem. 52, 589–595 (2013)
Liao, P.-Q., She, J.-Q., Zhang, J.-P.: Metal-organic frameworks for electrocatalysis. Coord. Chem. Rev. 373, 22–48 (2018)
Schneemann, A., Bon, V., Schwedler, I., Senkovska, I., Kaskel, S., Fischer, R.A.: Flexible metal-organic frameworks. Chem. Soc. Rev. 43, 6062–6096 (2014)
Elsaidi, S.K., Mohamed, M.H., Banerjee, D., Thallapally, P.K.: Flexibility in metal-organic frameworks: a fundamental understanding. Coord. Chem. Rev. 358, 125–152 (2018)
Lee, J.H., Kim, T.K., Suh, M.P., Moon, H.R.: Solvent-induced single-crystal to single-crystal transformation of a Zn4O-containing doubly interpenetrated metal-organic framework with a pcu net. CrystEngComm 17, 8807–8811 (2015)
Lee, J.H., Park, S., Jeoung, S., Moon, H.R.: Single-crystal-to-single-crystal transformation of a coordination polymer from 2D to 3D by [2 + 2] photodimerization assisted by a coexisting flexible ligand. CrystEngComm 19, 3719–3722 (2017)
Pedersen, C.J.: Cyclic polyethers and their complexes with metal salts. J. Am. Chem. Soc. 89, 7017–7036 (1967)
Liu, Z., Nalluri, S.K.M., Stoddart, J.F.: Surveying macrocyclic chemistry: from flexible crown ethers to rigid cyclophanes. Chem. Soc. Rev. 46, 2459–2478 (2017)
Zhang, H., Zou, R., Zhao, Y.: Macrocycle-based metal-organic frameworks. Coord. Chem. Rev. 292, 74–90 (2015)
Emerson, A.J., Chahine, A., Batten, S.R., Turner, D.R.: Synthetic approaches for the incorporation of free amine functionalities in porous coordination polymers for enhanced CO2 sorption. Coord. Chem. Rev. 365, 1–22 (2018)
Stackhouse, C.A., Ma, S.: Azamacrocycle-based metal organic frameworks: design strategies and applications. Polyhedron 145, 154–165 (2018)
Suh, M.P., Moon, H.R.: Coordination polymer open frameworks constructed of macrocyclic complexes. Adv. Inorg. Chem. 59, 39–79 (2007)
Barefield, E.K.: Coordination chemistry of N-tetraalkylated cyclam ligands-A status report. Coord. Chem. Rev. 254, 1607–1627 (2010)
Corriu, R.J.P., Embert, F., Guari, Y., Reyé, C., Guilard, R.: Coordination chemistry in the solid: evidence for coordination modes within hybrid materials different from those in solution. Chem. Eur. J. 8, 5732–5741 (2002)
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)
Zhu, X., Lü, J., Li, X., Gao, S., Li, G., Xiao, F., Cao, R.: Syntheses, structures, near-Infrared, and visible luminescence of lanthanide-organic frameworks with flexible macrocyclic polyamine ligands. Cryst. Growth Des. 8, 1897–1901 (2008)
Zhu, X.-D., Tao, T.-X., Zhou, W.-X., Wang, F.-H., Liu, R.-M., Liu, L., Fu, Y.-Q.: A novel lead(II) porous metal–organic framework constructed from a flexible bifunctional macrocyclic polyamine ligand. Inorg. Chem. Commun. 40, 116–119 (2014)
Gao, W.-Y., Niu, Y., Chen, Y., Wojtas, L., Cai, J., Chen, Y.-S., Ma, S.: Porous metal–organic framework based on a macrocyclic tetracarboxylate ligand exhibiting selective CO2 uptake. CrystEngComm 14, 6115–6117 (2012)
Spek, A.L.: PLATON SQUEEZE: a tool for the calculation of the disordered solvent contribution to the calculated structure factors. Acta Crystallogr., Sect. C: Struct. Chem. 71, 9–18 (2015)
Gao, W.-Y., Chen, Y., Niu, Y., Williams, K., Cash, L., Perez, P.J., Wojtas, L., Cai, J., Chen, Y.-S., Ma, S.: Crystal engineering of an nbo topology metal–organic framework for chemical fixation of CO2 under ambient conditions. Angew. Chem. Int. Ed. 53, 2615–2619 (2014)
Zhu, X.-D., Lin, Z.-J., Liu, T.-F., Xu, B., Cao, R.: Two novel 3d-4f heterometallic frameworks assembled from a flexible bifunctional macrocyclic ligand. Cryst. Growth Des. 12, 4708–4711 (2012)
Carné-Sánchez, A., Bonnet, C.S., Imaz, I., Lorenzo, J., Tóth, É, Maspoch, D.: Relaxometry studies of a highly stable nanoscale metal–organic framework made of Cu(II), Gd(III), and the macrocyclic DOTP. J. Am. Chem. Soc. 135, 17711–17714 (2013)
Ariñez-Soriano, J., Albalad, J., Pérez-Carvajal, J., Imaz, I., Busqué, F., Juanhiux, J., Maspoch, D.: Two-step synthesis of heterometallic coordination polymers using a polyazamacrocyclic linker. CrystEngComm 18, 4196–4204 (2016)
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)
Choi, H.J., Suh, M.P.: Synthesis, crystal structure, and properties of a 3-D network assembled by nickel(II) macrocyclic complex and terephthalato bridge. Inorg. Chem. 38, 6309–6312 (1999)
Moon, H.R., Kim, J.H., Suh, M.P.: Redox-active porous metal–organic framework producing silver nanoparticles from AgI ions at room temperature. Angew. Chem. Int. Ed. 44, 1261–1265 (2005)
Choi, H.J., Suh, M.P.: Self-assembly of molecular brick wall and molecular honeycomb from nickel(II) macrocycle and 1,3,5-benzenetricarboxylate: guest-dependent host structures. J. Am. Chem. Soc. 120, 10622–10628 (1998)
Choi, H.J., Lee, T.S., Suh, M.P.: Self-assembly of a molecular floral lace with one-dimensional channels and inclusion of glucose. Angew. Chem. Int. Ed. 38, 1405–1408 (1999)
Suh, M.P., Choi, H.J., So, S.M., Kim, B.M.: A new metal-organic open framework consisting of threefold parallel interwoven (6,3) nets. Inorg. Chem. 42, 676–678 (2003)
Hyun, S., Kim, T.K., Kim, Y.K., Moon, D., Moon, H.R.: Guest-driven structural flexibility of 2D coordination polymers: synthesis, structural characterizations, and gas sorption properties. Inorg. Chem. Commun. 33, 52–56 (2013)
Kim, H., Suh, M.P.: Flexible eightfold interpenetrating diamondoid network generating 1D channels: selective binding with organic guests. Inorg. Chem. 44, 810–812 (2005)
Almáši, M., Zeleňák, V., Zukai, A., Kuchár, J., Čejka, J.: A novel zinc(II) metal–organic framework with a diamond-like structure: synthesis, study of thermal robustness and gas adsorption properties. Dalton Trans. 45, 1233–1242 (2016)
Moon, H.R., Suh, M.P.: Flexible and redox-active coordination polymer: control of the network structure by pendant arms of a macrocyclic complex. Eur. J. Inorg. Chem. 2010, 3795–3803 (2010)
Kim, Y.K., Hyun, S., Lee, J.H., Kim, T.K., Moon, D., Moon, H.R.: Crystal-size effects on carbon dioxide capture of a covalently alkylamine-tethered metal-organic framework constructed by a one-step self-assembly. Sci. Rep. 6, 19337 (2016)
Choi, H.J., Suh, M.P.: Highly selective CO2 capture in flexible 3D coordination polymer networks. Angew. Chem. Int. Ed. 48, 6865–6869 (2009)
Hyun, S., Lee, J.H., Jung, G.Y., Kim, Y.K., Kim, T.K., Jeoung, S., Kwak, S.K., Moon, D., Moon, H.R.: Exploration of gate-opening and breathing phenomena in a tailored flexible metal–organic framework. Inorg. Chem. 55, 1920–1925 (2016)
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).
Conflict of interest
The authors declare that they do not have any conflict of interest.
About this article
Cite this article
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). https://doi.org/10.1007/s10847-018-0855-4
- Metal–organic frameworks
- Pendant arms
- Structural control
- Open metal sites