Abstract
Cucurbit[n]urils (Q[n]s), a relatively new class of macrocyclic hosts with a rigid hydrophobic cavity and two identical carbonyl-fringed portals, have attracted much attention since the first member of the Q[n]-family, cucurbit[6]uril (Q[6]), was structurally identified in 1981 by Mock and co-workers. The interactions of the rigid cavities and negative portals of Q[n]s have resulted in the development of two almost mutually exclusive areas of study, namely Q[n]-based host–guest chemistry and Q[n]-based coordination chemistry. However, researches has revealed that Q[n]-based host–guest inclusion interactions may be influenced by metal ion coordination at the Q[n] portals, and in turn, coordination of metal ions at the Q[n] portals could be promoted by the formation of Q[n]-based inclusion host–guest complexes. Thus, this review provides an overview of related advances and achievements involving such a combination of Q[n]-based host–guest chemistry and Q[n]-based coordination chemistry, which could become an emerging branch, that is, Q[n]-based host–guest-metal ion chemistry. In particular, it could be useful in the treatment of wastewater, kinetic studies, drug delivery, the construction of novel supramolecular frameworks, metal-catalyzed reactions, recognition or response to metal cations, and so on.
Similar content being viewed by others
References
Cong, H., Ni, X.L., Xiao, X., Huang, Y., Zhu, Q.J., Xue, S.F., Tao, Z., Lindoy, L.F., Wei, G.: Synthesis and separation of cucurbit[n]urils and their derivatives. Org. Biomol. Chem. 14, 4335–4364 (2016)
Lee, J.W., Samal, S., Selvapalam, N., Kim, H.J., Kim, K.: Cucurbituril homologues and derivatives: new opportunities in supramolecular chemistry. Acc. Chem. Res. 36, 621–630 (2003)
Kim, K.: Mechanically interlocked molecules incorporating cucurbituril and their supramolecular assemblies. Chem. Soc. Rev. 31, 96–107 (2002)
Lagona, J., Mukhopadhyay, P., Chakrabarti, S., Isaacs, L.: The cucurbit[n]uril family. Angew. Chem. Int. Ed. 44, 4844–4870 (2005)
Kim, K., Selvapalam, N., Ko, Y.H., Park, K.M., Kim, D., Kim, J.: Functionalized cucurbiturils and their applications. Chem. Soc. Rev. 36, 267–279 (2007)
Isaacs, L.: Cucurbit[n]urils: from mechanism to structure and function. Chem. Commun. (2009). doi:10.1039/B814897J
Dsouza, R.N., Pischel, U., Nau, W.M.: Fluorescent dyes and their supramolecular host/guest complexes with macrocycles in aqueous solution. Chem. Rev. 111, 7941–7980 (2011)
Pemberton, B.C., Raghunathan, R., Volla, S., Sivaguru, J.: From containers to catalysts: supramolecular catalysis within cucurbiturils. Chem. Eur. J. 18, 12178–12190 (2012)
Masson, E., Ling, X.X., Joseph, R., Kyeremeh-Mensah, L., Lu, X.Y.: Cucurbituril chemistry: a tale of supramolecular success. RSC Adv. 2, 1213–1247 (2012)
Liu, Y.L., Yang, H., Wang, Z.Q., Zhang, X.: Cucurbit[8]uril-based supramolecular polymers. Chem. Asian J. 8, 1626–1632 (2013)
Sindelar, V., Silvi, S., Parker, S.E., Sobransingh, D., Kaifer, A.E.: Proton and electron transfer control of the position of cucurbit[n]uril wheels in pseudorotaxanes. Adv. Funct. Mater. 17, 694–701 (2007)
Wang, W., Kaifer, A.E.: Cucurbituril and cyclodextrin complexes of dendrimers. Adv. Polym. Sci. 222, 205–235 (2009)
Gadde, S., Batchelor, E.K., Kaifer, A.E.: Electrochemistry of redox active centres encapsulated by non-covalent methods. Aust. J. Chem. 63, 184–194 (2010)
Gadde, S., Kaifer, A.E.: Cucurbituril complexes of redox active guests. Cur. Org. Chem. 15, 27–38 (2011)
Mandadapu, V., Day, A.I., Ghanem, A.: Cucurbituril: chiral applications. Chirality 26, 712–723 (2014)
Montes-Garcia, V., Perez-Juste, J., Pastoriza-Santos, I., Liz-Marzan, L.M.: Metal nanoparticles and supramolecular macrocycles: a tale of synergy. Chem. Eur. J. 20, 10874–10883 (2014)
Isaacs, L.: Stimuli responsive systems constructed using cucurbit[n]uril-type molecular containers. Acc. Chem. Res. 47, 2052–2062 (2014)
Assaf, K.I., Nau, W.M.: Cucurbiturils: from synthesis to high-affinity binding and catalysis. Chem. Soc. Rev. 44, 394–418 (2015)
Ma, X., Zhao, Y.L.: Biomedical Applications of supramolecular systems based on host–guest interactions. Chem. Rev. 115, 7794–7839 (2015)
Hou, X.S., Ke, C.F., Stoddart, J.F.: Cooperative capture synthesis: yet another playground for copper-free click chemistry. Chem. Soc. Rev. 45, 3766–3780 (2016)
Tian, J., Chen, L., Zhang, D.W., Liu, Y., Li, Z.T.: Supramolecular organic frameworks: engineering periodicity in water through host–guest chemistry. Chem. Commun. 52, 6351–6362 (2016)
Liu, J., Lan, Y., Yu, Z.Y., Tan, C.S.Y., Parker, R.M., Abell, C., Scherman, O.A.: Cucurbit[n]uril-based microcapsules self-assembled within microfluidic droplets: a versatile approach for supramolecular architectures and materials. Acc. Chem. Res. 50, 208–217 (2017)
Sayed, M., Pal, H.: Supramolecularly assisted modulations in chromophoric properties and their possible applications: an overview. J. Mater. Chem. C. 4, 2685–2706 (2016)
Tian, J., Zhang, L., Wang, H., Zhang, D.W., Li, Z.T.: Supramolecular polymers and networks driven by cucurbit[8]uril-guest pair encapsulation in water. Supramol. Chem. 28, 769–783 (2016)
Sokolov, M.N., Dybtsev, D.N., Fedin, V.P.: Supramolecular compounds of cucurbituril with molybdenum and tungsten chalcogenide cluster aqua complexes. Russ. Chem. Bull. Int. Ed. 52, 1041–1060 (2003)
Gerasko, O.A., Sokolov, M.N., Fedin, V.P.: Mono- and polynuclear aqua complexes and cucurbit[6]uril: Versatile building blocks for supramolecular chemistry. Pure Appl. Chem. 76, 1633–1646 (2004)
Fedin, V.P.: New lines of research in chemistry of chalcogenide complexes: from clusters to supramolecular compounds. Russ. J. Coordin. Chem. 30, 151–158 (2004)
Lü, J., Lin, J.X., Cao, M.N., Cao, R.: Cucurbituril: a promising organic building block for the design of coordination compounds and beyond. Coord. Chem. Rev. 257, 1334–1356 (2013)
Ni, X.L., Xiao, X., Cong, H., Liang, L.L., Chen, K., Cheng, X.J., Ji, N.N., Zhu, Q.J., Xue, S.F., Tao, Z.: Cucurbit[n]uril-based coordination chemistry: from simple coordination complexes to novel poly-dimensional coordination polymers. Chem. Soc. Rev. 42, 9480–9508 (2013)
Ni, X.L., Xue, S.F., Tao, Z., Zhu, Q.J., Lindoy, L.F., Wei, G.: Advances in the lanthanide metallosupramolecular chemistry of the cucurbit[n]urils. Coord. Chem. Rev. 287, 89–113 (2015)
Behrend, R.; Meyer, E.; Rusche, F.: Mittheilungen aus dem organixch-chemixchen Laboratorium der Technischen Hochxcbule zu Hannover. Liebigs Ann. Chem. 339, 1–37 (1905)
Freeman, W.A., Mock, W.L., Shih, N.Y.: Cucurbituril. J. Am. Chem. Soc. 103, 7367–7368 (1981)
Wu, Y., Xu, L., Shen, Y., Wang, Y., Zou, L., Wang, Q., Jiang, X., Liu, J., Tian, H.: The smallest cucurbituril analogue with high affinity for Ag+. Chem Common. (2017). doi:10.1039/C7CC01729D
Li, Q., Qiu, S.C., Zhang, J., Chen, K., Huang, Y., Xiao, X., Zhang, Y., Li, F., Zhang, Y.Q., Xue, S.F., Zhu, Q.J., Tao, Z., Lindoy, L.F., Wei, G.: Twisted cucurbit[n]urils. Org. Lett. 18, 4020–4023 (2016)
Zhao, W.X., Wang, C.Z., Chen, L.X., Cong, H., Xiao, X., Zhang, Y.Q., Xue, S.F., Huang, Y., Tao, Z., Zhu, Q.J.: A hemimethyl-substituted cucurbit[7]uril derived from 3α-methylglycoluril. Org. Lett. 17, 5072–5075 (2015)
Jon, S.Y., Selvapalam, N., Oh, D.H., Kang, J.K., Kim, S.Y., Jeon, Y.J., Lee, J.W., Kim, K.: Facile synthesis of cucurbit[n]uril derivatives via direct functionalization: expanding utilization of cucurbit[n]uril. J. Am. Chem. Soc. 125, 10186–10187 (2003)
Zhao, N., Lloyd, G.O., Scherman, O.A.: Monofunctionalised cucurbit[6]uril synthesis using imidazolium host–guest complexation. Chem. Commun. 48, 3070–3072 (2012)
Ayhan, M.M., Karoui, H., Hardy, M., Rockenbauer, A., Charles, L., Rosas, R., Udachin, K., Tordo, P., Bardelang, D., Ouari, O.: Comprehensive synthesis of monohydroxy-cucurbit[n]urils (n = 5, 6, 7, 8): high purity and high conversions. J. Am. Chem. Soc. 137, 10238–10245 (2015)
Ayhan, M.M., Karoui, H., Hardy, M., Rockenbauer, A., Charles, L., Rosas, R., Udachin, K., Tordo, P., Bardelang, D., Ouari, O.: Comprehensive synthesis of monohydroxy-cucurbit[n]urils (n = 5, 6, 7, 8): high purity and high conversions. J. Am. Chem. Soc. 138, 2060 (2016)
Huang, W.H., Zavalij, P.Y., Isaacs, L.: Folding of long-chain alkanediammonium ions promoted by a cucurbituril derivative. Org. Lett. 10, 2577–2580 (2008)
Lucas, D., Minami, T., Iannuzzi, G., Cao, L., Wittenberg, J.B., Anzenbacher, Jr.P., Isaacs, L.: Templated synthesis of glycoluril hexamer and monofunctionalized cucurbit[6]uril derivatives. J. Am. Chem. Soc. 133, 17966–17976 (2011)
Vinciguerra, B., Cao, L., Cannon, J.R., Zavalij, P.Y., Fenselau, C., Isaacs, L.: Synthesis and self-assembly processes of monofunctionalized cucurbit[7]uril. J. Am. Chem. Soc. 134, 13133–13140 (2012)
Cao, L., Isaacs, L.: Daisy chain assembly formed from a cucurbit[6]uril derivative. Org. Lett. 14, 3072–3075 (2012)
Cao, L., Hettiarachchi, G., Briken, V., Isaacs, L.: Cucurbit[7]uril containers for targeted delivery of oxaliplatin to cancer cells. Angew. Chem. Int. Ed. 52, 12033–12037 (2013)
Vinciguerra B., Zavalij P.Y., Isaacs L.: Synthesis and recognition properties of cucurbit[8]uril derivatives. Org. Lett. 17, 5068–5071 (2015)
Bockus, A.T., Smith, L.C., Grice, A.G., Ali, O.A., Young, C.C., Mobley, W., Leek, A., Roberts, J.L., Vinciguerra, B., Isaacs, L.: Cucurbit[7]uril-tetramethylrhodamine conjugate for direct sensing and cellular imaging. J. Am. Chem. Soc. 138, 16549–16552 (2016)
Liang, L.L., Ni, X.L., Zhao, Y., Chen, K., Xiao, X., Zhang, Y.Q., Redshaw, C., Zhu, Q.J., Xue, S.F., Tao, Z.: Construction of Cucurbit[7]uril Based Tubular Nanochannels Incorporating Associated [CdCl4]2− and Lanthanide Ions. Inorg. Chem. 52, 1909–1915 (2013)
Zhao, Y., Liang, L.L., Chen, K., Ji, N.N., Cheng, X.J., Xiao, X., Zhang, Y.Q., Xue, S.F., Zhu, Q.J., Dong, N., Tao, Z.: [CdCl4]2– anion-induced coordination of alkaline earth metal ions to cucurbit[7]uril, corresponding supramolecular self-assemblies and potential application. Dalton Trans. 43, 929–932 (2014)
Cong, H., Zhao, Y., Liang, L.L., Chen, K., Chen, X.J., Xiao, X., Zhang, Y.Q., Zhu, Q.J., Xue, S.F., Tao, Z.: Cucurbituril-based supramolecular self-assemblies formed in the presence of alkali metal and cadmium ions. Eur. J. Inorg. Chem. (2014). doi:10.1002/ejic.201400004
Li, Q., Qiu, S.C., Zhang, Y.Q., Xue, S.F., Tao, Z., Prior, T.J., Redshaw, C., Zhu, Q.J., Xiao, X.: Supramolecular assemblies constructed from inverted cucurbit[7]uril and lanthanide cations: synthesis, structure and sorption properties. RSC Adv. 6, 77805–77810 (2016)
Qiu, S.C., Li, Q., Chen, K., Zhang, Y.Q., Zhu, Q.J., Tao, Z.: Absorption properties of an inverted cucurbit[7]uril-based porous coordination polymer induced by [ZnCl4]2− anions. Inorg. Chem. Commun. 72, 50–53 (2016)
Liang, L.L., Zhao, Y., Chen, K., Xiao, X., Clegg, J.K., Zhang, Y.Q., Tao, Z., Xue, S.F., Zhu, Q.J., Wei G.: One-dimensional coordination polymers of lanthanide cations to cucurbit[7]uril built using a range of tetrachloride transition-metal dianion structure inducers. Polymers 5, 418–430 (2013)
Chen, K., Cong, H., Xiao, X., Zhang, Y.Q., Xue, S.F., Tao, Z., Zhu, Q.J., Wei, G.: Hydroquinone-induced framework based on direct coordination of rubidium ions to cucurbit[7]uril. CrystEngComm 13, 5105–5110 (2011)
Chen, K., Liang, L.L., Cong, H., Xiao, X., Zhang, Y.Q., Xue, S.F., Zhu, Q.J., Tao, Z.: p-Hydroxybenzoic acid-induced formation of a novel framework based on direct coordination of caesium ions to cucurbit[8]uril. CrystEngComm 14, 3862–3864 (2012)
Ni, X.L., Xiao, X., Cong, H., Zhu, Q.J., Xue, S.F., Tao, Z.: Self-assemblies based on the “outer-surface interactions” of cucurbit[n]urils: new opportunities for supramolecular architectures and materials. Acc. Chem. Res. 47, 1386–1395 (2014)
Buschmann, H.J.: Novel host–guest mechanism: precipitation of many organic molecules from aqueous solution. Festkoerperphys Werkstofforsch 44, 114–122 (1990)
Hoffmann, R., Knoche, W., Fenn, C.: Host–guest complexes of cucurbituril with 4-methylbenzylammonium ion, alkali-metal cations and NH4 +. J. Chem. Soc. Faraday Trans. 90, 1507–1511 (1994)
Buschmann, H.J., Gardberg, A., Rader, D., Schollmeyer, E.: The decolorization of textile wastewater by formation of dye inclusion compounds, part 5, influence of textile auxiliaries. Textilveredlung 28, 179–182 (1993)
Buschmann, H.J., Schollmeyer, E.: Decreasing the concentration of heavy metals in wastewater from textile finishing operations. Textilveredlung 28, 182–184 (1993)
Buschmann, H.J.: Selective removal of dyes and heavy metals from wastewaters of the textile industry. Vom Wasser. 84, 263–269 (1995)
Buschmann, H.J.: Cucurbituril complexes with dyes and other organic molecules. Biol. Abwasserreinig 9, 101–129 (1997)
Karcher, S., Kornmueller, A., Jekel, M.: Removal of reactive dyes with the cage compound cucurbituril. Biol. Abwasserreinig 9, 131–152 (1997)
Karcher, S., Kornmüller, A., Jekel M.: Effects of alkali and alkaline-earth cations on the removal of reactive dyes with cucurbituril. Acta Hydrochim. Hydrobiol. 27, 38–42 (1999)
Karcher, S., Kornmüller, A., Jekel M.: Removal of reactive dyes by sorption/complexation with cucurbituril. Wat. Sci. Tech. 40, 425–433 (1999)
Tang, H., Fuentealba, D., Ko, Y.H., Selvapalam, N., Kim, K., Bohne, C.: Guest binding dynamics with cucurbit[7]uril in the presence of cations. J. Am. Chem. Soc. 133, 20623–20633 (2011)
Jeon, Y.M., Kim, J., Whang, D., Kim, K.: Molecular container assembly capable of controlling binding and release of its guest molecules: reversible encapsulation of organic molecules in sodium ion complexed cucurbituril. J. Am. Chem. Soc. 118, 9790–9791 (1996)
Dongmok Whang, Jungseok Heo, Joo Hyun Park, Kimoon Kim: A Molecular Bowl with Metal Ion as Bottom: reversible Inclusion of Organic Molecules in Cesium Ion Complexed Cucurbituril. Angew. Chem. Int. Ed. 37, 78–80 (1998)
Choudhury, S.D., Mohanty, J., Pal, H., Bhasikuttan, A.C.: Cooperative metal ion binding to a cucurbit[7]uril-thioflavin T complex: demonstration of a stimulus-responsive fluorescent supramolecular capsule. J. Am. Chem. Soc. 132, 1395–1401 (2010)
Nau, W.M.: Under control. Nat. Chem. 2, 248–250 (2010)
Fedin, V.P., Virovets, A.V., Sokolov, M.N., Dybtsev, D.N., Gerasko, O.A., Clegg, W.: Supramolecular assemblies based on cucurbituril adducts of hydrogen-bonded molybdenum and tungsten incomplete cuboidal aqua complexes. Inorg. Chem. 39, 2227–2230 (2000)
Dybtsev, D.N., Gerasko, O.A., Virovets, A.V., Sokolov, M.N., Fedin, V.P.: Unexpected guest-controlled formation of two-layered structure in supramolecular adduct of [W3S4(H2O)9]4+ and cucurbituril. Inorg. Chem. Commun. 3, 345–349 (2000)
Liu, J.X., Lin, R.L., Long, L.S., Huang, R.B., Zheng, L.S.: A novel inclusion complex form between Q[10] host and Q[5] guest stabilized by potassium ion coordination. Inorg. Chem. Commun. 11, 1085–1087 (2008)
Thuery, P.: Supramolecular assemblies built from lanthanide ammoniocarboxylates and cucurbit[6]uril. CrystEngComm 14, 8128–8136 (2012)
Blanco, E., Quintana, C., Hernández, P.: An electrochemical study of cucurbit[6]uril–cadmium(II) interactions and the effect of electrolyte cations and guest molecules. Anal. Lett. 48, 783–795 (2015)
Thuéry, P.: Second-sphere complexation of thorium(IV) by cucurbit[6]uril with included perrhenate counterions–crystal structure and hirshfeld surface analysis. Eur. J. Inorg. Chem. 12, 2037–2040 (2015)
Mu, L., Yang, X.B., Xue, S.F., Zhu, Q.J., Tao, Z., Zeng, X.: Cucurbit[n]urils induced room temperature phosphorescence of quinoline derivatives. Anal. Chim. Acta 597, 90–96 (2007)
Lu, X., Masson, E.: Silver-promoted desilylation catalyzed by ortho- and allosteric cucurbiturils. Org. Lett. 12, 2310–2313 (2010)
Koner, A.L., Márquez, C., Dickman, M.H., Nau, W.M.: Transition-metal-promoted chemoselective photoreactions at the cucurbituril rim. Angew. Chem. Int. Ed. 50, 545–548 (2011)
Zhu, J.H., Li, C.Y., Liu, S.P., Liu, Z.F., Li, Y.F., Hu, X.L.: Calcium-stimulus-responsive cucurbit[7]uril–thioflavin Tsupramolecular nanocapsule for fluoride sensing and logic operation. Sen. Actuat. B 198, 255–259 (2014)
Dutta Choudhury, S., Bhasikuttan, A.C., Pal, H., Mohanty, J.: Surfactant-induced aggregation patterns of thiazole orange: A photophysical study. Langmuir. 27, 12312–12321 (2011)
Mooi, S.M., Heyne, B.: Size does matter: How to control organization of organic dyes in qqueous environment using specific ion effects. Langmuir. 28, 16524–16530 (2012)
Shinde, M.N., Dutta Choudhury, S., Barooah, N., Pal, H., Bhasikuttan, A.C., Mohanty, J.: Metal-ion-mediated assemblies of thiazole orange with cucurbit[7]uril: a photophysical study. J. Phys. Chem. B. 119, 3815–3823 (2015)
Aliaga, M.E., Garcia-Rio, L., Pessêgo, M., Montecinos, R., Fuentealba, D., Uribe, I., Martín-Pastor, M., García-Beltrán, O.: Host–guest interaction of coumarin-derivative dyes and cucurbit[7]uril: leading to the formation of supramolecular ternary complexes with mercuric ions. New J. Chem. 39, 3084–3092 (2015)
Geng, Q.X., Cong, H., Tao, Z., Lindoy, L.F., Wei, G.: Cucurbit[7]uril-improved recognition by a fluorescent sensor for cadmium and zinc cations. Supramol. Chem. 28, 784–791 (2016)
Geng, Q.X., Wang, F., Cong, H., Tao, Z., Wei, G.: Recognition of silver cations by a cucurbit[8]urilinduced supramolecular crown ether. Org. Biomol. Chem. 14, 2556–2562 (2016)
Pandey, S., Soni, V.K., Choudhary, G., Sharma, P.R., Sharma, R.K.: Understanding behaviour of vitamin-C guest binding with the cucurbit[6]uril host. Supramol. Chem. 29, 387–394 (2017)
Zhang, J., Tang, Q., Gao, Z.Z., Qiu, S.C., Huang, Y., Tao, Z.: Supramolecular assemblies mediated by metal ions in aqueous solution and their analysis applications. Chem. Eur. J. doi:10.1002/chem.201700478
Li, W., Kuehne, N.W., Dallin, E., Gordon, R., Hof, F.: A supramolecular indicator displacement assay for acetyl amantadine, a proxy biomarker for spermidine/spermine N1-acetyltransferase (SSAT) activity. Can. J. Chem. 94, 969–975 (2016)
Manna, A., Chakravorti, S.: Switching of emission of a styryl dye in cucurbit[7]uril: a comprehensive experimental and theoretical study. Spectrochim. Acta A 140, 241–247 (2015)
Banik, D., Kuchlyan, J., Roy, A., Kundu, N., Sarkar, N.: Stimuli-sensitive breathing of cucurbit[7]uril cavity: monitoring through the environment responsive fluorescence of 1′-hydroxy-2′-acetonaphthone (HAN). J. Phys. Chem. B 119, 2310–2322 (2015)
Acknowledgements
We acknowledge the support of the National Natural Science Foundation of China (Nos. 21601090 and 51663005), the Graduate Student’s Fund for innovation of Guizhou University (No. 2016011) and Natural Science Foundation of Jiangsu, China (No. BK20160943).
Author information
Authors and Affiliations
Corresponding authors
Rights and permissions
About this article
Cite this article
Yao, Y.Q., Chen, K., Hua, Z.Y. et al. Cucurbit[n]uril-based host–guest-metal ion chemistry: an emerging branch in cucurbit[n]uril chemistry. J Incl Phenom Macrocycl Chem 89, 1–14 (2017). https://doi.org/10.1007/s10847-017-0733-5
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10847-017-0733-5