Cage Structured Compounds


Cage Structured Compounds

Anita Gupta, H. Kaur, Ishika Aggarwal, Koushiki Chatterjee

This chapter has targeted the features of inorganic cage compounds, their classification, and their overabundant applications. The term ‘Cage’ is utilized as a specific term for three-dimensional structures which have a definite and rigid geometry. There can be various atomic positions in the cage, these positions can operate as branching origins and additional ligands can be introduced at these positions. Recent advances in the synthetic chemistry and strategies adopted for the synthesis of cage compounds with special attention to Calixarenes and Cryptophanes have played an analytical role in the development of Biomedical Applications, drug freightage systems, sensing, bio-imaging, and other smart materials. The adsorption of dye from industrial wastewater by the functionalized Calixarene cage e.g. Dinitro Calix [4] arene cage (DNCC) was tested for the first time [1]. Recent research indicates that Cryptophane cages can also adopt different configurations and demonstrate various applications [2]. During the 1970s, a founding work by Corbett and Simon on rare-earth halides led to the establishment of the fact that these highly cluster skeleton electron-deficient clusters always involve an interstitial atom inside the metal cluster cage. A novel development in the field of coordination chemistry of integral cage molecules and their ligand complexes has been extensively researched for their budding application as building blocks in polymers [3]. Caged structure complexes, one of its kind in supramolecular chemistry have always garnered the attention of the scientific community worldwide. This book chapter is an initiative to instill the essence of the caged compound with its striking features and a plethora of applications.

Cage Compounds, Calixarenes, Cryptophanes, Metal Cluster Cage, Supramolecular Chemistry

Published online 2/10/2024, 18 pages

Citation: Anita Gupta, H. Kaur, Ishika Aggarwal, Koushiki Chatterjee, Cage Structured Compounds, Materials Research Foundations, Vol. 162, pp 81-98, 2024


Part of the book on Thermoelectric Polymers

[1] F. Temel, M. Turkyilmaz, S. Kucukcongar, Removal of methylene blue from aqueous solutions by silica gel supported calix[4]arene cage: Investigation of adsorption properties, Eur. Polym. J. 125 (2020) 109540.
[2] 0.D. Negra, Access to the Syn diastereomers of cryptophane cages using HFIP, Chem. Commun. 58 (2022) 3330-3333.
[3] J. Wachter, Coordination Polymers with Group 15/16 Element Building Blocks, in: J. Reedijk, K. Poeppelmeier (Eds.), Comprehensive Inorganic Chemistry II, Elsevier: Amsterdam, 2013, p. 933-952.
[4] K. Svoboda, R. Yasuda, Principles of two-photon excitation microscopy and its applications to neuroscience, Neuron. 50 (2006) 823-839.
[5] Y. Fang, Catalytic reactions within the cavity of coordination cages, Chem. Soc. Rev. 48 (2019) 4707-4730.
[6] J. Liu, M. Chen, H. Cui, Recent progress in environmental applications of metal-organic frameworks, Water Sci. Technol. 83 (2021) 26-38.
[7] N. Manousi, Extraction of metal ions with metal-organic frameworks, Molecules, 24 (2019) 4605.
[8] M. Shen, Antibacterial applications of metal-organic frameworks and their composites, Compr. Rev. Food Sci. Food Saf. 19 (2020) 1397-1419.
[9] E.-S.M. El-Sayed, D. Yuan, Metal-organic cages (MOCs): From discrete to cage-based extended architectures, Chem. Lett. 49 (2020) 28-53.
[10] D. Zhang, Metal-organic cages for molecular separations. Nat. Rev. Chemi. 5 (2021) 168-182.
[11] A. Tarzia, K.E. Jelfs, Unlocking the computational design of metal-organic cages, Chem. Commun. 58 (2022) 3717-3730.
[12] E. Raee, Y. Yang, T. Liu, Supramolecular structures based on metal-organic cages, Giant 5 (2021) 100050.
[13] G.C.E. Davies, Caged compounds: Photorelease technology for control of cellular chemistry and physiology, Nat. Methods 4 (2007) 619-628.
[14] A. Katoch, N. Goyal, S. Gautam, Applications and advances in coordination cages: Metal-Organic Frameworks, Vacuum 167 (2019) 287-300.
[15] C.Y. Zhu, M. Pan, C.Y. Su, Metal‐organic cages for biomedical applications, Isr. J. Chem. 59 (2019) 209-219.
[16] D.T. Walters, Utilization of a nonemissive triphosphine ligand to construct a luminescent gold (I)-box that undergoes mechanochromic collapse into a helical complex, J. Am. Chem. Soc. 140 (2018) 7533-7542.
[17] J.H. Zhang, Recent advances of application of porous molecular cages for enantioselective recognition and separation, J. Separ. Sci. 43 (2020) 134-149.
[18] P.P. Neelakandan, A. Jiménez, J.R. Nitschke, Fluorophore incorporation allows nanomolar guest sensing and white-light emission in M 4 L 6 cage complexes, Chem. Sci. 5 (2014) 908-915.
[19] A. Giri, Cavitand and molecular cage-based porous organic polymers, ACS Omega 5 (2020) 28413-28424.
[20] P.R. Bautista, Metal-organic frameworks in green analytical chemistry, Separations, 6 (2019) 33.
[21] S. Xie, J. Zhang, N. Fu, B. Wang, Application of homochiral alkylated organic cages as chiral stationary phases for molecular separations by capillary gas chromatography, Molecules 21 (2016) 1466.
[22] L. Feng, K.Y. Wang, G.S. Day, The chemistry of multi-component and hierarchical framework compounds, Chem. Soc. Rev. 48 (2019) 4823-4853.
[23] I. Jahović, Cages meet gels: Smart materials with dual porosity, Matter, 4 (2021) 2123-2140.
[24] A.D. Kelkar, D.J. Herr, J.G. Ryan, Nanoscience and nanoengineering: Advances and applications, CRC Press, 2014.
[25] E.J. Lee, N.K. Lee, I.-S. Kim, Bioengineered protein-based nanocage for drug delivery, Adv. Drug Deliv. Rev. 106 (2016) 157-171.
[26] R.J. Drout, L. Robison, O.K. Farha, Catalytic applications of enzymes encapsulated in metal-organic frameworks, Coord. Chem. Rev. 381 (2019) 151-160.
[27] H. Shet, A comprehensive review of caged phosphines: Synthesis, catalytic applications, and future perspectives, Organic Chem. Front. 8 (2021). 1599-1656.
[28] T. Traoré, Scalable synthesis of cryptophane-1.1. 1 and its functionalization, Org. Lett. 12 (2010) 960-962.
[29] Y. Voloshin, I. Belaya, R. Krämer, Cage metal complexes: Clathrochelates revisited, 2017, Springer.
[30] A. Casini, B. Woods, M. Wenzel, The promise of self-assembled 3D supramolecular coordination complexes for biomedical applications, ACS Publications, 2017, p. 14715-14729.
[31] A.K. Gupta, Mapping the Assembly of Metal-Organic Cages into Complex Coordination Networks, 2017.
[32] A. Dondoni, Synthesis and characterization of calix[4]arene-based copolyethers and polyurethanes Ionophoric properties and extraction abilities towards metal cations of polymeric calix[4]arene urethanes, Polymer 45 (2004) 6195-6206.
[33] C.D. Gutsche, Topics in calixarene chemistry, J. Incl. Phenom. Macrocycl. Chem. 7 (1989) 61-72.
[34] C.D. Gutsche, B. Dhawan, K. No, Calixarenes. 4. The synthesis, characterization, and properties of the calixarenes from p-tert-butylphenol, J. Am. Chem. Soc. 103 (1981) 3782-3792.
[35] U. Balami, D.K. Taylor, Electrochemical responsive arrays of sulfonatocalixarene groups prepared by free radical polymerization, Reactive Funct. Polym. 81 (2014) 54-60.
[36] A.R. Mendes, Linear and crosslinked copolymers of p-tert-butylcalix[4]arene derivatives and styrene: New synthetic approaches to polymer-bound calix[4]arenes. Reactive Funct. Polym. 65 (2005) 9-21.
[37] Y. Yang, T.M. Swager, Main-chain calix[4]arene elastomers by ring-opening metathesis polymerization, Macromolecules 40 (2007) 7437-7440.
[38] T.C. Gokoglan, A novel architecture based on a conducting polymer and calixarene derivative: Its synthesis and biosensor construction, RSC Adv. 5 (2015) 35940-35947.
[39] Y. Zhang, Robust cationic calix[4]arene polymer as an efficient catalyst for cycloaddition of epoxides with CO2, Indus. Eng. Chem. Res. 59 (2019) 7247-7254.
[40] Z. Zhu, D. Liu, Q. Ren, Y. Tan, Microcapsule dispersion of poly (calix[4]arene-piperazine) for hazardous metal cations removal from waste water, Iranian Polym. J. 28 (2019) 697-706.
[41] T. Nekrasova, Structural and dynamic characteristics of a star-shaped calixarene-containing polymer in aqueous solutions: The formation of mixed-shell micelles in the presence of poly (methacrylic acid), Polym. Sci. Series A 57 (2015) 6-12.
[42] A. Ten’kovstev, A. Razina, M. Dudkina, Synthesis and complexing behavior of amphiphilic starlike calix[4]arenes, Polym. Sci. Series B 56 (2014) 274-281.
[43] A.M. Shumatbaeva, The pH-responsive calix[4]resorcinarene-mPEG conjugates bearing acylhydrazone bonds: Synthesis and study of the potential as supramolecular drug delivery systems, Colloids Surf. A Physicochem. Eng. Asp. 589 (2020) 124453.
[44] P.F. Gou, W.P. Zhu, Z.Q. Shen, Calixarene‐centered amphiphilic A2B2 miktoarm star copolymers based on poly (ε‐caprolactone) and poly (ethylene glycol): synthesis and self‐assembly behaviors in water, J. Polym. Sci. Part A: Polym. Chem. 48 (2010) 5643-5651.
[45] T. Kirila, Thermosensitive star-shaped poly-2-ethyl-2-oxazine. Synthesis, structure characterization, conformation, and self-organization in aqueous solutions, Eur. Polym. J. 120 (2019) 109215.
[46] R. Zadmard, Recent progress to construct calixarene-based polymers using covalent bonds: Synthesis and applications, RSC Adv. 10 (2020) 32690-32722.
[47] S. Suharso, Synthesis of a Novel Calix[4]resorcinarene-Chitosan Hybrid, Oriental Journal of Chemistry, 2018.
[48] Y. Agrawal, J. Pancholi, J. Vyas, Design and synthesis of calixarene, 2009.
[49] U. Trivedi, S. Menon, Y. Agrawal, Polymer supported calix[6]arene hydroxamic acid, a novel chelating resin, Reactive Funct. Polym. 50 (2002) 205-216.
[50] M. Gidwani, S. Menon, Y. Agrawal, Chelating polycalixarene for the chromatographic separation of Ga (III), In (III) and Tl (III), Reactive Funct. Polym. 53 (2003) 143-156.
[51] K. Su, Azo-bridged calix[4]resorcinarene-based porous organic frameworks with highly efficient enrichment of volatile iodine, ACS Sustain. Chem. Eng. 6 (2018) 17402-17409.
[52] T. Tilki, An approach to the synthesis of chemically modified bisazocalix[4]arenes and their extraction properties, Tetrahedron 61 (2005) 9624-9629.
[53] B. Turner, M. Botoshansky, Y. Eichen, Extended calixpyrroles: Meso‐substituted calix [6] pyrroles, Angew. Chem. Int. Ed.. 37 (1998) 2475-2478.<2475::AID-ANIE2475>3.0.CO;2-7
[54] D. Xie, C.D. Gutsche, Synthesis and reactivity of calix[4]arene-based copper complexes, J. Org. Chem. 63 (1998) 9270-9278.
[55] D.W. Yoon, H. Hwang, C.H. Lee, Synthesis of a strapped calix[4]pyrrole: Structure and anion binding properties, Ang. Chem. Int. Ed. 41 (2021) 1757-1759.<1757::AID-ANIE1757>3.0.CO;2-0
[56] D. Siswanta, Calix[4]resorcinarene-chitosan hybrid via amide bond formation, Asian J. Chem. 27 (2015).